Materials Science for Solar Energy Conversion Systems - C. G. Granqvist 1991

RENEWABLE ENERGY SERIES
Editor-in-Chief: A A M Sayigh
Pergamon Titles of Related Interest

BANHIDI
Radiant Heating S y s t e m s : Design and Applications
BEI
M o d e r n P o w e r Station Practice, 3rd edition
HARRISON
Geothermal Heating
HORIGOME
Clean and Safe Energy Forever
MCVEIGH
Sun P o w e r , 2nd edition
SAITO
Heat Pumps
SAYIGH
Energy C o n s e r v a t i o n in Buildings
SAYIGH
Energy and the Environment: into the 1990s, 5-vol set
SAYIGH & MCVEIGH

Solar Air Conditioning and Refrigeration
STECCO & MORAN

A Future for Energy
TREBLE
Generating Electricity from the Sun
Pergamon Related Journals (free specimen copy gladly sent on

request)
Energy
Energy C o n s e r v a t i o n and Management
Geothermics
Heat R e c o v e r y S y s t e m s and C H P
International J o u r n a l of Heat and M a s s T r a n s f e r
International J o u r n a l of H y d r o g e n E n e r g y
Progress in Energy and C o m b u s t i o n Science
Renewable Energy
Solar Energy
MATERIALS SCIENCE
FOR SOLAR
ENERGY CONVERSION SYSTEMS
Edited by
C. G. GRANQVIST
Physics Department,
Chalmers University of Technology, Sweden
PERGAMON PRESS
OXFORD NEW YORK · SEOUL . TOKYO
U.K. Pergamon Press pic, Headington Hill Hall,
Oxford 0X3 OBW, England
U.S.A. Pergamon Press Inc., 395 Saw Mill River Road,
Elmsford, NY 10523, U.S.A.
KOREA Pergamon Press Korea, KPO Box 315, Seoul 110-603,
Korea
JAPAN Pergamon Press, 8th Floor, Matsuoka Central Building,
1-7-1 Nishi-Shinjuku, Shinjuku-ku, Tokyo 160, Japan
Copyright © 1991 Pergamon Press pic

All Rights Reserved. No part of this publication may be
reproduced, stored in a retrieval system or transmitted in any
form or by any means: electronic, electrostatic, magnetic tape,
mechanical, photocopying, recording or otherwise, without
permission in writing from the publisher.
First edition 1991
Library of Congress Cataloging in Publication Data
Materials science for solar energy conversion systems/edited by
C. G. Granqvist.—1st ed.
p. cm.—(Renewable energy series)
1. Solar energy—Materials. I. Granqvist, Claes G. II. Series.
TJ812.7.M4 1991 621.47—dc20 91-811
British Library Cataloguing in Publication Data

Granqvist, C. G .
Materials science for solar energy conversion systems. -
(Renewable energy)
I. Title II. Series
621.47028
ISBN 0-08-040937-7
Printed in Great Britain by BPCC Wheatons Ltd, Exeter

FOREWORD
R a p i d advances in materials science n o w m a k e possible n e w vistas in solar

energy conversion systems. Thus today's technology allows high quality
s u r f a c e c o a t i n g s t o b e u s e d in energy-efficient f e n e s t r a t i o n a n d in s p e c t r a l l y
s e l e c t i v e s o l a r a b s o r b e r s . B u l k m a t e r i a l s a r e a v a i l a b l e for t r a n s p a r e n t
t h e r m a l i n s u l a t i o n a n d for f l u o r e s c e n t s o l a r c o n c e n t r a t o r s . C h r o m o g e n i c
windows, polymeric light-pipes, and radiative cooling materials are
e x a m p l e s o f t e c h n o l o g i e s t h a t h o l d p r o m i s e for r a p i d f u t u r e d e v e l o p m e n t .
Chemical materials and photochemical processes are being seriously
c o n s i d e r e d for e n e r g y s t o r a g e .
T h i s b o o k c o n c e n t r a t e s o n n e w a d v a n c e s in m a t e r i a l s s c i e n c e w i t h
p a r t i c u l a r a t t e n t i o n to a p p l i c a t i o n s , p e r f o r m a n c e , c h a r a c t e r i z a t i o n ,
laboratory manufacturing, industrial production, reliability, and cost. T h e
b o o k c o n s i s t s o f a n i n t r o d u c t o r y c h a p t e r a n d five t o p i c a l c h a p t e r s d e a l i n g
w i t h different, y e t h i g h l y i n t e g r a t e d , subjects in m a t e r i a l s s c i e n c e a s a p p l i e d
to s o l a r e n e r g y c o n v e r s i o n s y s t e m s . T h e first t o p i c a l c h a p t e r is Optical Pro-
perties of Inhomogeneous Two-Component Materials by G.A. Niklasson.
T h i s t h e o r e t i c a l t r e a t i s e p r o v i d e s a b a c k g r o u n d to m u c h o f t h e b a s i c w o r k o n
s p e c t r a l l y s e l e c t i v e r a d i a t i v e p r o p e r t i e s in t h e s u b s e q u e n t c h a p t e r s .
Transparent Insulation Materials by Platzer and Wittwer deals with
different a p p r o a c h e s to c o n v e c t i o n s u p p r e s s i o n in t r a n s p a r e n t m a t e r i a l s .
T h e s e n o v e l m a t e r i a l s h a v e a h i g h p o t e n t i a l for i n c r e a s i n g t h e e f f i c i e n c y o f
solar thermal conversion systems and of other energy-related applications.
Selectively Solar-Absorbing Surface Coatings: Optical Properties and
Degradation by G.A. Niklasson and C.G. Granqvist introduces selective
a b s o r p t i o n o f s o l a r e n e r g y a n d d i s c u s s e s the p r o p e r t i e s o f c u r r e n t l y a v a i l a b l e
s u r f a c e c o a t i n g s , w i t h p a r t i c u l a r c o n s i d e r a t i o n o f r e c e n t p r o g r e s s in t h e
u n d e r s t a n d i n g o f d e g r a d a t i o n p h e n o m e n a . Energy-Efficient Windows:
Present and Forthcoming Technology by C.G. Granqvist presents up-to-date
r e s e a r c h a n d d e v e l o p m e n t that w i l l p r o v i d e i m p o r t a n t o p p o r t u n i t i e s for
improved energy-efficient windows. This chapter also covers the design
criteria for different c l i m a t e s a n d r e v i e w s m e a n s to fulfil t h e s e t h r o u g h
p r o p e r m a t e r i a l s s e l e c t i o n . C o n c e p t s s u c h as l a r g e - a r e a c h r o m o g e n i c s a n d
a n g u l a r s e l e c t i v i t y - that h a v e b e e n f o r w a r d e d o n l y d u r i n g t h e p a s t f e w y e a r s
- a r e d i s c u s s e d . T h e last c h a p t e r , Materials for Radiative Cooling to Low
Temperatures by C.G. Granqvist and T.S. Eriksson, introduces the idea of
e m p l o y i n g t h e c l e a r s k y as a h e a t s i n k for r a d i a t i v e c o o l i n g . It is s h o w n that
vii
u n d e r c e r t a i n c o n d i t i o n s a t e m p e r a t u r e difference c a n b e o b t a i n e d u s i n g
s u i t a b l y d e s i g n e d m a t e r i a l s : s o m e results o f s e l e c t e d field tests a r e i n c l u d e d .
E a c h o f t h e c o n t r i b u t o r s h a s s e t a l a n d m a r k in the field o f m a t e r i a l s s c i e n c e ,
p a r t i c u l a r l y w i t h r e g a r d to r e n e w a b l e e n e r g y utilization. W e h o p e t h a t this
first b o o k in t h e ' R e n e w a b l e E n e r g y ' s e r i e s , Materials Science for Solar
Energy Conversion Systems, w i l l b e i n v a l u a b l e to all s c i e n t i s t s , e n g i n e e r s ,
a n d i n d u s t r i a l i s t s w o r k i n g in this a n d r e l a t e d a r e a s .
A.A.M. Sayigh
viii
Chapter 1
INTRODUCTION T O MATERIALS SCIENCE FOR SOLAR

ENERGY CONVERSION SYSTEMS
C.G. Granqvist
Physics Department
Chalmers University of Technology and University of Gothenburg
S-412 96 Gothenburg, S w e d e n
ABSTRACT
S e v e r a l p a t h w a y s for r e n e w a b l e e n e r g y c o n v e r s i o n a r e i n t r o d u c e d . M a t e r i a l s for
specific s o l a r e n e r g y a p p l i c a t i o n s h a v e o p t i c a l p r o p e r t i e s t a i l o r e d to t h e r e q u i r e -
m e n t s set b y t h e r a d i a t i o n in o u r s u r r o u n d i n g s . T h i s "natural" r a d i a t i o n is
o u t l i n e d , a n d t h e g o a l s o f m a t e r i a l s s c i e n c e for s e v e r a l s o l a r e n e r g y c o n v e r s i o n
systems are discussed.
I. RENEWABLE ENERGY CONVERSION PATHWAYS
T h e l i m i t e d a v a i l a b i l i t y o f fossil a n d n u c l e a r fuels, a n d t h e i r e n v i r o n m e n t a l
i m p a c t s , h a v e l e d to a g r o w i n g a w a r e n e s s o f the i m p o r t a n c e o f r e n e w a b l e e n e r g y
sources. Political considerations and incidental market fluctuations m a y h a v e
s h o r t t e r m effects, b u t t h e y w i l l n o t offset t h e t e n d e n c y that r e n e w a b l e e n e r g y
s o u r c e s , a n d t h e m a t e r i a l s for i m p l e m e n t i n g their a s s o c i a t e d b e n i g n t e c h n o l o g i e s ,
a r e g o i n g t o p l a y a n e v e r - i n c r e a s i n g r o l e b o t h in the i n d u s t r i a l i z e d a n d less d e v e -
l o p e d c o u n t r i e s . G i v e n this s i t u a t i o n , m a t e r i a l s s c i e n c e for r e n e w a b l e e n e r g y
c o n v e r s i o n s y s t e m s - w h i c h this b o o k is all a b o u t - is s u r e t o b e o f g r o w i n g i m p o r -
t a n c e . T h e t o p i c lies at the c r o s s r o a d s o f b a s i c p h y s i c s a n d c h e m i s t r y , m a t e r i a l s
fabrication, and energy technology. Besides providing great intellectual challenges
to t h e m a t e r i a l s s c i e n t i s t , this field offers p e r s o n a l s a t i s f a c t i o n : its g o a l s a r e n o t to
d e v e l o p m e a n s o f m a s s d e s t r u c t i o n or l u x u r y i t e m s for t h e affluent f e w , b u t r a t h e r
to p r o m o t e s u s t a i n a b l e d e v e l o p m e n t a n d a d e c e n t q u a l i t y o f life for all
humankind.
T h e importance o f renewable energy sources are currently attracting widespread

a t t e n t i o n . O n e m a n i f e s t a t i o n o f this i n t e r e s t is t h e r e c e n t r e p o r t b y t h e W o r l d
C o m m i s s i o n o n E n v i r o n m e1n t a n d D e v e l o p m e n t ( a l s o k n o w n a s t h e " B r u n d t l a n d
Report"), w h i c h states t h a t
1
2 Materials Science for Solar Energy Conversion Systems
renewable sources /.../ should form the foundation of the global energy structure
during the 21st century. Most of these sources are currently problematic but given
innovative development, they could supply the same amount of primary energy
the planet now consumes. However, achieving these use levels will require a
programme of coordinated research, development, and demonstration projects
/.../ to ensure the rapid development of renewable energy.
T h e p r e s e n t b o o k c a n b e v i e w e d as a n a t t e m p t t o g i v e s o m e m a t e r i a l s s c i e n c e
i n p u t i n t o t h e r e s e a r c h a n d d e v e l o p m e n t c a l l e d for i n t h e B r u n d t l a n d R e p o r t .
2
Figure 1 gives a schematic representation of renewable energy conversion. Solar
e n e r g y c a n b e c o n v e r t e d i n t o useful f o r m s t h r o u g h p a t h w a y s i n t h e g e o s p h e r e ,
b i o s p h e r e a n d t e c h n o s p h e r e . T h u s m a s s f l o w i n t h e a t m o s p h e r e c a n b e u s e d for
w i n d p o w e r , a n d w a t e r flow c a n b e u s e d for h y d r o e l e c t r i c / h y d r o m e c h a n i c p o w e r ,
w a v e p o w e r , a n d tidal p o w e r . H e a t g r a d i e n t s i n t h e s e a m a y b e useful for o c e a n
t h e r m a l e n e r g y c o n v e r s i o n ( O T E C ) . I n t h e b i o s p h e r e , s o l a r e n e r g y is r e q u i r e d for
p h o t o s y n t h e s i s l e a d i n g to f o o d p r o d u c t i o n a n d to e n e r g y c o n v e r s i o n b a s e d o n
b i o m a s s a n d b i o g a s . T h e t e c h n o s p h e r e g i v e s a m u l t i t u d e o f o p t i o n s for m a n m a3 de
c o l l e c t o r s o f s o l a r e n e r g y a n d for e n e r g y - e f f i c i e n t p a s s i v e d e s i g n i n a r c h i t e c t u r e .
A m o n g the collectors, o n e c a n distinguish between those utilizing thermal
c o n v e r s i o n ("solar c o l l e c t o r s " ) a n d q u a n t u m c o n v e r s i o n ("solar c e l l s " ) .
Geosphere | | Biosphere | | Technosphere
Solar
radiation
j
1Φ 40
ation
tors
ings
ade
tyle
Ο w :
ics
m
Ε Φ
C
S M φ ΦΦ
75
CO JO
φ
> 9 c ε 2
(GsΦ
Ε υ S
LU < α
(0
Q Ο £ Έ
<
"3
ω
2
Ο υ
Ρ o» s
1
|
1
conversion |
Conservation
conversion
Thermal
Recycling
Biomass
Passive
Quantum
design
thermal
Biogas
OTEC
Hydro
Wave
Geo-
Wind
j
1
1
Useful Energy
Fig. 1. Renewable energy conversion pathways. ( F r o m Ref. 2).

Introduction to Materials Science for Solar Energy 3
G e o t h e r m a l e n e r g y - w h i c h d o e s n o t r e l y o n s o l a r r a d i a t i o n - is a v i a b l e s o u r c e o f
e n e r g y in c e r t a i n l o c a t i o n s . F i n a l l y , p o l i t i c a l d e c i s i o n s a n d l e g i s l a t i v e a c t i o n s , as
w e l l as i n d i v i d u a l c o n v i c t i o n , c a n l e a d to a " n o n - c o n s u m p t i o n i s t " l i f e s t y l e
i n v o l v i n g e n e r g y c o n s e r v a t i o n a n d m a t e r i a l s r e c y c l i n g a n d h e n c e to a d e c r e a s e in
the d e m a n d o n p r i m a r y e n e r g y .
F r o m F i g . 1 it s h o u l d b e o b v i o u s that v e r y m a n y k i n d s o f m a t e r i a l s c a n b e e m -
p l o y e d for r e n e w a b l e e n e r g y c o n v e r s i o n . T h u s , for e x a m p l e , n e w h i g h s t r e n g t h
p o l y m e r i c a n d m e t a l l i c m a t e r i a l s a r e o f i n t e r e s t for w i n d e n e r g y a n d for O T E C
i n s t a l l a t i o n s . It f o l l o w s that it is n o t p r a c t i c a l to c o n s i d e r m a t e r i a l s for all o f t h e
a p p l i c a t i o n s m e n t i o n e d in F i g . 1 as a s e l f - c o n t a i n e d g r o u p . H o w e v e r , o n e c a n
s i n g l e o u t " m a t e r i a l s for s o l a r e n e r g y c o n v e r s i o n " as a c a t e g o r y w h o s e p r o p e r t i e s
a r e t a i l o r e d s p e c i f i c a l l y to m e e t the r e q u i r e m e n t s set b y3t h e s p e c t r a l c o n t e n t a n d
i n t e n s i t y o f t h e r a d i a t i o n in o u r n a t u r a l s u r r o u n d i n g s . S u c h m a t e r i a l s , m a n y o f
w h i c h a r e m o s t useful as thin s u r f a c e c o a t i n g s , a r e d i s c u s s e d in this b o o k . M o r e
specifically, t h e b o o k m a i n l y c o n s i d e r s t h e s c i e n c e o f m a t e r i a l s o f r e l e v a n c e for
t h e r m a l c o n v e r s i o n in m a n m a d e c o l l e c t o r s a n d for e n e r g y - e f f i c i e n t p a s s i v e d e s i g n
in a r c h i t e c t u r e .
IL NATURAL RADIATION
T h e b a s i c p r i n c i p l e s o f efficient s o l a r e n e r g y c o n v e r s i o n s y s t e m s c a n b e g r a s p e d
o n l y if o n e h a s a c l e a r i d e a o f the r a d i a t i o n that p r e v a i l s in o u r n a t u r a l s u r r o u n -
d i n g s . T h i s r a d i a t i o n is i n t r o d u c e d in Fig. 2, w h3e r e the different s p e c t r a a r e d r a w n
with a c o m m o n logarithmic wavelength scale.
A l l m a t t e r e m i t s r a d i a t i o n . T h e p r o p e r t i e s o f this r a d i a t i o n a r e c o n v e n i e n t l y
d i s c u s s e d b y s t a r t i n g w i t h the ideal b l a c k b o d y , w h o s e e m i t t e d s p e c t r u m - k n o w n as
t h e P l a n c k s p e c t r u m - is u n i q u e l y d e f i n e d if the a b s o l u t e t e m p e r a t u r e is k n o w n .
P l a n c k ' s l a w is a c o n s e q u e n c e o f t h e q u a n t u m n a t u r e o f r a d i a t i o n . P a r t (a) o f F i g . 2
d e p i c t s P l a n c k s p e c t r a for four t e m p e r a t u r e s . T h e v e r t i c a l s c-a l e3d e n o t e s p o w e r p e r
u n i t a r e a a n d w a v e l e n g t h i n c r e m e n t ( h e n c e the u n i t G W m ) . T h e s p e c t r a a r e
b e l l - s h a p e d a n d c o n f i n e d to the 2 < λ < 1 0 0 μιη r a n g e . T h e p e a k s in t h e s p e c t r a are
d i s p l a c e d t o w a r d s h o r t e r w a v e l e n g t h as the t e m p e r a t u r e g o e s u p ; this is r e f e r r e d to
as W i e n ' s d i s p l a c e m e n t l a w . A t r o o m t e m p e r a t u r e the p e a k lies at a b o u t 1 0 μ ι η .
T h e r m a l r a d i a t i o n f r o m a m a t e r i a l is o b t a i n e d b y m u l t i p l y i n g t h e P l a n c k s p e c t r u m
b y a n u m e r i c a l factor - t h e e m i t t a n c e - w h i c h is less than u n i t y . I n g e n e r a l , t h e
e m i t t a n c e is w a v e l e n g t h d e p e n d e n t .
F i g u r e 42 ( b ) r e p r o d u c e s a s o l a r s p e c t r u m for r a d i a t i o n o u t s i d e t h e e a r t h ' s a t m o s -
p h e r e . T h e c u r v e h a s a b e l l s h a p e d e f i n e d b y the s u n ' s s u r f a c e t e m p e r a t u r e
( ~ 6 0 0 0 ° C ) . O n e o b s e r v e s that t h e s o l a r s p e c t r u m is l i m i t e d to t h e 0 . 2 5 < λ < 3 μ ι η
i n t e r v a l , s o that t h e r e is a l m o s t n o o v e r l a p w i t h the s p e c t r a for t h e r m a l r a d i a t i o n .
H e n c e o n e c a n h a v e s u r f a c e s w h o s e p r o p e r t i e s a r e e n t i r e l y different w i t h r e g a r d to
t h e r m a l a n d s o l a r r a d i a t i o2n . T h e i n t e g r a t e d a r e a u n d e r t h e c u r v e g i v e s t h e s o l a r
c o n s t a n t ( 1 3 5 3 ± 2 1 W m ~ ) ; this is the l a r g e s t p o s s i b l e p o w e r d e n s i t y o n a s u r f a c e
o r i e n t e d p e r p e n d i c u l a r to t h e s u n in t h e a b s e n c e o f a t m o s p h e r i c e x t i n c t i o n .
^ I
3
ι ι ι ι 111| ι ι r ι ι ι 1111 î—ι ι ι ι I I I 11_
08|GW/m
0l r \
Γ 100°C^/ \ Blackbody Ζ
- 0,06 50 / \ radiation -
a
- 0.04 00 5
-0.02 ^ Î O ^ ^ ^ ~
2 3
- [GW/m ]À
- 1.6 Λ Soiar radiation -
b_ 49 I \ (extraterrestrial) _
- I \
- 0.8 J \
- 04 / >v
0— — • —
η un r
Atmospheric J
6
0 , I I absorptance -
c Ζ Ι Ι A (sea level) I
Γ"1
r UÉI\I U Λ
j ]
α_ Q3 Relative sensitivity of human _
. - eye (photopic state)
- 0.6 - -
; Relative photon efficiency
Γ ^ J I I
fi
I M M I
for Igreen
I I
algae I L I I I I I I l l
I I I I I I i
020,2 0 / 5! 1 2 (Chlorella5 1 vulgaris)
0 2 0 5 0 1 0 0
ο r\ Wavelength (jjm| J
Fig. 2 . S p e c t r a for (a) b l a c k b o d y r a d i a t i o n p e r t a i n i n g to f o u r
temperatures, (b) solar radiation outside the earth's a t m o -
s p h e r e , (c) t y p i c a l a b s o r p t a n c e a c r o s s t h e full a t m o s p h e r i c
e n v e l o p e , (d) relative sensitivity o f the h u m a n e y e a n d
r e l a t i v e p h o t o n efficiency o f g r e e n a l g a e . ( F r o m R e f . 3 ) .
T h e s o l a r e n e r g y c o n v e r s i o n s y s t e m s o f p r e s e n t c o n c e r n a r e to b e p l a c e d at g r o u n d
l e v e l , a n d it is o f o b v i o u s i n t e r e s t to c o n s i d e r to w h a t e x t e n t a t m o s p h e r i c a b s o r p -
tion influences solar irradiation and thermal emission. Figure 2(c) illustrates a
t y p i c a l a b s o r p t i o n s p5e c t r u m v e r t i c a l l y a c r o s s t h e full a t m o s p h e r i c e n v e l o p e at c l e a r
w e a t h e r c o n d i t i o n s . T h e s p e c t r u m is f o u n d to b e q u i t e c o m p l i c a t e d w i t h b a n d s o f
high absorption - caused mainly by water vapour, carbon dioxide, and ozone - and
i n t e r v e n i n g b a n d s o f h i g h t r a n s p a r e n c y . It is e v i d e n t that t h e m a j o r i t y o f t h e s o l a r
r a d i a t i o n c a n b e t r a n s m i t t e d d o w n to g r o u n d l e v e l , a n d o n l y p a r t s o f t h e u l t r a -
v i o l e t (λ < 0.4 μιη) a n d i n f r a r e d (λ > 0.7 μιη) tails a r e s t r o n g l y d a m p e d . T h e - 2
m a x i m u m p o w e r d e n s i t y p e r p e n d i c u l a r to t h e s u n is l i m i t e d to a b o u t 1 0 0 0 W m .
T h e r m a l r a d i a t i o n f r o m a s u r f a c e e x p o s e d to t h e c l e a r s k y is s e e n to b e s t r o n g l y
a b s o r b e d e x c e p t in t h e 8 < λ < 13 μ ι η r a n g e , w h e r e t h e t r a n s m i t t a n c e c a n b e l a r g e
Introduction to Materials Science for Solar Energy 5
p r o v i d e d t h a t t h e h u m i d i t y is m o d e r a t e l y l o w . T h e t h e r m a l r a d i a t i o n c a n b e l a r g e
in t h e 8-13 μιτι i n t e r v a l , a n d h e n c e o n e c o n c l u d e s t h a t a n o n - n e g l i g i b l e p a r t o f the
emitted energy can g o straight through the atmosphere. This p h e n o m e n o n
c o n s t i t u t e s t h e b a s i s for r a d i a t i v e c o o l i n g .
F i g u r e 2 ( d ) i l l u s t r a t e s t w o b i o p h y s i c a l c o n s t r a i n t s o f i n t e r e s t for a p p l i c a t i o n s . T h e
s o l i d c u r v e s h o w s t h e r e l a t i v e s p e c t r a l s e n s i t i v i t y o f t h e h u m a n e y e in its light-
a d a p t e d ( p h o t o p i c ) state. T h e b e l l 6 - s h a p e d c u r v e e x t e n d s a c r o s s t h e 0.4 < λ < 0.7 μ ι η
i n t e r v a l w i t h its p e a k at 0 . 5 5 5 μ ι η . I n its d a r k n e s s - a d a p t e d ( s c o t o p i c ) s t a t e , t h e
e y e ' s s e n s i t i v i t y is d i s p l a c e d a b o u t 0.05 μ ι η t o w a r d s h o r t e r w a v e l e n g t h s . H e n c e a
l a r g e p a r t o f t h e s o l a r e n e r g y c o m e s as infrared r a d i a t i o n . P h o t o s y n t h e s i s in p l a n t s
o p e r a t e s w i t h w a v e l e n g t h s in a p p r o x i m a t e l y the s a m e r a n g e a s t h o s e for t h e
h u m a n e y e , w h i c h is o f o b v i o u s r e l e v a n c e for g r e e n h o u s e a p p l i c a t i o n s . A n
e x a m p l e o f t h e r e l a t i v e p h o t o n efficiency for g r e e n a l g a e is g i v e n b y t h e d a s h e d
curve.
III. S O M E GOALS OF MATERIALS SCIENCE FOR SOLAR

ENERGY CONVERSION SYSTEMS, AND BOOK OUTLINE
T h e different t y p e s o f a m b i e n t r a d i a t i o n a r e s p e c t r a l l y s e l e c t i v e , i.e., c o n f i n e d to
w e l l - d e f i n e d a n d often n o n - o v e r l a p p i n g w a v e l e n g t h r a n g e s , as a p p a r e n t f r o m F i g .
2. T h i s is o f m a j o r s i g n i f i c a n c e a n d , in fact, t h e g o a l o f m a t e r i a l s s c i e n c e for s o l a r
e n e r g y c o n v e r s i o n s y s t e m s is to d e v e l o p m a t e r i a l s - often s u r f a c e c o a t i n g s - w h i c h
t a k e a d v a n t a g e o f t h e s p e c i f i c f e a t u r e s o f the a m b i e n t r a d i a t i o n . T h e f o l l o w i n g
properties and materials are of particular relevance:
(1) H i g h t r a n s m i t t a n c e o f s o l a r r a d i a t i o n c a n b e a c h i e v e d in m a t e r i a l s w i t h
p o r o u s o r c e l l u l a r c o n f i g u r a t i o n s that p r e v e n t air c i r c u l a t i o n . S u c h
m a t e r i a l s s u p p r e s s c o n v e c t i v e h e a t transfer a n d p r o m o t e t h e r m a l
insulation.
(2) H i g h absorption of solar radiation can be c o m b i n e d with l o w emittance o f

thermal radiation b y use of spectrally selective surfaces. T h e s e materials are
o f i n t e r e s t for efficient p h o t o t h e r m a l c o n v e r s i o n o f s o l a r e n e r g y .
(3) H i g h transmittance of solar radiation can b e c o m b i n e d w i t h l o w emittance

of thermal radiation, and high transmittance of visible light can b e
c o m b i n e d w i t h h i g h r e f l e c t a n c e o f infrared s o l a r r a d i a t i o n . S u r f a c e c o a t i n g s
w i t h t h e s e p r o p e r t i e s a r e o f g r e a t i n t e r e s t for e n e r g y - e f f i c i e n t f e n e s t r a t i o n in
cold and hot climates, respectively.
(4) M a t e r i a l s w i t h h i g h l y a n g u l a r - d e p e n d e n t r a d i a t i v e p r o p e r t i e s c a n b e u s e d in
s e v e r a l different w a y s i n e n e r g y - e f f i c i e n t f e n e s t r a t i o n .
(5) C o a t i n g s w i t h r a d i a t i v e p r o p e r t i e s that can b e c h a n g e d to m a t c h differing

d e m a n d s o f h e a t i n g a n d l i g h t i n g a r e o f o b v i o u s i n t e r e s t for a c h i e v i n g
e n e r g y - e f f i c7i e n t b u i l d i n g s . T h e r e l e v a n t m a t e r i a l s h a v e " c h r o m o g e n i c "
properties.
(6) T h e h i g h a t m o s p h e r i c t r a n s m i t t a n c e in t h e 8-13 μ ι η w a v e l e n g t h r a n g e c a n
b e u s e d for c h a n n e l l i n g e n e r g y from s k y - f a c i n g surfaces i n t o s p a c e . T h u s it
is p o s s i b l e to d e v i s e m a t e r i a l s for efficient p a s s i v e c o o l i n g t o t e m p e r a t u r e s
w e l l b e l o w t h e air t e m p e r a t u r e .
I t e m s (1) - (6) a r e c o v e r e d in s e v e r a l topical c h a p t e r s b e l o w . T h e y a r e p r e c e d e d b y a

t h e o r e t i c a l t r e a t i s e o n Optical Properties of Inhomogeneous Two-Component
Materials b y G . A . N i k l a s s o n . T h i s c h a p t e r d i s c u s s e s m a t t e r s o f i n t e r e s t for u n d e r -
s t a n d i n g s o m e b a s i c m a t e r i a l s s c i e n c e d i s c u s s e d in t h e t o p i c a l c h a p t e r s . H o w e v e r ,
it is n o t t h e c a s e that a d e t a i l e d u n d e r s t a n d i n g o f t h e - s o m e t i m e s r a t h e r i n v o l v e d
a n d t e c h n i c a l - e x p o s i t i o n in t h e t h e o r y c h a p t e r is a p r e r e q u i s i t e for g r a s p i n g t h e
topical p r e s e n t a t i o n s . T h e first topical c h a p t e r is r e l a t e d to i t e m ( 1 ) ; it is e n t i t l e d
Transparent Insulation Materials a n d is a u t h o r e d b y W . P l a t z e r a n d V . W i t t w e r .
I t e m (2) is t r e a t e d in a d i s c u s s i o n o n Selectively Solar-Absorbing Surface Coatings:
Optical Properties and Degradation by G.A. Niklasson and C.G. Granqvist. Items
(3)-(5) a r e g i v e n a u n i f i e d a n d e x t e n s i v e p r e s e n t a t i o n e n t i t l e d Energy-Efficient
Windows: Present and Forthcoming Technology b y C . G . G r a n q v i s t . T h e final
c h a p t e r o f t h e b o o k is r e l a t e d to i t e m (6) a n d c o v e r s Materials for Radiative
Cooling to Low Temperatures; it is a u t h o r e d b y C . G . G r a n q v i s t a n d T . S . E r i k s s o n .
T h e a i m o f t h e b o o k is to g i v e a d e t a i l e d a n d u p - t o - d a t e p r e s e n t a t i o n o f s e v e r a l k e y
a s p e c t s o f m a t e r i a l s s c i e n c e for solar e n e r g y c o n v e r s i o n s y s t e m s , e x c l u d i n g t h o s e
r e l y i n g o n q u a n t u m c o n v e r s i o n . It s h o u l d b e r e m e m b e r e d , t h o u g h , t h a t e v e n
w i t h this r e s t r i c t i o n t h e r e a r e s e v e r a l i n t e r e s t i n g a n d i m p o r t a n t m a t e r i a l s that a r e
n o t d i s c u s s e d ; a m o n g t h e s e a r e reflector m a t e r i a l s , light c o n c e n t r a t o r s , t h e r m a l
storage media, and others.
REFERENCES
1. W o r l d C o m m i s s i o n o n E n v i r o n m e n t a n d D e v e l o p m e n t , Our Common
Future ( O x f o r d U n i v e r s i t y P r e s s , O x f o r d , U K , 1 9 8 7 ) , p. 1 5 .
2. C . G . G r a n q v i s t , in Energy and the Environment into the 1990s, e d i t e d b y
A . A . M . S a y i g h ( P e r g a m o n , O x f o r d , U K , 1 9 9 0 ) , V o l . 3, p . 1 4 6 5 ; A p p l . P h y s . A
5 2 , 8 3 (1991).
3. C . G . G r a n q v i s t , Spectrally Selective Surfaces for Heating and Cooling
Applications (SPIE Opt. Engr. Press, Bellingham, U S A , 1989).
4. M . P . T h e k a e k a r a , in Solar Energy Engineering, edited by A.A.M. Sayigh
( A c a d e m i c , N e w Y o r k , 1 9 7 7 ) , p. 37.
5. K . Y a . K o n d r a t y e v , Radiation in the Atmosphere (Academic, N e w York,
1969).
6. G . W y s z e c k i a n d W . S . Stiles, in Color Science, 2 n d e d i t i o n ( W i l e y , N e w
Y o r k , 1 9 8 2 ) , p. 2 5 6 .
7. C M . L a m p e r t a n d C . G . G r a n q v i s t , e d i t o r s , Large-area Chromogenics:
Materials and Devices for Transmittance Control ( S P I E O p t . E n g r . P r e s s ,
B e l l i n g h a m , U S A , 1 9 9 0 ) ; C . G . G r a n q v i s t , Crit. R e v . S o l i d S t a t e M a t e r . S c i .
1 6 , 2 9 1 (1990).
Chapter 2
OPTICAL PROPERTIES OF INHOMOGENEOUS

TWO-COMPONENT MATERIALS
G.A. Niklasson
Physics Department
ABSTRACT
E f f e c t i v e m e d i u m a n d m u l t i p l e s c a t t e r i n g t h e o r i e s for t h e o p t i c a l p r o p e r t i e s o f
two-component materials are reviewed. Such materials h a v e n u m e r o u s appli-
c a t i o n s in t h e field o f c o a t i n g s for e n e r g y efficiency. T h e t r a n s m i t t a n c e a n d
r e f l e c t a n c e o f a c o a t i n g or s l a b o f a c o m p o s i t e c a n b e o b t a i n e d f r o m t h e effective
dielectric and magnetic permeabilities of the material. For materials with
inhomogeneities m u c h smaller than the wavelength o f the i m p i n g i n g radiation,
the effective d i e l e c t r i c p e r m e a b i l i t y c a n b e e v a l u a t e d in t h e q u a s i s t a t i c l i m i t . W e
r e v i e w t h e r i g o r o u s B e r g m a n - M i l t o n b o u n d s for t h e e f f e c t i v e d i e l e c t r i c p e r m e a -
b i l i t y as w e l l as v a r i o u s effective m e d i u m t h e o r i e s that h a v e b e e n p u t f o r w a r d for
d e s c r i b i n g t h e o p t i c a l p r o p e r t i e s o f specific m i c r o s t r u c t u r e s . S p e c i f i c a l l y w e treat
t h e effects o f p a i r a n d t h r e e - p o i n t c o r r e l a t i o n s o n t h e b o u n d s a n d o b t a i n n o v e l
effective m e d i u m t h e o r i e s t a k i n g t h e s e effects i n t o a c c o u n t . M a t e r i a l s w i t h l a r g e
i n h o m o g e n e i t i e s o n t h e o r d e r of, o r l a r g e r t h a n , the w a v e l e n g t h m u s t b e d e s c r i b e d
b y different t h e o r i e s . T h e effective m a g n e t i c p e r m e a b i l i t y m u s t b e t a k e n i n t o
a c c o u n t . T h e s p e c u l a r r e f l e c t a n c e , the d i r e c t t r a n s m i t t a n c e a n d t h e diffuse
s c a t t e r i n g a r e t r e a t e d b y u s e o f a four flux t h e o r y .
I. INTRODUCTION
A n u n d e r s t a n d i n g o f t h e o p t i c a l p r o p e r t i e s o f i n h o m o g e n e o u s m a t e r i a l s is v e r y
i m p o r t a n t in t h e d e v e l o p m e n t a n d o p t i m i z a t i o n o f v a r i o u s c o a t i n g s for e n e r g y
efficiency. A p p l i c a t i o n s s u c h as s o l a r a b s o r p t i o n , r a d i a t i v e c o o l i n g a n d e n e r g y
efficient w i n d o w s h a v e p r o m p t e d a l a r g e i n t e r e s t in c o m p o s i t e m a t e r 1 ials. M a n y
c o a t i n g s u s e d for s e l e c t i v e a b s o r p t i o n o f s o l a r e n e r g y a r e o f this c l a s s . C o m p o s i t e s
o f m e t a l p a r t i c l e s in a n i n s u l a t o r m a t r i x d i s p l a y -5
a v e r y g o o d s e l e c t i v i t y , a n d h6a7
ve
been produced 8 b y electrochemical t e c h n i q u e s / electron-beam evaporation '
a n d s p u t9 tering. Another example of composite selective absorbers are paint
c o a t i n g s w h i c h c o n s i s t o f a n a b s o r b i n g p i g m e n t d i s p e r s e d in a b i n d e r m a t e r i a l .
7
For radiative cooling applications solar reflecting and infrared-transmitting

p i g m e n t e d p o l y m e r foils a r e o f interest, as 1w 0 e l l as c e r a m i c s w h i c h p r o b a b l y c o n s i s t
of a mixture of an oxide phase and v o i d s . A s a final e x a m p l e w e m e n t i o n that
m a n y v i s i b l y t r a n s m i t t i n g c o a t i n g s w i t h l o w e m i t t a n c e - o f u s e for e n e r g y - e f f i c i e n t
w i n d o w s - i n c o r p o r a t e thin m e t a l films. It has r e c e n t l y b e e n s h o w n t h a t an i m -
p r o v e d p e r f o r m a n c e c a n b1 e1 a c h i e v e d b y i n h o m o g e n e o u s " n e t w o r k " f i l m s c l o s e to
the percolation threshold. T h e a i m o f this c h a p t e r is to r e v i e w t h e o r e t i c a l
descriptions of the optical properties of two-component materials. T h e s e theories
a r e often v e r y useful in t h e s t u d y o f m a t e r i a l s for e n e r g y - e f f i c i e n t a p p l i c a t i o n s .
H o w e v e r , this c h a p t e r is n o t a p r e r e q u i s i t e for t h e r e s t o f t h e b o o k , a n d t h e r e a d e r
m a i n l y i n t e r e s t e d in t e c h n i c a l a p p l i c a t i o n s m a y p r o c e e d d i r e c t l y to t h e t o p i c a l
chapters.
I n t h e d e v e l o p m e n t o f c o m p o s i t e thin films it is o f p r i m e i m p o r t a n c e to e s t a b l i s h
t h e c o n n e c t i o n b e t w e e n t h e p r o p e r t i e s o f the c o m p o s i t e a n d t h o s e o f t h e c o n s t i -
t u e n t s . T h i s facilitates m a t e r i a l s s e l e c t i o n a n d o p t i m i z a t i o n o f p r a c t i c a l c o a t i n g s .
T h e o p t i c a l p r o p e r t i e s o f c o m p o s i t e m a t e r i a l s c a n b e d e s c r i b e d in t h e q u a s i s t a t i c
a p p r o x i m a t i o n if the s i z e o f t h e i n h o m o g e n e i t i e s is m u c h s m a l l e r t h a n t h e
wavelength o f electromagnetic radiation. T h e optical properties o f the material
a r e o b t a i n e d f r o m t h e effective d i e l e c t r i c p e r m e a b i l i t y o f t h e c o m p o s i t e w h i c h c a n
b e r e l a t e d to t h e d 1 i e l e4
2c t -r i c1p e r m e a b i l i t i e s o f t h e c o n s t i t u e n t s b y e f f e c t i v e m e d i u m
theories ( E M T ' s ) . T h e s e theories are also sensitively d e p e n d e n t u p o n the
actual m i c r o g e o m e t r y of the composite material. Actually a rigorous expression
for the effective d i e l e c t r i c p e r m e a b i l i t y c a n o n l y b e o b t a i n e d if t h e d e t a i l e d
g e o m e t r i c a l a r r a n g e m e n t (i.e., t h e η - p o i n t c o r r e l a t i o n f u n c t i o n s ) o f t h e c o n s t i -
t u e n t s a r e k n o w n . W h e n l i m i t e d s t r u c t u r a l i n f o r m a t i o n is a v a i l a b l e , as is a l w a y s
t h e c a s e in p r a c t i c e , t h e v a r i o u s E M T ' s c a n g i v e n o m o r e t h a n a p p r o x i m a t e
e x p r e s s i o n s . H o w e v e r it 1is 8 5p o-s s i1b l e to o b t a i n r i g o r o u s b o u n d s for t h e e f f e c t i v e
dielectric p e r m e a b i l i t y . W h e n m o r e s t r u c t u r a l i n f o r m a t i o n is i n c o r p o r a t e d
into the b o u n d s , they b e c o m e m o r e narrow. For large size inhomogeneities the
q u a s i s t a t i c a p p r o x i m a t i o19 n is n o t v a l i d a n d t h e c o n c e p t o f an e f f e c t i v e m e d i u m
encounters difficulties. Scattering becomes important and the optical properties
c a n b e d2 e s c2
0r i b-e d2 i n t h e f r a m e w o r k o f r a d i a t i v e transfer a n d m u l t i p l e s c a t t e r i n g
theory. In the c a s e o f v e r y l a r g e p a r t i c l e s , s i m p l i f i c a t i o n s a r e a g a i n p o s s i b l e
and geometric optics can be used.
In this c h a p t e r t h e v a r i o u s t h e o r i e s that h a v e b e e n p u t f o r w a r d to d e s c r i b e t h e
optical properties o f composite materials are reviewed. W e will consider mate-
rials w i t h i n h o m o g e n e i t i e s o f a n y s i z e , b u t o u r t r e a t m e n t is r e s t r i c t e d to t w o -
c o m p o n e n t m a t e r i a l s . I n S e c . II b e l o w w e m a k e a b r i e f d e s c r i p t i o n o f t h i n film
o p t i c s . H e r e t h e t r a n s m i t t a n c e a n d r e f l e c t a n c e o f a thin film a r e r e l a t e d to t h e
d i e l e c t r i c a n d m a g n e t i c p e r m e a b i l i t i e s o f the film m a t e r i a l . S o m e m o d e l s o f t h e
d i e l e c t r i c p e r m e a b i l i t y , w h i c h g i v e i n s i g h t i n t o the p h y s i c a l p h e n o m e n a i n v o l v e d ,
a r e a l s o d e s c r i b e d . I n S e c . I l l w e treat the c a s e o f s m a l l i n c l u s i o n s o f t h e c o m p o -
n e n t s o f t h e c o m p o s i t e m a t e r i a l . T h e effective d i e l e c t r i c p e r m e a b i l i t y is t h e n
e v a l u a t e d in t h e q u a s i s t a t i c a p p r o x i m a t i o n . W e d e s c r i b e t h e r i g o r o u s b o u n d s a n d
effective m e d i u m t h e o r i e s t h a t a r e v a l i d in this l i m i t , a n d c o n s i d e r c a s e s w h e r e
different a m o u n t s o f i n f o r m a t i o n a b o u t t h e c o m p o s i t e is k n o w n , n a m e l y t h e
15
d i e l e c t r i c p e r m e a b i l i t i e s a n d v o l u m e fractions o f t h e c o n s t i t u e1
n6t s a n d i s o t r o p y o f
t h e s t r u c t u r e . T h i s l e a d s to t h e W i e n e r , H a s h i n - S h t r i k m a n a n d B e r g m a n -
Optical Properties of Inhomogeneous Two-component Materials 9
1 17
8
M i l t o n ' b o u n d s . S i m p l e effective m e d i u m t h e o r i e s for t h e d i e l e c t r i c
p e r m e a b i l i t y a r e a p p l i c a b l e to s p e c i a l m i c r o s t r u c t u r e s .
R e c e n t a d v a n c e s in t h e c h a r a c t e r i z a t i o n o f c o m p o s i t e m a t e r i a l s h a v e m a d e it
p r a c t i c a l to i n c o r p o r a t e m o r e i n f o r m a t i o n a b o u t t h e g e o m e t r y t h a n t h e v o l u m e
fractions a n d t h e c o n d i t i o n o f i s o t r o p y i n t o r i g o r o u s b o u n d s a n d effective
m e d i u m t h e o r i e s . I n S e c . I V w e treat t h e s i t u a t i o n w h e n t h e p a i r a n d t h r e e - p o i n t
correlation functions are known. This k2 i3
n d o f t h e o r y h a s s o far o n l y b e e2n 2 46a p p l i e d
to c e r t a i n c a27
s e s , i.e., to fractal s t r u c t u r e s a n d r a n d o m m i x t u r e s o f h a r d " or
p e n e t r a b l e s p h e r e s in a m a t r i x .
In S e c . V w e treat t h e c a s e o f i n h o m o g e n e i t i e s w i t h l a r g e r s i z e s , w h e r e t h e q u a s i -
static a p p r o x i m a t i o n is n o t a p p l i c a b l e . O n e m a y d e r i v e e x t e n d e d effective 19
m e d i u m t h e o r i e s that d e s c r i b e s o m e a s p e c t s o f t h e o p t i c a l p r o p e r t i e s in this c a s e .
H o w e v e r , w h e n s c a t t e r i n g is o f i m p o r t a n c e a c o m p l e t e l y different 2 20a p-p r2o a c h is
n e c e s s a r y , a n d r a d i a t i v e transfer o r m u l t i p l e s c a t t e r i n g t h e o r y h a s to b e u s e d .
It t u r n s o u t t h a t in m a n y c a s e s , e.g. w h e n c o n s i d e r i n g c o a t i n g s , i m p o r t a n t
s i m p l i f i c a t i o n s c a n b e m a d e . A four-flux t h e o r y that is sufficiently a c c u r a t e for
c o m p a r i s o n s w i t h s p e c t r o p h o t o m e t r i c d a t a o n i n h o m o g e n e o u s m a t e r i a l s is
d e s c r i b e d . S o m e final r e m a r k s a r e m a d e in S e c . V I .
IL THIN FILM OPTICS AND THE DIELECTRIC PERMEABILITY.
W h e n s t u d y i n g t h e o p t i c a l p r o p e r t i e s o f a m a t e r i a l o n e g e n e r a l l y m e a s u r e s the
r e f l e c t a n c e a n d t r a n s m i t t a n c e as a f u n c t i o n o f w a v e l e n g t h a n d a n g l e o f i n c i d e n c e .
T h e s e q u a n t i t i e s a r e f u n c t i o n s o f t h e d i e l e c t r i c a n d m a g n e t i c p e r m e a b i l i t i e s o f the
m a t e r i a l . C o n v e r s e l y , it is p o s s i b l e to e v a l u a t e for e x a m p l e t h e d i e l e c t r i c p e r m e a -
b i l i t y f r o m c a r e f u28
lly chosen combinations o f experimental transmittance and
reflectance d a t a . I n this s e c t i o n t h e t h e o r y o f the o p t i c a l p r o p e r t i e s o f a thin film
o n a s u b s t r a t e is d e s c r i b e d . A s a first s t e p w e c o n s i d e r l i g h t i n c i d e n t t o w a r d s t h e
b o u n d a r y b e t w e e n t w o m e d i a d e n o t e d i a n d j . T h e a n g l e to t h e s u r f a c e n o r m a l is
0 j , as i n d i c a t e d in F i g . 1. T h e m e d i a a r e c h a r a c t e r i z e d b y t h e i r c o m p l e x d i e l e c t r i c
a n d m a g n e t i c p e r m e a b i l i t i e s , ε^, j a n d μ|, j . Part o f the l i g h t is r e f l e c t e d at the
boundary(r*J) a n d p a r t is t r a n s m i t t e d (W) t h r o u g h t h e b o u n d a r y . W e d i s t i n g u i s h
b e t w e e n l i g h t w i t h s - p o l a r i s a t i o n (E v e c t o r s n o r m a l to t h e p l a n e s p a n n e d b y the
incident, reflected a n d transmitted b e a m s ) and with p-polarisation ( H vectors
n o r m a l t o t h e s a m e p l a n e ) . F r o m M a x w e l l ' s e q u a t i o n s , o n e c2a9n o b t a i n t h e w e l l
k n o w n F r e s n e l ' s r e l a t i o n s for t h e r e f l e c t e d field a m p l i t u d e s :
2 2 12
n cos0i - - ^ ( n j - n> s i n ^ ) /
t
2 2 1 2 (1)
ni cosOi + ^7 ( n | - n ^ s i n ^ ) /
J
\e ί / 'i ,p
\ s,ρ
Fig. 1. Definitions of symbols entering Fresnel's relations.
1
^ - n | 2 cosOi - ni (nf - s h ^ ) ^
rpij Β= ,
^ - η | 2 cosOi + ^ (n;2 - s i r ^ ) ^
2nj cos9i
2 (3)
^ cosGi + — ( 2 - s u v ^ ) ^
nj n i
1 J cos9;
2m m ! L
tp ) =~ . (4)
μ n|2 cosOi + ^ ( n f - ni2 s i i ^ ) ^
—
ί
H e r e nj a n d nj d e n o t e t h e refractive i n d i c e s of the m e d i a ; t h e y a r e g i v e n b y
ni = ( e i W ) l / 2 , (5)
a n d a n a l o g o u s l y for nj. F r e s n e l ' s r e l a t i o n s c a n b e u s e d to d i s c u s s t h e o p t i c a l

p r o p e r t i e s o f a thin film o n a substrate. W e c o n s i d e r the g e o m e t r y s p e c i f i e d in Fig.
2 a n d let (2) d e n o t e the film (of t h i c k n e s s d) a n d (3) the s u b s t r a t e . A m e d i u m (1)
s u r r o u n d s t h e c o a t e d s u b s t r a t e . F u r t h e r , w e let (f) signify light i n c i d e n t f r o m the
frontside a n d (b)1signify 22 31light 22 i1n 2c i d3e3n t 2from
31 the 3b a1c k s i d e . E q u a t i o n s (1) - (4) yield
e x p r e s s i o n s for r , r , t , t , t , t , r a n d t . N e g l e c t i n g t h e effect o f the
b a c k s i d e o f t h e s u b s t r a t e , t h e30a m p l i t u d e r e f l e c t a n c e a n d t r a n s m i t t a n c e for the film,
Γ2 a n d t2, a r e o b t a i n e d f r o m
r r1 s2 +2 3 e2ri 5s 6
2s "
α l+2 r 2sr3 2s ieô ' < )
©
ambient
0
® d film
® substrate
Fig. 2.
®
G e o m e t r y u s e d for d i s c u s s i n g the o p t i c s o f a thin film o n a
substrate.
1 t l2 y ^ e i S
s (7)
••2s = I + 1 2 2 3 2 i 6
r sr s e
b b fb f b
R e l a t i o n s o f t h e s a m e f o r m a r e e a s i l y f o u n d for r , t , r ' , t > as w e l l . In
2 s2 s2 p 2 p
E q s . (6) a n d 30 ( 7 ) , δ is t h e p h a s e c h a n g e o f the light b e a m u p o n t r a v e r s i n g t h e film.
Specifically
12
2πά
( ε μ - ε ! μ] s i n ^ ) / , (8)
22
w h e r e λ d e n o t e s t h e w a v e l e n g t h o f light. T h e m e a s u r a b l e o p t i c a l q u a n t i t i e s fa r e
t h e light i n t e n s i t i e s . T h e y a30
r e d e n o t e d b y capital letters, i.e., for e x a m p l e R , a n d
2 s
are given by the f o r m u l a e
b= £b 2 1 ,r
(9)
W' 2s,p ' >
T 2 (sε 3μ=1) ΐ2/ 2 α ) 8θ 3 s, t 2

(10)
( ê3) V c o s e 1 ' '
(ε! 1 2 c/ o s 9 3
μ 3)νζ
(11)
(ε μ ι ) COS0!
3
b b b b
In a d d i t i o n t h e e x p r e s s i o n s for T
2 asn d T 2 apr e o b t a i n e d f r o m t 2 asn d t 2 by
p
i n t e r c h a n g i n g t h e i n d i c e s 1 a n d 3 in E q s . ( 1 0 ) a n d ( 1 1 ) a b o v e .
If the s u b s t r a t e is m e t a l l i c , t h e t r a n s m i t t a n c e is z e r o a n d o nfl y t h e r e f l e c t a n c e h a s to
b e c o n s i d e r e d . In this c a s e it is i m m e d i a t e l y g i v e n b y R2s,p - I f t h e s u b s t r a t e is
t r a n s p a r e n t , a m o r e c o m p l i c a t e d s i t u a t i o n e x i s t s , a n d m u l t i p l e r e f l e c t i o n s in t h e
s u b s t r a t e m u s t b e t a k e n i n t o a c c o u n t . T h e s e a r e i n c o h e r e n t for l a r g e s u b s t r a t e
thicknesses and m u s t b e included through addition of the intensities o f the
m u l t i p l y reflected b e a m s . T h e final e x p r e s s i o n s for t h e r e f l e c t a n c e a n d t h e

transmittance are
f
R f
T 2 T b* > R
S 2 s 3s ,
s = R2s + Λ _ t > _ h (12)
i-R RP3s
2 s
Ts =T 2/ 3sT 1 3
l-R
2 s 3' s
">R < >
31 31
where R 3 , and T 3 a r e o b t a i n e d from r and t
Sp sp s p s pb y r e l a t i o n s a n a l o g o u s to
E q s . (9) - (11).
30
T h e t r e a t m e n t a b o v e c a n e a s i l y b e g e n e r a l i z e d to m u l t i p l e l a y e r f i l m s . T h i s is
m o s t c o n v e n i e n t l y d o n e b y u s e o f the c h a r a c t e r i s t i c m a t r i x t e c h n i q u e .
W e h a v e n o w r e l a t e d t h e t r a n s m i t t a n c e a n d r e f l e c t a n c e o f a t h i n film o n a s u b -
strate to t h e d i e l e c t r i c a n d m a g n e t i c p e r m e a b i l i t i e s . In g e n e r a l , t h e s e q u a n t i t i e s a r e
c o m p l e x a n d w a v e l e n g t h d e p e n d e n t . F o r h o m o g e n e o u s m a t e r i a l s in t h e ultra-
31 w a v e l e n g t h r a n g e s o n e m a y set t h e m a g n e t i c p e r m e a -
v i o l e t , v i s i b l e a n d infrared
bility μ e q u a l to u n i t y . T h i s is h o w e v e r n o t g3 e1n e r a l l y the c a s e for l o n g e r w a v e -
l e n g t h s , for e x a m p l e in the m i c r o w a v e r e g i o n . M a g n e t i c p e r m e a b i l i t i e s different
f r o m u n i t y m u s t a l s o b e i n c l u d e d in c e r t a i n i n h o m o g e n e o u s m a t e r i a l s as w e c o m e
b a c k to in S e c . V b e l o w .
T h e d i e l e c t r i c p e r m e a b i l i t y often s h o w s a c o m p l i c a t e d b e h a v i o u r in t h e i n f r a r e d
r a n g e a n d at s h o r t e r w a v e l e n g t h s . T h e f r e q u e n c y d e p e n d e n t d i e l e c t r i c p e r m e a -
bility is e x p r e s s e d b y
ε(ω) = ει (ω) + ίε2(ω). (14)
W e n e x t d i s c u s s t h e g e n e r a l f o r m o f ε ( ω ) for different homogeneous materials. In

m a n y c a s e s o n e c a n c o n s i d e r this function to b e a s u m o f i n d i v i d u a l c o n t r i b u t i o n s
o r i g i n a t i n g fίr o m different e l e3m
2 e n t a r y e x c i t a t i o n s . In t e r m s o f s u s c e p t i b i l i t i e s
χί = + ίχ , one can w r i t e
2
e = V1 E + P+Hx +F C%/ (15)
w h e r e V E = v a l e n c e e l e c t r o n s , P H = p h o n o n s , a n d F C = free c a r r i e r s ( u s u a l l y elec-
t r o n s ) . T h e v a r i o u s s u s c e p t i b i l i t i e s c a n e a s i l y b e d i s t i n g u i s h e d i f their r e s o n a n c e s
fall in w e l l s e p a r a t e d w a v e l e n g t h r e g i o n s . F o r a p a r t i c u l a r χ*, t h e c o n t r i b u t i o n far
f r o m its r e s o n a n c e is real a n d c o n s t a n t .
F i g u r e 3 g i v e s a s c h e m a t i c r e p r e s e n t a t i o n o f t h e χ^. T h e νΕ r e a l a n d Ρi mΗ aginary parts

are consistent with the Kramers-Kronig relations. For χ a n d χ , o n e c a n often
r e p r e s e n t t h e s u s c e p t i b i l i t i e s b y a s u m o f d a m p e d L o r e n t z o s c i l l a t o r s , i.e., b y
expressions of the kind
^0
xLorentz =—
G ) [ / - (£r
— —
- ΐωΓ
, (
1) 6
w h e r e Ω is t h e o s c i l l a t o r s t r e n g t h , c u l is t h e r e s o n a n c e f r e q u e n c y a n d Γ rνΕepresents
0
t h e w i d t h o f t h e r e s o n a n c e p e a k . F o r m o s t i n s u l a t o r s a n d g o o d m e t a l s , χ ΡΗ is
r e s o n a n t in t h e u l t r a v i o l e t o r t h e b l u e pFaC
r t o f the v i s i b l e s p e c t r u m , w h i l e χ is
r e s o n a n t in t h e t h e r m a l infrared. F o r x one can m a k e use o f the D r u d e theory,
at least for a first-order d e s c r i p t i o n . T h e s u s c e p t i b i l i t y c a n b e w r i t t e n
τ 1 1 1 1 ι 1 1 1 Γ
V V E V E
0
M J Λ
Vr^r— A
N S S S S S S S s
o ^^
u
Ο I ι ι ι ι I l ι ι ι ι
0,01 0.1 1 10 0.01 0.1 1 10
Energy (eV) Energy (eV)
Fig. 3. C o n t r i b u t i o n s to t h e d i e l e c t r i c p e r m e a b i l i t y f r o m s u s c e p t i -
bilities d u e to v a l e n c e e l e c t r o n s ( V E ) , p h o n o n s ( P H ) a n d free
carriers ( F C ) .
2
1
2C û p
X-Drude = (17)
ω + ίωγ '
w h e r e ω is t h e p l a s m a f r e q u e n c y a n d γ r e p r e s e n t s t h e w i d t h o f t h e r e s o n a n c e .
ρ
M o r e e l a b o r a t e free-electron t h e o r i e s m a y b e r e q u i r e d for fully q u a n t i t a t i v e
a s s e s s m e n t s . It is s e e n that χ ϋ π ι ά ε c a nFC b e o b t a i n e d b y s e t t i n g c û l = 0 in t h e FC
e x p r e s s i o n for χ ^ ο Γ ε η ί ζ B e l o w ω , % ] becomes strongly negative while % 2
ρ
b e c o m e s s t r o n g l y p o s i t i v e , as a p p a r e n t f r o m F i g . 3. T h e l o c a t i o n o f c o d e p e n d s o n
p
t h e free e l e c t r o n d e n s i t y . F o r a m e t a l , c o is n o r m a l l y in t h e u lΡ tΗ
raviolet. For a
p F C
d o p e d s e m i c o n d u c t o r , ω c a n b e in t h e infrared. In a m e t a l , χ is u s u a l l y n o t
ρ
a p p a r e n t o w i n g to t h e d o m i n a t i n g i n f l u e n c e o f % . T h e l o w e s t p a r t o f F i g . 3
illustrates t h e e n s u i n g p e r f o r m a n c e o f ε for the c a s e o f a h e a v i l y d o p e d s e m i -
conductor.
T h e dielectric permeability o f m a n y metals, semiconductors and insulators have

b e e n d e r i v e d f r o m o p3t i 3
c3
a l4m e a s u r e m e n t s . E x t e n s i v e t a b u l a t i o n s c a n b e f o u n d in
d i f f e r e n t h a n d b o o k s ' , at l e a s t for t h e m o r e c o m m o n h o m o g e n e o u s m a t e r i a l s .
In t h e r e m a i n d e r o f this c h a p t e r w e will b e c o n c e r n e d w i t h m e t h o d s for o b t a i n i n g
the permeabilities o f i n h o m o g e n e o u s materials from the permeabilities of the
homogeneous constituents.
ΙΠ. R I G O R O U S B O U N D S AND EFFECTIVE M E D I U M THEORIES
I n this s e c t i o n w e c o n s i d e r t h e o p t i c a l p r o p e r t i e s o f i n h o m o g e n e o u s m a t e r i a l s in
t h e q u a s i s t a t i c a p p r o x i m a t i o n . T h i s is v a l i d w h e n t h e s i z e o f t h e i n h o m o g e n e i t i e s
o r p a r t i c2l e s is m u c h less t h a n t h e w a v e l e n g t h o f light, o r m o r e p r e c i s e l y w h e n
2 π ε ^ / α / λ « 1. H e r e α is the p a r t i c l e r a d i u s a n d ε™ d e n o t e s t h e l a r g e s t o f the
d i e l e c t r i c p e r m e a b i l i t i e s o f the m a t e r i a l s . In the q u a s i s t a t i c c a s e t h e o p t i c a l
p r o p e r t i e s o f the m a t e r i a l a r e u n i q u e l y d e s c r i b e d b y an effective d i e l e c t r i c
p e r m e a b i l i t y , ε. B e c a u s e t h e field is a l m o s t c o n s t a n t o v e r a p a r t i c l e , e l e c t r o s t a t i c
a r g u m e n t s c a n b e u s e d to d e r i v e ε. W e n o w p r e s e n t r i g o r o u s b o u n d s o n "ε that
h o l d w h e n different a m o u n t s o f s t r u c t u r a l i n f o r m a t i o n is k n o w n , as w e l l a s
effective m e d i u m t h e o r i e s that a r e fairly g o o d a p p r o x i m a t i o n s for m a n y p r a c t i c a l
c o m p o s i t e m a t e r i a l s . O u r d i s c u s s i o n is r e s t r i c t e d to t h r e e - d i m e n s i o n a l t w o -
component composites.
W e first c o n s i d e r t h e s i t u a t i o n w h e n o n l y the d i e l e c t r i c p e r m e a b i l i t i e s o f the t w o

p h a s e s , ε a a n d ερ, a r e k n o w n . T h e b o u n d s o n the d i e l e c t r i c p e r m e a b i l i t y in this
c a s e a r e g i v e n b y the e x t r e m a l m i c r o s t r u c t u r e s s h o w n in F i g . 4 . T h e y a r e l a y e r e d
s t r u c t u r e s o r i e n t e d in different d i r e c t i o n s w i t h r e s p e c t to t h e a p p l i e d e l e c t r i c field.
T h e v o l u m e fractions o f t h e t w o p h a s e s , f a a n d f , are d e f i n e d in F i g . 4. W h e n the
B
field is o r i e n t e d p a r a l l e l to t h e l a y e r s the s t r u c t u r e is e q u i v a l e n t , in a n e l e c t r o s t a t i c
p i c t u r e , to m a n y c a p a c i t o r s c o n n e c t e d in parallel. H e n c e w e o b t a i n for t h e effective
d i e l e c t r i c p e r m e a b i l i t y o f this s t r u c t u r e
(18)
MICROSTRUCTURES
WIENER BOUNDS
(b)
A VA VA VA VA ^ ^ ^ ^ \
E
I ^ Ρ ^ I | y / / / / / / / / / / / / / / / * *
A W ^ \ ^ \ À ' / / / / / / / / / / / / / / / , Κ
B d d A =
" V B V B
Fig. 4 . L a y e r e d m i c r o s t r u c t u r e s u s e d to d e r i v e t h e W i e n e r b o u n d s
o n t h e effective d i e l e c t r i c p e r m e a b i l i t y . T h e e l e c t r i c field is
d e n o t e d b y E.
S i m i l a r l y w h e n t h e field is o r i e n t e d p e r p e n d i c u l a r l y to the l a y e r s w e u s e t h e
f o r m u l a for c a p a c i t o r s c o n n e c t e d in series a n d o b t a i n
=
Ε
F F )
*B2 A Α + B *b ·
E q u a t i o n (18) c o r r e s p o n d s to n o s c r e e n i n g o f the field w h i l e E q . (19) c o r r e s p o n d s to

m a x i m u m s c r e e n i n g . T h e15r i g o r o u s b o u n d s o n ε d e s c r i b e d b y t h e s e e q u a t i o n s w e r e
first o b t a i n e d b y W i e n e r . I f ε A a n d ε a r e real E q s . (18) a n d (19) d e s c r i b e the
Β
b o u n d s o n ε w h e n ε Α , ε , f^ a n d fg are k n o w n .
Β
H o w e v e r w e a r e m a i n l y i n t e r e s t e d in the m o r e g e n e r a l c a s e o f c o m p l e x d i e l e c t r i c
p e r m e a b i l i t i e s . H e r e the b o u n d s c a n b e d e p i c t e d as lines in the c o m p l e x ëf-plane
enclosing the region of allowe1 37
d v5a l u e s o f ε. M e t h o d s for d e r i v i n g t h e s e b o u n d s
h a v e b e e n g i v e n b y B e r g m a n ' a n d Milton."18,36,37 bounds are obtained
from t h e a n a l y t i c a l p r o p e r t i e s o f ε as 38 a function o f t h e p e r m e a b i l i t i e s o f t h e1 36
7
c o m p o n e n t s as g i v e n b y B e r g m a n . Alternatively, variational p r i n c i p l e s ' can
a l s o b e u s e d . T h e W i e n e r b o u n d s , E q s . (18) a n d ( 1 9 ) , h o l d for t h e c a s e o f c o m p l e x ε",
i r r e s p e c t i v e o f m i c r o s t r u c t u r e . O n l y ε A a n d ε n e e d to b e k n o w n . A s fA a n d
Β
f5 = 1 - fA a r e v a r i e d E q . (18) traces o u t a straight l i n e b e t w e e n ε ^ a n d ε , w h i l e
Β
Eq. (19) b e c o m e s a c i r c u l a r arc j o i n i n g ε^ a n d εβ. A n e x a m p l e o f t h e s e b o u n d s is
g i v e n in F i g . 5.
N o w w e i n c o r p o r a t e g r a d u a l l y m o r e s t r u c t u r a l i n f o r m a t i o n in t h e b o u n d s o n t h e
effective d i e l e c t r i c p e r m e a b i l i t y . First the c a s e w h e n t h e v o l u m e f r a c t i o n s Î A a n d
ίβ a r e k n o w n in a d d i t i o1n 1to 38 ε6A -a n d1 ε is c o n s i d e r e d . It c a n b e s h o w n t h a t the
Β
b o u n d s take the f o r m '
ε 2Γ « 1 1 « 1 I 1
fA
=0.4 .
-ίο ο ίο ε1
Fig. 5. R i g o r o u s b o u n d s for t h e effective d i e l e c t r i c p e r m e a b i l i t y o f
a t w o - c o m p o n e n t c o m p o s i t e w i t h ε Α= - 8 + 10i a n d ε Β= 5.
T h e s e v a l u e s w e r e c h o s e n to o b t a i n a g o o d d i s p l a y o f t h e
features o f the b o u n d s . T h e lines j o i n i n g t h e p o i n t s ε Αa n d ε Β
denote the W i e n e r bounds ε Β ] and εΒ 2 · T h e lightly shaded area
is e n c l o s e d b y the b o u n d s for a n i s o t r o p i c c o m p o s i t e s , ε Β 3 and
ε*Β4· H e r e f A w a s set e q u a l to 0.4. T h e m e d i u m s h a d e d a r e a
is e n c l o s e d b y t h e b o u n d s for i s o t r o p i c c o m p o s i t e s , ε Β 5 and
εΒ6· F i n a l l y , t h e h e a v i l y s h a d e d a r e a is e n c l o s e d b y t h e fourth
o r d e r b o u n d s , w i t h t h e s t r u c t u r a l p a r a m e t e r χ e q u a l to 0 . 1 .
FA ^ B ( C A ' Β ) Ε , ΟΛ Π
εΒ 3 = Β + Ε 7T~( : <2°)
ε Β+ L f B( ε Α- ε Β )
and
^ΒΕΑ (Ε Β - ΑΕ >
εΒ 4 = Α Ε + 77~, : / <21
)
ε Α+ ί ί Α( ε Β- ε Α)
w h e r e L is a n effective d e p o l a r i s a t i o n factor that c a n v a r y b e t w e e n z e r o a n d u n i t y .
T h e b o u n d s o f E q s . (20) a n d ( 2 1 ) b e c o m e c i r c u l a r arcs in the ε p l a n e j o i n i n g ε Β( ί 1 Α)
and ε Β 2(ίA ) , as s e e n in Fig. 5. T h e e x t e n s i o n s o f t h e c i r c u l a r a r c s p a s s t h r o u g h t h e
p o i n t s ε Αa n d ε Β , r e s p e c t i v e l y . W h e n ε Αa n d ε Βa r e real E q s . ( 2 0 ) a n d ( 2 1 ) g i v e
b o u n d s for the real ε for t h e c a s e w h e n f A , f Ba n d L a r e k n o w n , as s h o w n first b y
H a s h i n a n d S h t r i k m a n . 16 T h e a r e a w i t h i n t h e b o u n d s c o r r e s p o n d s t o t h e effective
d i e l e c t r i c p e r m e a b i l i t i e s o f a n i s o t r o p i c c o m p o s i t e s . S u c h m a t e r i a l s h a v e in g e n e r a l
t h r e e p r i n c i p a l ë's r e l a t e d to t h e t h r e e p r i n c i p a l d i r e c t i o n s o f t h e s t r u c t u r e .
E v e n n a r r o w e r b o u n d s a r e o b t a i n e d for t h e c a s e o f i s o t3r5o p i c c o m p o s i3
t6
e s . F o r the
c a s e o f c o m p l e x ε t h e y w e r e first d e r i v e d b y B e r g m 13a n a n d M i l t o n . S u b s e -
q u e n t l y t h e b o u n d s w e r e r e f o r m u l a t e d b y A s p n e s in a c o n v e n i e n t w a y . I n this
c h a p t e r w e e m p l o y t h e latter f o r m u l a t i o n a n d w r i t e
ε =—τ : : ε . (22)
2e + f A^B + ^Β Α
h
Here is t h e d i e l e c t r i c p e r m e a b i l i t y for a n i m a g i n a r y m a t e r i a l in w h i c h the
p h a s e s A a n d Β a r e t a k e n to b e e m b e d d e d . It r e p r e s e n t s t h e p r o p e r t i e s o f t h e
average neighbourhood of inclusions of materials A and B. T h e Bergman-Milton
b o u n d s ε*Β5 a n d ε ^ a r e o b t a i n e d w h e n
e X 2 3
h = Â + (I-X)EB < )
and
1 1 1
eh' = « A " + (Ι-χ)εβ· , (24)
r e s p e c t i v e l y . H e r e χ is a s t r u c t u r a l p a r a m e t e r w h i c h c a n t a k e v a l u e s b e t w e e n z e r o
a n d u n i t y a n d is r e l a t e d to t h e p a i r a n d t h r e e - p o i n t c o r r e l a t i o n f u n c t i o n s o f t h e
m a t e r i a l . T h e e v a l u a t i o n o f this p a r a m e t e r is d i s c u s s e d in S e c . I V . W h e n χ is
varied, the b o u n d s ε 5 and ε £ form two circular arcs, w h i c h join the points
Β Β
r e p r e s e n t i n g ε 3 a n d ε 4 for L = 1 / 3 , as s h o w n in F i g . 5. T h e s e a r c s e n c l o s e the
εp o s s i b l e e'sa for nΒi s o t r o p iΒc c o m p o s i t e s . T h e e x17
t e n s i o n s o f the a r c s p a s s t h r o u g h
Βΐ(^Α) d ε 2 ( Î A ) / r e s p e c t i v e l y . B e r g m a n h a s s h o w n t h a t t h e b o u n d g i v e n b y
Β
E q s . (22) a n d ( 2 4 ) is n o t a t t a i n a b l e a n d c a n b e s o m e w h a t i m p r o v e d .
B y i n c o r p o r a t i n g m o r e s t r u c t u r a l i n f o r m a t i o n , i.e., h i g h e r - o r d e r c o r r e l a t i o n
f u n c t i o n s , i n t o t h e t h1
e8o r y a w h o l e h i e r a r c h y o f n a r r o3w3 e7
9r b o u n d s c a n b e o b t a i n e d ,
as s h o w n b y M i l t o n a n d M i l t o n a n d M c P h e d r a n . ' W e r e t u r n to this p o i n t in
S e c . I V w h e r e w e d i s c u s s b o u n d s for t h e c a s e w h e n t h e p a r a m e t e r χ is k n o w n .
R e c e n t l y t h e t h e o r y o f r i g o r o u s b o u n d s o n t h e4c o2 0m -p l e4x ε h a s a l s o b e e n a p p l i e d to
materials with m o r e than two c o m p o n e n t s .
In t h e r e s t o f this s e c t i o n w e w i l l c o n s i d e r v a r i o u s t h e o r i e s for t h e e f f e c t i v e
d i e l e c t r i c p e r m e a b i l i t y that h o l d in s p e c i a l c a s e s . T h e s e s o c a l l e d e f f e c t i v e m e d i u m
theories are c o m p a r e d to the bounds outlined above. W e n o w specify s o m e
e x p l i c i t m i c r o s t r u c t u r e s a n d c a r r y o u t c a l c u l a t i o n s o f t h e e f f e c t i v e ε. E v e n if strictly
v a l i d o n l y for o n e m i c r o s t r u c t u r e t h e s e effective m e d i u m e x p r e s s i o n s a r e often
g o o d a p p r o x i m a t i o n s for m a n y m a t e r i a l s e n c o u n t e r e d in p r a c t i s e . T h e m i c r o -
s t r u c t u r e is r e p r e s e n t e d w i t h R a n d o m U n i t C e l l ( R U C ) m o d e l s w h i c h a r e s i m p l e
e n o u g h to p e r m i t a t h e o r e t i c a l t r e a t m e n t a n d y e t d o n o t l e a v e o u t t h e e s s e n t i a l
p h y s i c s . F i g u r e 6 a , b s h o w s t w o c a s e s w h i c h a r e r e g a r d e d as typical: a s e p a r a t e d -
g r a i n s t r u c t u r e , w i t h p a r t i c l e s o f "A" e m b e d d e d in a c o n t i n u o u s h o s t o f " B " , a n d
a n a g g r e g a t e s t r u c t u r e in w h i c h "A" a n d " B " e n t e r o n a n e q u a l f o o t i n g to f o r m a
space-filling r a n d o m mixture.
MICROSTRUCTURES
Separated-grain structure Aggregate structure
I » Material "A"; filling factor fA

I I Material " Β " ; filling factor 1-fA
RANDOM UNIT CELLS

Maxwell Garnett theory Bruggeman theory
^ Ratio of volumes -Probability fAof being "A"

determines fA Probability 1-fAof
being "B"
Fig. 6. P a r t s (a) a n d (b) d e p i c t t w o m i c r o s t r u c t u r e s o f t w o - p h a s e
c o m p o s i t e m a t e r i a l s . Parts (c) a n d (d) s h o w t h e c o r r e s -
p o n d i n g R U C ' s u s e d to d e r i v e the M a x w e l l G a r n e t t a n d
B r u g g e m a n E M T ' s . T h e R U C ' s are e m b e d d e d in t h e
effective m e d i a . ( F r o m Ref. 7 ) .
74 5
3 - 4
RUC's are n o w d e f i n e d ' s o as to a c c o u n t for the m a j o r f e a t u r e s o f t h e
m i c r o s t r u c t u r e s . T h e R U C is t a k e n to b e e m b e d d e d in a n e f f e c t i v e m e d i u m ,
w h o s e p r o p e r t i e s a r e as y e t u n d e f i n e d . F o r the s e p a r a t e d g r a i n s t r u c t u r e , t h e R U C
is a c o r e o f "A" s u r r o u n d e d b y a c o n c e n t r i c shell o f " B " , as d e p i c t e d in F i g . 6 c . T h e
r a t i o o f the c o r e v o l u m e to t h e shell v o l u m e is e q u a l to f . F o r t h e a g g r e g a t e
A
s t r u c t u r e , t h e i n h e r e n t s t r u c t u r a l e q u i v a l e n c e o f t h e c o m p o n e n t s is e n s u r e d b y
l e t t i n g t h e R U C h a v e a p r o b a b i l i t y f o f b e i n g "A" a n d a p r o b a b i l i t y fg o f b e i n g " B " ,
A
as s h o w n in F i g . 6 d . T h e R U C is s p h e r i c a l or n o n s p h e r i c a l d e p e n d i n g o n the
s h a p e o f a "typical" p a r t i c l e .
T h e b a s i c definition o f a n effective m e d i u m is that t h e R U C , w h e n e m b e d d e d in

the e f f e c t i v e m e d i u m , s h o u l d n o t b e d e t e c t a b l e in an e x p e r i m e n t u s i n g e l e c t r o -
m a g n e t i c r a d i a t i o n c o n f i n e d to a specific w a v e l e n g t h r a n g e . I n o t h e r w o r d s , the
e x t i n c t i o n o f the R U C s h o u l d b e the s a m e as if it w e r e r e p l a c e d w i t h a m a t e r4i6a l
c h a r a c t e r i z e d b y ε. T h i s c r i t e r i o n m a k e s it fruitful to u s e a r e c e n t l y d e r i v e d
"optical t h e o r e m " for a b s o r b i n g m e d i a ; it r e l a t e s t h e e x t i n c t i o n o f t h e s p h e r i c a l cell

c o m p a r e d to that o f t h e s u r r o u n d i n g m e d i u m , C , w i t h t h e s c a t t e r i n g a m p l i t u d e
e x t
in t h e d i r e c t i o n o f t h e i m p i n g i n g b e a m , S ( 0 ) , b y
C
e t =x 4 W
Re[S(0)/k^l , (25)
where
1
^ = 2πε /2/χ (26)
d e n o t e s t h e w a v e v e c t o r a m p l i t u d e 47in t h e e f f e c t i v e m e d i u m . E q u a t i o n ( 2 5 ) is s e e n
to b e a g e n e r a l i z a t i o n o f t h e u s u a l o p t i c a l t h e o r e m for n o n a b s o r b i n g m e d i a , b u t
in t h e p r e s e n t c a s e C
e t cxa n b e e i t h e r p o s i t i v e or n e g a t i v e . F r o m t h e definition o f
a n effective m e d i u m it n o w f o l l o w s that C = 0, i.e.,
et x
S(0) = 0 , (27)
w h i c h e x p r e s s e s t h e f u n d a m e n t a l 4p 4
r8
9o p e r t y o f an effective m e d i u m . This con-
dition has been proposed e a r l i e r ' in s o m e w h a t different c o n t e x t s .
T h e c o n d i t i o n o f E q . (27) is v e r y c o n v e n i e n t b e c a u s e S ( 4 0 ) 5c7
0a n e a s i l y b e o b t a i n e d for
spheres and coated spheres by the Lorenz-Mie t h e o r y . ' Below w e mainly de-
r i v e e f f e c t i v e m e d i u m t h e o r i e s w h e r e the R U C ' s h a v e a s p h e r i c a l g e o m e t r y , b u t
w e also c o m 4 m57
0e n t o n s o m e r e s u l t s for e l l i p s o i d s . F r o m L o r e n z - M i e t h e o r y S ( 0 ) c a n
be w r i t t e n ' a s a n e x p a n s i o n in e l e c t r i c a n d m a g n e t i c m u l t i p o l e s , o r a l t e r n a -
tively as a series e x p a n s i o n in ( k b ) w h e r e b is the R U C r a d i u s .
e 51
T h e M a x w e l l G a r n e t t ( M G ) t h e o r y c o r r e s p o n d s to t h e R U C50in F i g . 6 c . H e n c e w e
u s e t h e series a p p r o p r i a t e to a c o a t e d s p h e r e (cs) a n d o b t a i n
Β 5
„ (ε« - ε) ( ε + 2 ε ) + f Λ
( 2 ε + ε) ( ε - ε )
SCS(0) i(k b)3, Α Β Β Α Β
= e ( ε + 2ε) ( ε + 2 *ε ) + *f ( 2 ε - 2ε) (*ε - \ε ) + 0 [ ( k eb ) ] . (28)
Β Α Β Α Β Α Β
T h e filling factor is
3
a )
*A = b 3 ,
w h e r e a ( b ) is t h e r a d i u s o f t h e i n n e r (outer) s p h e r e in F i g . 6 c . I n t h e s m a l l s p h e r e
M Gb y setting t h e l e a d i n g t e r m
limit, t h e e f f e c t i v e m e d i u m c o n d i t i o n c a n b e satisfied
in E q . ( 2 8 ) e q u a l to z e r o . T h i s yields (with ε = ë )
^ - e Α
B. =f_ e ^ A )
gMG 2e ε + 2ε
+B Α Β
or, rewritten,
£?MG ε
= εΑ+ Β
2ε + 2£ (ε -ε )
Β Α Α Β )
ε + 2ε -ί (ε -ε )
Α Β Α Α Β
E q u a t i o n ( 3 0 ) o r ( 3 1 ) is t h e c o n s t i t u t i v e f o r m u l a for t h e M a x w e l l G a r n e t t E M T . B y
m a k i n g t h e r e p l a c e m e n t s A - > Β a n d Β - » A o n e o b t a i n s a n a l o g o u s r e l a t i o n s for
t h e i n v e r t e d s t r u c t u r e . O u r d e r i v a t i o n d o e s n o t r e q u i r e that f b e s m a l l .
A
H o w e v e r , it is c l e a r that for a sufficiently l a r g e filling factor o n e r e a c h e s a p o i n t
w h e r e the detailed particle-particle interactions must b e considered explicitly.
O b v i o u s l y , s u c h s t r u c t u r a l m u l t i p o l e f e a t u r e s can n o t b e e n c o m p a s s e d b y t h e M G
a p p r o a c h , a n d s u p p l e m e n t a r y i n f o r m a t i o n is r e q u i r e d . T o s h e d s o m e l i g h5 t2o n this
5 5
3 - 5
i s s u e , w e n o t e t h a t t h e M a x w e l l G a r n e t t t h e o r y is in a c c e p t a b l e a g r e e m e n t with
the r e c e n t l y d e r i v e d e x a c t t h e o r i e s for c u b i c a r r a n g e m e n t s o f i d e n t i c a l s p h e r e s
as l o n g as f < 0.4. F o r a p e r i o d i c a r r a n g e m e n t s - s u c h as t h o s e n o4r4m a l l y o c c u r r i n g
A
in e x p e r i m e n t a l s a m p l e s - t h e s t r u c t u r a l m u l t i p o l e s a r e e x p e c t e d to set in at
l o w e r filling factors s i n c e c l o s e a p p r o a c h a m o n g s t t h e s p h e r e s is p e r m i t t e d .
It s h o u l d b e n o t e d that t h e t w o M G e x p r e s s i o n s ( E q . 31 w i t h a n d w i t h o u t t h e
r e p l a c e m e n t s A <-» B ) a r e e q u i v a l e n t to the B e r g m a n - M i l t o n b o u n d s , E q s . ( 2 2 ) - ( 2 4 ) ,
w h e n χ = 0 a n d χ = 1, r e s p e c t i v e l y . T h e M G e x p r e s s i o n s a r e s i t u a t e d o n t h e p o i n t s
in t h e ε-plane w h e r e t h e t w o b o u n d s for i s o t r o p i c c o m p o s i t e s c r o s s ( s e e a l s o F i g . 8 ) .
T h e M a x w e l l G a r n e t t t h e o r y c a n a l s o b e e x t e n d e d to t h e c a s e o f e l l i p s o i d a l R U C s .
T h i s is n o t trivial, as d i s c u s s e d in Refs. 7 a n d 1 4 , b u t d e p e n d s o n t h e s h a p e o f t h e
s h e l l in t h e R U C . W h e n t h e shell in the R U C h a s t h e s a m e d e p o l a r i s a t i o n f a c t o r ,
L , as t h e i n n e r p a r t i c l e a s i m p l e r e s u l t is o b t a i n e d , n a m e l y the b o u n d s ε 3 a n d ε 4
Β Β
g i v e n b y E q s . (20) a n d (21). H e n c e t h e s e b o u n d s a r e a t t a i n e d b y a g e o m e t r y
c o n s i s t i n g o f a l i g n e d e l l i p s o i d s . F o r r a n d o m l y o r i e n t e d e l l i p s o i d s o n e h a s to
a v e r a g e o v e r t h e t h r e e p r i n c i p a l a x e s ; the r e s u l t for ε m u s t t h e n b e w i t h i n t h e
b o u n d s for i s o t r o p i c c o m p o s i t e s .
56
T h e B r u g g e m a n t h e o r y is d e r i v e d from4 57
0the R U C in F i g . 6 d . W e u s e t h e series
e x p a n s i o n for a s p h e r e (s) a n d o b t a i n '
3 5
S s (0) = i ( k b ) -^—z + Ο [ ( k b ) ] , (32)
e ε + 2ε c
w h e r e b is t h e r a d i u s o f t h e R U C in F i g . 6 d a n d ε d e n o t e s Β
ε Γ
Αor ε Β. C o n s i d e r i n g
a g a i n t h e s m a l l s p h e r e l i m i t , it is f o u n d that ( w i t h ε = ε )
ΒΓ ΒΓ
f
Α- ε ΒΓ
ε ε - ε ΒΓ
Β
Aε + 2-εRr + ( l - f A) ε +0„2-εRr = 0, (33)
Α Β
w h e r e w e h a v e i n v o k e d t h e p r o b a b i l i t y f for the R U C o f h a v i n g ε = ε a n d t h e
A Α
p r o b a b i l i t y f o f h a v i n g ε = ε . E q u a t i o n ( 3 3 ) is t h e c o n s t i t u t i v e f o r m u l a for t h e
B Β
B r u g g e m a n t h e o r y . F o r h i g h f ' s , the s t r u c t u r a l m u l t i p o l e effects a r e e x p e c t e d to
A
e n t e r as for the M a x w e l l G a r n e t t t h e o r y , b u t n o d e t a i l e d s t u d y h a s y e t a p p e a r e d .
N o t e that E q . ( 3 3 ) is s y m m e t r i c a l w i t h r e s p e c t to e x c h a n g e o f t h e c o m p o n e n t s o f
the material.
T w o o t h e r E5 M7 T ' s c a n b e d e r i v e d f r o m R U C5 a56 8r g u m e n t s . T h e s e a r e t h e t h e o r i e s o f
P i n g S h e n g ( P S ) a n d B r u g g e m a n - H a n a i ' ( B H ) . T h e f o r m e r is a c o m p o s i t i o -
n a l l y s y m m e t r i z e d f o r m o f t h e M a x w e l l G a r n e t t t h e o r y . T h e R U C , d e p i c t e d in F i g .
7 a , is a c o a t e d s p h e r e w h o s e c o r e a n d shell c a n b e e i t h57 e r "A" o r " B " . T h e r e l a t i v e
o c c u r r e n c e o f t h e t w o v a r i e t i e s o f R U C is d e t e r m i n e d b y c o u n t i n g t h e n u m b e r o f
e q u a l l y p o s s i b l e c o n f i g u r a t i o n s c o r r e s p o n d i n g to different p o s i t i o n s o f t h e i n n e r
s p h e r e in t h e R U C . W h e n "A" is t h e c o r e a n d " B " is t h e s h e l l , this n u m b e r is
V= ( ll - f AV 3 ) 3 . (34)
For the opposite situation w e obtain
v
2= (l-(l-f )V3)3 .
A (35)
T h i s a r g u m e n t r e q u i r e s that t h e i n n e r s p h e r e o f t h e R U C b e p l a c e d e c c e n t r i c a l l y .
W e approximate the e n s e m b l e o f various eccentric structures b y R U C ' s being
c o n c e n t r i c c o a t e d s p h e r e s . T a k i n g tc
h e ss m a l l s p h e r e l i m i t o f E q . ( 2 8 ) for P
e a cS
h of the
t w o v a r i e t i e s o f R U C a n d s e t t i n g I S ( 0 ) = 0 , it is f o u n d that ( w i t h ε ξ ë )
Vl (ε
Β- gPS) ( ε Α+ 2 ε Β) + f Α( 2 ε Β+ ε™) ( ε Α- ε Β) +
( ε + 2èTS) ( ε + 2 ε ) 4- 2 f ( ε - &S) ( ε - ε )
Β Α Β A Β Α Β
p
+ V
(ε - ë ρ
Α S ) ( ε Β+ 2 ε Α) + (1 - f Α) ( 2 ε Α+ ε ^Ρ) ( δε Β- ε Α)
* ( ε + 2 ε 5 ) ( ε + 2 ε ) + 2 (1 - f ) ( ε - ε ) ( ε - ε ) '
Α Β Α Α Α Β Α
E q u a t i o n ( 3 6 ) a p p r o a c h e s t h e M a x w e l l G a r n e t t r e s u l t s w h e n f is c l o s57 e to zero o r
A
u n i t y . It s h o u l d b e r e m a r k e d that P i n g S h e n g m a d e his d e r i v a t i o n s for t h e m o r e
g e n e r a l c a s e o f s p h e r o i d a l p a r t i c l e s ; w e h a v e c h o s e n to g i v e h e r e t h e m o r e t r a c t a b l e
f o r m u l a a p p r o p r i a t e to s p h e r i c a l p a r t i c l e s .
RANDOM UNIT CELLS

Ping Sheng theory Bruggeman-Hanai theory
33
^Probability ( l - f / ) o f - Ratio of volumes gives
being "A"with shell of/ "B". 33 f * A f / ( l - f A) .
Probability ( l - ( 1 - f AV ) o f
being "B"with shell of "A".
Ratio of volumes gives f A
.
Fig. 7. P a r t s (a) a n d (b) s h o w the R U C ' s u s e d to d e r i v e t h e P i n g
Sheng and Bruggeman-Hanai EMT's. (From Ref. 7 ) .
T h e B r u g g e m a n - H a n a i t h e o r y c a n b e o b t a i n e d f r o m t h e R U C in F i g . 7 b . It c o n s i s t s
o fΒΗ
a s p h e r i c a l c o r e o f "A" s u r r o u n d e d b y a shell w h o s e d i e l e c t r i c p e r m e a b i l i t y is
ε m i n u s t h e c o n t r i b u t i o n Δε f r o m t h e c o r e itself. T h i s is an i n t e r m e d i a t e
situation b e t w e e n those o f the M a x w e l l Garnett and B r u g g e m a n theories.
R e w r i t i n g E q . ( 2 8 ) w i t h tΒ
h e nΗo t a t i o n o f F i g . 7 b a n d t a k i n g t h e s m a l l s p h e r e limit, it
is f o u n d that ( w i t h ε = ε )
ΒΗ ΒΗ ΒΗ
- Δε ( ε + 2ε - 2Δε) + f ( 3 ε - 2Δε) ( ε - ε + Δε) = 0 , (37)
Α Α
w h e r e f is the r a t i o o f t h e M
v o l u m e o f the i n n e r s p h e r e to that o f t h e o u t e r s p h e r e .
T h e v o l u m e fraction o f " A in t h e R U C is f , a n d t h e v o l u m e f r a c t i o n in t h e shell
A
is f - Ai. T h i s yields
A
f-A£/(l-f ) . (38)
A
14
It is n o w s t r a i g h t f o r w a r d to p r o v e that
ΒΗ ΒΗ
ε a -ε ε ι/3
ε
— ε =(l-f M ) . (39)
A
Α " Β ε
Β
A f o r m u l a for t h e i n v e r t e d s t r u c t u r e is o b t a i n e5
d6 b y t h e r e p l a c e m e n t s A <-» B .
E q u a t i o58 56
n ( 3 9 ) w a s first d9
0e r i v e d b y B r u g g e m a n a n d h a s s i n c e b e e n s t u d i e d b y
H a n a i and o t h e r s . ' T h e t h e o r y is s o m e t i m e s c a l l e d t h e u n s y m m e t r i c a l
Bruggeman theory.
T h e o r i e s w h i c h c a n b e d e r i v e d f r o m s p h e r i c a l R U C s c o r r e s p o n d to i s o t r o p i c
s t r u c t u r e s a n d s h o u l d t h u s fall w i t h i n the B e r g m a n - M i l t o n b o u n d s ε 5 a n d ε . In
Β Β 6
Fig. 8 w e s h o w t h e s e b o u n d s in a s p e c i a l c a s e t o g e t h e r w i t h r e s u l t s f r o m t h e
effective m e d i u m t h e o r i e s d e s c r i b e d a b o v e . It is s e e n t h a t all t h e t h e o r e t i c a l
r e s u l t s fall i n s i d e t h e b o u n d s , w i t h t h e e x c e p t i o n o f the M G r e s u l t s w h i c h fall o n
t h e b o u n d s as n o t e d a b o v e .
Effective m e d i u m t h e o r i e s w h i c h a r e d e r i v e d from e l l i p s o i d a l u n i t cells c o r r e s -

p o n d i n g e n e r a l t o a n i s o t r o p i c s t r u c t u r e s a n d s h o u l d fall w i t h i n t h e w i d e r b o u n d s
ε 3 a n d ε ^ . O n l y if a c o m p l e t e l y r a n d o m o r i e n t a t i o n o f t h e e l l i p s o i d s in t h e
Β
m a t e r i a l is a s s u m e d w i l l t h e e f f e c t i v e d i e l e c t r i c p e r m e a b i l i t y fall w i t h i n t h e
B e r g m a n - M i l t o n b o u n d s for i s o t r o p i c s t r u c t u r e s .
T h e effective m e d i u m t h e o r i e s d e s c r i b e d in this s e c t i o n a r e often in fairly g o o d

agreement with measurements on metal-insulator composite coatings. However,
t h e e x p e r i m e n t a l d a t a s h o w different b e h a v i o u r d e p e n d i n g o n t h e m i c r o s t r u c t u r e
o f t h e c o a t i n g s . O n e t y p e o f c o m p o s i t e c o n s i s t s o f m e t a l p a r t i c l e s in a n a m o r p h o u s
i n s u l a t o r m a t r i x . H e r e t h e M a x w e l l G a r n e t t t h e o r y is u s u a l l y in g o o d a g r e e m e n t
w i t h t h e e x p e r i m e n t a l ε for l o w filling factors. T h i s is e x p e c t e d s i n c e t h e c o m p o -
site h a s a s e p a r a t e d - g r a i n structure. H o w e v e r , for f > 0.2 to 0.3 d i s c r e p a n c i e s start
to a p p e a r . A s n o t e d a b o v e , at s u c h h i g h filling factors t h e M G t h e o r y is p r o b a b l y
i n a d e q u a t e for d e s c r i b i n g t h e m u l t i p o l a r i n t e r a c t i o n s b e t w e e n t h e p a r t i c l e s . T h i s
t y p e o f c o m p o s i t e (the " M G type") i n c l u d e s C0-AI2O3 (Ref. 7 ) , AU-AI2O3 (Refs. 6 1 ,
6 2 ) , N i - A l 0 (Ref. 6 ) , N i - S i 0 a n d N i - M g O (Ref. 6 3 ) as w e l l as m e t a l - p o l y m e r
23 2
c o m p o s i t e s (Refs. 6 4 , 6 5 ) , a n d p r o b a b l y A g - S i 0 a n d A u - S i 0 (Ref. 6 6 ) . T h e
2 2
d e s c r i p t i o n o f t h e o p t i c a l p r o p e r t i e s o f " M G type" c o m p o s i t e s at h i g h filling factors
5 6 7 62 64
5
is a c o m p l i c a t e d p r o b l e m , a l t h o u g h in s o m e c a s e s t h e P i n g S h e n g t h e o r y w o r k s
remarkably w e l l . ' ' ' W e t a k e a different a p p r o a c h to this p r o b l e m in S e c . I V
below.
I • I ' I ι I
*2
MG
10
-
/ ·ΒΗ Λ
6
I BR J 9
V BH #
MG
2
I ι I ι I ι I
o 2 4 6 ε1
Fig. 8. B e r g m a n - M i l t o n b o u n d s for the e f f e c t i v e d i e l e c t r i c p e r m e a -

bility o f an i s o t r o p i c t w o - c o m p o n e n t c o m p o s i t e w i t h f = 0.4,
A
ε = - 8 + 10i a n d ε = 5. T h e s e v a l u e s w e r e a l s o u s e d in F i g . 5.
Α Β
T h e r e s u l t s o f the M a x w e l l G a r n e t t ( M G ) , B r u g g e m a n ( B r ) ,
Bruggeman-Hanai (BH) and Ping S h e n g (PS) theories are
indicated.
Another type of composite consists of a mixture of metal and crystalline insulator

g r a i n s . T h i s s t r u c t u r e is s i m i l a r to t h e a g g r e g a t e m o d e l in F i g . 6 b , s o w e call it t h e
"Br t y p e " c o m p o s i t e s t r u c t u r e . I n d e e d , the o p t i c a l p r o p e r t i e s c a n b e w e l l d e s c r i b e d
b y t h e B r u g g e m a n t h e o r y u p to q u i t e h i g h (f ~ 0.3 to 0.4) filling factors. E x a m p l e s
o f "Br t y p e " c o m p o s i t e s a r e A u - M g O (Refs. 6, 6 1 , 6 7 - 6 9 ) a n d A g - M =g O . T h e B r u g g e -
m a n theory predicts a metal-insulator transition w h e n f t a l 1 / 3 / b u t in e x p e r i -
m e
m e n t s t h e t r a n s i t i o n is often o b s e r v e d at h i g h e r filling factors. A p h e n o m e n o -
l o g i c a l e x t e n s i o n o f t h e B r u g g e m a n t h e o r y for t h e d e s c r i p t i o n o f t h e o p t i c a l
p r o7p0e r t i e s n e a r the m e t a l - i n s u l a t o r t r a n s i t i o n h a s b e e n w o r k e d o u7 t1b y B e r t h i e r et
al. T h i s t h e o r y , as w e l l as a r e n o r m a l i z a t i o n g r o u p c a l c u l a t i o n , s h o w t h e
qualitative features seen in experiments.
T o s u m u p , in this s e c t i o n w e h a v e g r a d u a l l y i n c o r p o r a t e d m o r e a n d m o r e
structural information into the derivation of rigorous b o u n d s on ε and effective
m e d i u m theories. T h e Wiener bounds, ε ] and ε , which are valid w h e n only
Β Β 2
the d i e l e c t r i c p e r m e a b i l i t y o f the c o n s t i t u e n t s a r e k n o w n , a r e a t t a i n e d for l a y e r
s t r u c t u r e s . T h e s e e x p r e s s i o n s h a v e r e c e n t l y b e7 e2n f o u n d v e r y useful for d e s c r i b i n g
the o p t i c a l p r o p e r t i e s o f l a y e r e d s u p e r l a t t i c e s . W h e n t h e filling factors o f t h e t w o
c o m p o n e n t s a r e a l s o k n o w n w e o b t a i n t h e w i d e r b o u n d s 8 5 3 a n d 6734 w h i c h h o l d
for a n i s o t r o p i c c o m p o s i t e s . T h e y a r e a t t a i n e d b y the M a x w e l l G a r n e t t t h e o r y for
oriented ellipsoids. For isotropic composites the Bergman-Milton b o u n d s £ 5 5 and
a r e f o u n d . T h e t w o p o i n t s w h e r e the b o u n d a r y circles i n t e r s e c t c o r r e s p o n d to
t h e M a x w e l l G a r n e t t t h e o r y for 17 s p h e r e s . T h e b o u n d £ 5 5 is a t t a i n e d b y c o m p o s i t e s
w h e r e b o t h p h a s e1 s7 p e r c o l a t e as s e e n from E q . ( 2 3 ) , w h i l e ε ^ c a n n o t b e a t t a i n e d b y
real c o m p o s i t e s .
In the next section w e will incorporate additional structural information into the
d e r i v a t i o n o f r i g o r o u s b o u n d s a n d effective m e d i u m t h e o r i e s b y u s e o f a s t r u c t u r a l
p a r a m e t e r r e l a t e d to t h e p a i r a n d t h r e e - p o i n t c o r r e l a t i o n f u n c t i o n s o f t h e m a t e r i a l .
IV. EFFECTS OF PAIR AND THREE-POINT CORRELATION

FUNCTIONS
T h e s t r u c t u r e o f a c o m p o s i t e m a t e r i a l c a n b e c o m p l e t e l y s p e c i f i e d b y v a r i o u s n-
p o i n t c o r r e l a t i o n functions. R 73e c e n t l y a v e r y g e n e r a l a p74p r o a c h to this p r o b l e m h a s
been published by T o r q u a t o and Torquato and S t e l l . T h e y define general
c o r r e l a t i o n f u n c t i o n s a n d s h o w h o w different d e s c r i p t i o n s a r e r e l a t e d to o n e
a n o t h e r . I n this s e c t i o n w e will o n l y c o n s i d e r t h e c o r r e l a t i o n f u n c t i o n s o f the
l o w e s t o r d e r s , n a m e l y t h e pair a n d t h r e e - p o i n t c o r r e l a t i o n f u n c t i o n s o f p a r t i c l e s
d i s p e r s e d in a m a t r i x . T h i s g e o m e t r y is s i m i l a r to the s e p a r a t e d - g r a i n s t r u c t u r e in
F i g . 6 a . W e a l s o briefly r e v i e w c o r r e l a t i o n effects in the c l a s s o f cell m a t e r i a l s ,
w h i c h c o r r e s p o n d s to t h e a g g r e g a t e s t r u c t u r e in Fig. 6 b . F r o m t h e c o r r e l a t i o n
f u n c t i o n s m o r e n a r r o w b o u n d s o n ε than t h o s e c o n s i d e r e d in S e c . I l l c a n b e
o b t a i n e d . S o m e n o v e l effective m e d i u m t h e o r i e s w h i c h t a k e i n t o a c c o u n t
information on the pair and three-point correlation functions are also described.
W e first c o n s i d e r a s t r u c t u r e c o n s i s t i n g o f s p h e r e s d i s p e r s e d in a c o n t i n u o u s
m a t r i x . I n o r d e r to o b t a i n m o r e r e s t r i c t i v e b o u n d s t h a n t h e B e r g m a n - M i l t o n
b o u n d s for i s o t r o p i c c o m p o s i t e s , w e m u s t e v a l u a t e t h e p a r a m e t e r χ w h i c h a p p e a r s
in E q s . ( 2 3 ) a n d ( 2 4 ) . T h e r e s u l t i n g b o u n d s w e d e n o t e the f o u r t h - o r d e r b o u n d s .
A n e x a m p l e o f t h e s e b o u n d s for χ = 0.1 is g i v e n b y the 75 d a r k e s t a r e a in F i g . 5. T h e
fourth-order b o u n d s w e r e first d e s c r i b e d b y B e r a n .
T h e structural parameter χ = x X3 is r e l a t e d to t h e p a i r c o r r e l a t i o n f u n c t i o n 2
, g74
6( r ) ,
2+ 2
a n d t h e t h r e e - p o i n t c o r r e l a t i o n function, g 3 ( r , r , r
1 21 32 ) ,3b y the e x p r e s s i o n s '
0 2 +1 0
X2 /+ dr
3f =1
-
A Σ « » J S2 ( D ^ ï 2 a '
= 27WÔ -
/ 2a
2 46 7
w h e r e a is t h e p a r t i c l e r a d i u s . Furthermore '
2 0 0
χ 9f
A
3 =
3 2 . f(Aπ) 1Σ
2 W + 1) J J d r
12 d r 23 [ g 3( r 1, r21 / r32 ) 3-
P f 4 1
fl2/+2
- g2 frl2> g2 (Γ23) 1 / + l < 21 · Î23)
Γ +ΐ 2/Γ+2 2/ 3
/ 2 < >
where r
mn a n d r mn a r e v e c t o r d i s t a n c e s b e t w e e n p a r t i c l e s m a n d η a n d unit v e c t o r s
in d i r e c t i o n m to n, r e s p e c t i v e l y . T h e t h r e e - p o i n t c o r r e l a t i o n f u n c t i o n is d e n o t e d
b y g , P / i are Legendre polynomials, and r
3 + mn a r e t h e a b s o l u t e v a l u e s o f t h e
p a r t i c l e - p a r t i c l e d i s t a n c e s . N o t e that Refs. 2 4 a n d 7 6 u s e a p a r a m e t e r Κ w h i c h is
r e l a t e d to χ b y Κ = 2 f ( l - f ) x / 9 .
A A
T h e p a r a m e t e r χ h a s b e e n e v a l u a t e d for s o m e77s i m p l e m o d e l s t r u c t u r e s . A
p a r t i c u l a r l y 7s i7
m78p l e c a s e is a fractal s t r u c t u r e w h e r e t h e p a i r c o r r e l a t i o n function
is g i v e n b y '
' (ξ/rp-D 2α<τ<ξ

g W= « (42)
2
. 1 Γ>ξ.
H e r e D is t h e fractal d i m e n s i o n a n d ξ is the c o r r e l a t i o n l e n g t h o f t h e s t r u c t u r e .
T h e c o r r e l a t i o n l e n g t h signifies t h e u p p e r cutoff a n d 2a t h e l o w e r cutoff to t h e
r a n g e o v e r w h i c h t h e s t r u c t u r e is fractal. T h e filling factor o f t h e s t r u c t u r e is
r e l a t e d to t h e u p p e r a n d l o w e r cutoffs b y
a λ-D
f = L*(~) , (43)
where L 77* is a m e a s u r e o f t h e "holes" in t h e s t r u c t u r e a n d r e l a t e d to t h e l a c u -

narity. It c a n t a k e v a l u e s b e t w e e n z e r o a n d 7 9
unity. A similar relation has been
u s e d to d e t e r m i n e t h e p o r o s i t y o f s a n d s t o n e s . W h e n the particles are touching,
t h e p a r a m e t e r L * is e q u a l to unity. It will b e s e e n that this c a s e g i v e s t h e h i g h e s t
v a l u e o f x.
W e first c o n s i d e r t h e i n t e g r a l o v e r the p a i r c o r r e l a t i o n f u n c t i o n , x . Inserting

2
E q . ( 4 2 ) in E q . ( 4 0 ) , o n e c a n i m m e d i a t e l y e v a l u a t e the i n t e g r a l to o b t a i n
3 D
x 3f ^ /(/ + !) J}{L " _
2 " 2 (1-0 ^ (2/ - D + 4 ) 22/+1 2a ~
0 0
3L* / ( / + 1)
' 2 ( l - f ) fΣf | (/ ο2ι/ -_ D
η +, 4 ) \2Λ2/-D
ο2/ Π ++ 44 / (44)
w h e r e w e h a v e u s e d E q . ( 4 3 ) . T h e v a l u e o f x is o n l y w e a k l y d e p e n d e n t o n f for
2
f < 0.1.
T h e p a r a m e t e r X 3 h a s to b7 e6e v a l u a t e d n u m e r i c a l l y . W e e v a l u a t e d E q . ( 4 1 ) u s i n g
the method of F e l d e r h o f . T h e c a l c u l a t i o n w a s p e r f o r m e d for a m o d e l t h r e2e3-
p o i n t c o r r e l a t i o n f u n c t i o n v a l i d for at l e a s t s o m e fractal s t r u c t u r e s , n a m e l y
r r
g3 ( l2> r i 3 , r ) - g2 fri ) g2 ( 23) =
22 3 23 3 3
= 2.5 + ξ 6 - ^ [ ( r r )D" + ( r r )D~ - ( r r )I> ] /2. (45)
23 1 3 13 1 2 12 2 3
In F i g . 9 , x a n d X 3 a r e d e p i c t e d as a function o f fractal d i m e n s i o n w h e n L * = 1 a n d
2
t h e filling factor g o e s t o z e r o . It is s e e n that t h e effect o f t h r e e - p o i n t c o r r e l a t i o n s is
s m a l l for D < 2 , b u t it b e c o m e s m o r e i m p o r t a n t for h i g h e r fractal d i m e n s i o n s .
P h y s i c a l l y it is e x p e c t e d that χ s h o u l d i n c r e a s e t o w a r d s u n i t y as D c o m e s c l o s e to
three. It s h o u l d b e n o t e d that q u i t e different m e a n - f i e l8 d0 a p p r o a c h e s to t h e o p t i c a l
p r o p e r t i e s o f fractal c l u s t e r s h a v e also b e e n p r o p o s e d .
τ r
£0.15- / -
io.i - 2 y j .
x
0.05- /
FRACTAL DIMENSION
Fig. 9. S t r u c t u r a l p a r a m e t e r s x a n d X 3 as a function o f fractal
2
d i m e n s i o n in the l i m i t o f l o w filling factor. T h e c a l c u l a t i o n s
w e r e p e r f o r m e d for fractal s t r u c t u r e s w i t h L * = 1.
Recently the information available on χ has increased substantially and accurate

c o m p u t a t i o n s h a v e b e e n p e r f o r m e d for r a n d o m d i s t r i b u t i o n s o f s p h e r e s d i s p e r s2e6d
in a m a t r i x . T h e c a s e o f i m p e24 netrable or hard spheres was treated b y F e l d e r h o f
and by Torquato and L a d o . I m p r o v e d v a l u e s25
o f χ as a function o f filling factor
w e r e later c o m p u t e d b y B e a s l e y a n d T o r q u a t o . Another simple model considers
r a n d o m d i s t r i b u t i o n s o f s p h e r e s that a r e a l l o w e d to p e n2e t8r7
1a t e o n e a n o t h e r . In this
case values of χ were computed by Torquato and S t e l l . '
T h e c a s e o f s p h e r e s w2i t8 h7
2 an a r b i t r a r y d e g r e e o f p e n e t r a b i l i t y h a s a l s o b e e n
thoroughly s t u d i e d . ' For example one m a y consider spheres with a hard core
a n d a p e n e t r a b l e shell. T h e s p h e r e s a r e t a k e n to b e r a n d o m l y d i s t r i b u t e d b u t
s u b j e c t to t h e c o n d i t i o n t h a t t h e y m a y n o t p e n e t r a t e e a c h o t h e r s ' c o r e s . T h e
penetrable sphere model (PSM) and impenetrable sphere model (ISM) are
o b t a i n e d in t h e l i m i t s o f n o c o r e a n d n o s h e l l , r e s p e c t i v e l y . T h e I S M c a n b e
c o n s i d e r e d as a g e n e r a l i z a t i o n o f the M a x w e l l G a r n e t t t h e o r y in o r d e r t o i n c l u d e
p a i r a n d t h r e e - p o i n t c o r r e l a t i o n effects. T h e P S M , o n t h e o t h e r h a n d , c o r r e s p o n d s
to a q u i t e different g e o m e t r y in t h a t a h i g h e r c o n n e c t i v i t y b e t w e e n t h e p a r t i c l e s is
o b t a i n e d . It m a y b e a v i a b l e m o d e l for s i n t e r e d or p a r t i a l l y s i n t e r e d c o m p o s i t e s .
T h e c o m p u t a t i o n o f s t r u c t u r a l p a r a m e t e r s o f r a n d o m d i s t r i b u t i o n s o f s p h e r e s is
rather involved and a 2 d e2t5a8i7
1l e d e x p o s i t i o n falls o u t s i d e t h e s c o p e o f this c h a p t e r . I n
Fig. 10 l i t e r a t u r e d a t a ' ' o n t h e s t r u c t u r a l p a r a m e t e r χ is s h o w n a s a function o f
filling factor for t h e I S M a n d P S M m o d e l s . A s e x p e c t e d t h e P S M s h o w s a g r e a t e r
departure from the M a x w e l l Garnett theory ( x = 0 ) than the I S M .
. ι ι r - y
0 8
- S C M / -
Ρ0.6- / A
s / /
g 0.4 - / PSM _
X0.2- / y '
0.2 0.4 0.6 0.8
FILLING F A C T O R
Fig. 1 0 . S t r u c t u r a l p a r a m e t e r χ as a function o f filling f a c t o r for
s p h e r i c a l cell m a t e r i a l s ( S C M ) as w e l l as for d i s p e r s i o n s o f
p e n e t r a b l e s p h e r e s ( P S M ) (Refs. 2 7 , 8 1 ) a n d i m p e n e t r a b l e
s p h e r e s ( I S M ) (Ref. 2 5 ) .
S o far w e h a v e o n l y t r e a t e d g e n e r a l i z a t i o n s o f t h e s e p a r a t e d - g r a i n s t r u c t u r e
d e p i c t e d in F i g . 6 a . W e a l s o m a k e s o m e c o m m e n t s o n t h e s t r u c t u r a l p a r a m e t e r χ
for c o m p o s i t e s h a v i n g a n a g g r e g a t e s t r u c t u r e as s h o w n in F i g 8 .36 b . S u c h c o m p o s i t e s
83
a r e a l s o c a l l e d cell m a t e r i a l s , a c o n c e p t i n t r o d u c e d b y M i l l e r . A cell m a t e r i a l is
d e f i n e d b y the f o l l o w i n g r e q u i r e m e n t s : (1) s p a c e is c o m p l e t e l y filled w i t h cells;
(2) t h e cells a r e d i s t r i b u t e d so that the m a t e r i a l is s t a t i s t i c a l l y h o m o g e n e o u s a n d
i s o t r o p i c ; a n d (3) t h e m a t e r i a l or p r o p e r t y o f a cell is s t a t i s t i c a l l y i n d e p e n d e n t o f
t h e o t h8 e3r cells. T h e f o u r t h - o r d e r b o u n d s for cell m a t e r i a l s 39w e r e d e r i v e d b y
M i l l e r a n d further a n a l y z e d b y M c P h e d r a n a n d M i l t o n . F o r cell m a t e r i a l s
c o m p o s e d o f r a n d o m l y o r i e n t e d s p h e r o i d a l cells 39w i t h d e p o l a r i z a t i o n factors L | , L
2
a n d L3 t h e y o b t a i n e d t h e f o l l o w i n g e x p r e s s i o n for t h e s t r u c t u r a l p a r a m e t e r x:
x = (1 - fA> Ρ + fA (1 " P> / W6)
where
2 2 2
p = [3(L +L +L
1 2 3)-l]/2. (47)
F o r t h e c a s e o f s p h e r i c a l cells E q . (47) r e d u c e s to ρ = 0, w h i c h y i e l d s χ = f .
A
Obviously, composites described by the Bruggeman theory have the same value of
χ as a s p h e r i c a l cell m a t e r i a l . F r o m F i g . 10 w e s e e that d i s p e r s i o n s o f i m p e n e t r a b l e
s p h e r e s h a v e p r o p e r t i e s q u i t e c l o s e to t h e M a x w e l l G a r n e t t t h e o r y ( x = 0 ) , w h i l e
dispersions of penetrable spheres should have properties intermediate between
those o f the M a x w e l l Garnett and B r u g g e m a n theories.
R e c e n t l y t h e r e h a s b e e n a n i n c r e a s i n g i n t e r e s t in t h e f o r m u l a t i o n o f e f f e c t i v e
m e d i u m t h e o r i e s t a k i n g i n t o a c c o u n t c o r r e l a t i o n effects. V a r i o u s s c h e m e s h a v e
b e e n d e v i s e d for i m p r o v i n g t h e M a x w e l l G a r n e t t t h e o r y b y i n c l u d i n g d i p o l e -
d i p o l e a n d h i g h e r m u l t i p o l4 e 8
i4n t e r a c t i o n s b e t w e e n t h e p a r t i c l e s . R a n d o m u n i t cells
c o n t a i n i n g 8m5 a n y p a r t i c l e s ' a n d the effect o f t o p o l o g i c a l d i s o r d e r in t h e lattice
g a s m o d e l h a v e b e e n s t u d i e d . Effects o f t h e pair c o r r e l a t i8o n8 68f u n c t i o n in effective
m e d i u m e x p r e s s i o n s is a n o t h e r s u b j e c t o f c u r r e n t i n t e r e s t . " A thorough study
o f d i p o l e a n d m u l t i p o l e i n t e8r9
a c t i o n s in d i l u t e d i s p e r s i o n s o f s p h e r e s w a s c a r r i e d
out b y Felderhof and J o n e s . H o w e v e r , because the pair correlation and three-
point correlation functions both enter into the calculation of the fundamental
s t r u c t u r a l p a r a m e t e r x , w e b e l i e v e that a n y effective m e d i u m t h e o r y w h i c h is to b e
v a l i d o v e r a r a n g e o f filling factors m u s t i n c l u d e b o t h p a i r a n d t h r e e - p o i n t
contributions. Theories including just the pair correlation function should b e
g o o d o n l y for l o w filling factors. Effective m e d i u m t h e o r i e s w h i2c h939 d0
1e p e n d
e x p l i c i t l y o n t h e v a l u e o f χ h a v e o n l y r e c e n t l y b e g u n to a p p e a r . ' ' We
c o n c l u d e this s e c t i o n w i t h t w o e x a m p l e s o f s u c h t h e o r i e s a n d a p p l y t h e m to
relevant experimental situations.
First w e consider gas evaporated metal particle coatings. T h e y are p r o d u c e d b y

evaporation of m 92e t a l in a f e w T o r r o f an i n e r t g a s , s o m e t i m e s w i t h a s m a l l a d d i -
tion o f o x y2g e93n . T h i s p r o c e s s l e a d s to l a r g e m e t a l p a r t i c l e a g g r e g a t e s w i t h a fractal
structure. ' W h e n collected on a substrate, the aggregates are connected over
m a c r o s c o p i c d i s t a n c e s . T h e d e p o s i t s a r e s o o t y , l o o s e l y p a c k e d p o w d e r s , w h e r e the
v o l u m e fraction o f p a r t i c l e s is t y p i c a l l y less than a f e w p e r c e n t . T h e c o a t i n g s h a v e
a s t r u c t u r e w h e r e b o t h p h a s e s p e r c o l a t e , i.e., t h e p a r t i c l e p h a s e a n d t h e s u r r o u n d -
i n g air. T h i s m e a n s that t h e effective m e d i u m t h e o r y g i v e n b y E q s . ( 2 2 ) a n 2 d3(23)
94
s h o u l d b e a g o o d a p p r o x i m a t i o n for the o p t i c a l p r o p e r t i e s o f t h e c o a t i n g s . The
fractal d i m e n s i o n s o f n o n m a g n e t i c g a s e v a p o r a t e d a g g r e g a t e s a r e t y p i c a l l y in the
r a n g e 1.9 to 2. T h u s a v a l u e o f χ o f a b o u t 0.09 to 0.10 s h o u l d b e u s e d in t h e t h e o r e -
tical c a l c u l a t i o n .
W e n o w a p p l y this t h e o r y to the c a s e w h e r e e a c h m e t a l p a r t i c l e is c o a t e d b y a n
o x i d e s h e l l . T h i s is i n t r o d u c e d b y p e r f o r m i n g the e v a p o r a t i o n w i t h o x y g e n m i x e d
in t h e g a s p r e s e n t d u r i n g t h e p r o c e s s . F o r the d i e l e c t r i c47
permeability of the particle
p h a s e w e u s e t h e f o r m u l a for a c o a t e d s p h e r e w h i c h i s
ε + 2ε<. + 2 Ω ( e - e )
Μ M c
ε
Α= ec ε + 2 e - Ω ( ε - e )— , (48)
Μ c Μ c
where is t h e dielectric p e r m e a b i l i t y o f t h e m e t a l c o r e , e is that o f t h e o x i d e
c
c o a t i n g a n d Ω is the v o l u m e fraction o f m e t a l in t h e p a r t i c l e . It s h o u l d b e k e p t in
m i n d t h a t E q . ( 4 8 ) t a k e s i n t o a c c o u n t o n l y t h e d i p o l e t e r m s in t h e i n t e r a c t i o n
b e t w e e n c o r e a n d c o a t i n g . W h e n t h e sizes o f the m e t a l p a r t i c l e s a r e l e s s t h a n the

m e a n free p a t h o f t h e c o n d u c t i o n e l e c t r o n s in t h e p e r t i n e n t m e t a l , mus9 t 9b5
6e
c o r r e c t e d for b o u n d a r y s c a t t e r i n g o f c o n d u c t i o n e l e c t r o n s in t h e p a r t i c l e s . '
In F i g . 11 e x p e r i m e n t a l a n d t h e o r e t i c a l t r a n s m i t t a n c e for a l a y e r o f g a s e v a p o r a t e d
o x i d e c o a t e d a l u m i n i u m p a r t i c l e s is s h o w n . W e h a v e u s e d t h e t h e o r y p r e s e n t e d
a b o v e to e v a l u a t e t h e effective d i e l e c t r i c p e r m e a b i l i t y o f t h e l a y e r s , a n d o b t a i n e d
the transmittance of the layers (divided b y the transmittance of the substrates)
f r o m t h e s t a n d a r d F r e s n e l r e l a t i o n s in S e c . I I . A s i n p u t d a t a 9
w e97
8u s e d t h e e x p e r i -
9 180 0
mentally determined dielectric permeability of a l u m i n i u m ' and evaporated
AI2O3. ' T h e e x p e r i m e n t a l l y d e t e r m i n e d v a l u e for t h e d i a m e t e r o f t h e
a l u m i n i u m c o r e (~ 22 n m ) , t h e filling factor f ~ 0.01 a n d a v a l u e for t h e w e i g h t p e r
u n i t a r e a 0.15 g / m , w h i c h is w i t h i n t h e e r r o r b a r s o f t h e e x p e r i m e n t a l v a l u e , w e r e
also used.
τ 1 1 r
0.8-
* 0.6- / /
t 7
Z _ j/ OXIDE C O A T E D AI P A R T I C L E S .
0 4 2
Ρ _ // EXP W/A~0.1-0.3g/m _
2
Q 2- It T H E O R Y W / A =0.15g/m _
J X=0.09
7 , , • •
200 300 400 500 600

WAVELENGTH (nm)
Fig. 1 1 . T r a n s m i t t a n c e as a f u n c t i o n o f w a v e l e n g t h for o x i d e - c o a t e d
a l u m i n i u m p a r t i c l e s p r o d u c e d b y g a s e v a p o r a t i o n . T h e full
curve denotes experimental results, and the dashed curve
d e n o t e s c a l c u l a t e d v a l u e s . T h e filling f a c t o r for t h e p a r t i c l e s
was 0.01, the diameter of the aluminium core w a s 2 n m and
the v o l u m e fraction, Ω, o f a l u m i n i u m in t h e p a r t i c l e s w a s20 . 2 5 .
T h e w e i g h t p e r unit a r e a in the c a l c u l a t i o n s w a s 0 . 1 5 g / m ,
w h i c h is w i t h i n the e r r o r b a r s o f t h e e x p e r i m e n t a l v a l u e as
s h o w n in t h e inset. C a l c u l a t i o n s w e r e c a r r i e d o u t u s i n g the
E M T for fractal s t r u c t u r e s w i t h s t r u c t u r a l p a r a m e t e r χ = 0 . 0 9 .
( F r o m Ref. 2 3 ) .
T h e a g r e e m e n t b e t w e e n t h e o r y a n d e x p e r i m e n t is s a t i s f a c t o r y . T h e e x p e r i m e n t a l
c u r v e s h o w s a p r o m i n e n t a b s o r p t i o n p e a k at λ ~ 1 9 0 n m w i t h a s h o u l d e r o n t h e
l o n g w a v e l e n g t h s i d e . T h e s e features are p r e s e n t in all g a s e v a p o r a t e d o x i d e c o a t e d
a l u m i n i u m s a m p l e s that w e h a v e s t u d i e d . T h e t h e o r e t i c a l c u r v e s h o w s a s h a r p e r
s t r u c t u r e w i t h p e a k s at 1 9 0 n m a n d 2 4 0 n m . T h e a b s o r p t i o n p e a k at λ ~ 1 9 0 n m is
d u e to t h e l o c a l i z e d p l a s m a r e s o n a n c e o f t h e c o n d u c t i o n e l e c t r o n s in i n d e p e n d e n t
a l u m i n i u m p a r t i c l e s , w h i l e t h e p e a k at λ ~ 2 4 0 n m is a c o n s e q u e n c e o f t h e
percolation structure.
A l o n g s t a n d i n g p r o b l e m in t h e field o f o p t i c a l p r o p e r t i e s o f i n h o m o g e n e o u s
m a t e r i a l s is t h e a p p l i c a b i l i t y o f effective m e d i u m d e s c r i p t i o n s in t h e i n f r a r e d a n d
far infrared w a v e l e n g t h r a n g e s . In p a r t i c u l a r an e n1h1a0n c e d a b s o r p t i o n o f s m a l l
m e t a l p a r t i c l e s h a s b e e n f o u n d in t h e far i n f r a r e d , which has thrown some
doubt on the applicability of current theories. T h e g o o d a g r e e m e n t b e t w e e n theory
a n d e x p e r i m e n t in F i g . 11 p r o m p t e d u s to s t u1 d2y0g a s e v a p o r a t e d o x i d e c o a t e d
a l u m i n i u m p a r t i c l e s a l s o in t h e far i n f r a r e d . G a1s e0 1v3a p2
0o r a t e d m e t a l p a r t i c l e s
d i s p l a y a s t r i k i n g l y h i g h a b s o r p t i o n in this r a n g e ' a n d a r e 1c o01n 2
v e1
0n i e n t for
s u c h s t u d i e s . T h e s a m p l e s u s e d for far infrared m e a s u r e m e n t s ' had particles
w i t h a m e d i a n d i a m e t e r o f ~ 8.4 n m , the filling factor w a s92~ 0 . 0 1 5 , a n d t h e fraction
o f u n o x i d i z e d a l u m i n i u m in t h e p a r t i c l e s w a s e s t i m a t e d to b e Ω 98 ~ 0.35. I n o u r99
c o m p u t a t i o n s w e u s e d t h e d i e l e c t r i c p e r m e a b i l i t i e s o f a l u m i n i u m a n d AI2O3.
T h e e's for a l u m i n i u m w e r e c o r r e c t e d for b o u n d a r y s c a t t e r i n g o f c o n d u c t i o n
e l e c t r o n s in t h e m e t a l c o r e s . In F i g . 12 w e s h o w1 t h0 1e 2B10e r g m a n - M i l t o n b o u n d s for a
wavelength of 200 μιη, the experimental v a l u e ' o f ε w i t h e r r o r b a r s a n d the
t h e o r e t i c a l v a l u e for a fractal s t r u c t u r e w i t h b o t h p h a s e s p e r c o l a t i n g a n d x = 0 . 1 . It is
s e e n t h a t t h e r e is a b o u t a factor o f 2 difference b e t w e e n t h e o r y a n d e x p e r i m e n t .
T h u s m o s t o f t h e p r e v i o u s l y r e p o r t e d d i s c r e p a n c i e s in t h e far i n f r a r e d a b s o r p t i o n
o f m e t a l p a r t i c l e s c a n p r o b a b l1 y4b0e a s c r i b e d to structural effects. T h i s c o n c l u s i o n h a s
also been reached b y o t h e r s . A n assessment of the remaining discrepancy
between theory and experiment requires m o r e detailed experiments with accurate
structural characterisation.
791
O u r s e c o n d e x a m p l e c o n c e r n s C0-AI2O3 c o a t i n g s ' w h i c h a r e efficient s e l e c t i v e
absorbers o f solar energy. These coatings were produced by electron b e a m
c o e v a p o r a t i o n f r o m t w o s o u r c e s , a n d c o n s i s t o f 1 0 - 3 0 À c o b a7 lt particles dispersed
in a n a m o r p h o u s m a t r i x o f m i x e d c o b a l t - a l u m i n i u m - o x i d e . T h e p a r t i c l e s a r e to a
g o o d a p p r o x i m a t i o n d i s p e r s e d91r a n d o m l y in the o x i d e a n d a r e p r e f e r e n t i a l l y
s u r r o u n d e d b y an o x i d e s h e l l for filling factors u p to 0.6-0.7. W e m o d e l this
m a t e r i a l as a s y s t e m o f r a n d o m l y d i s p e r s e d i m p e n e t r a b l e o x i d e - c o a t e d c o b a l t
s p h e r e s , d i s p e r s e d in a m a t r i x o f the s a m e o x i d e . T h91 e d i e l e c t r i c p e r m e a b i l i t y o f the
p a r t i c l e s is91g i v e n b y E q . ( 4 8 ) , w h e r e Ω w a s e s t i m a t e d to b e ~ 0.75 b y e q u a t i n g the
o b s e r v e d c o n d u c t i v i t y t h r e s h o l d at f ~ 0.15 to 0.20 w i t h t h e p e r c o l a t i o n t h r e s h o l d
for o x i d e - c o a t e d s p h e r e s . F o r filling factors a b o v e t h e c o n d u c t i v i t y t h r e s h o l d , b o t h
p h a s e s a r e p r o b a b l y p e r c o l a t i n g a n d E25
q s . (22) a n d ( 2 3 ) c a n b e u s e d w i t h χ g i v e n b y
t h e v a l u e s for i m p e n e t r a b l e s p h e r e s in F i g . 1 0 . W e call this s c h e m e t h e R a n d o m
H a r d Coated Spheres (RHCS) theory.
W h e n t h e filling factor is l e s s t h a n 0 . 1 5 , t h e M a x w e l l G a r n e t t t h e o r y is a b l e to
p r o d u c e g o o d a g r e e m e n t w i t h e x p e r i m e n t s . In fact, for s u c h l o w filling f a c t o r s the
M G a n d R H C S t h e o r i e s a r e n o t m u c h different. F i g . 13 s h o w s t h e i m a g i n a r y p a r t
o f t h e d i e l e c t r i c p e r m e a b i l i t y for C0-AI2O3 c o a t i n g s w i t h different filling factors. It

is s e e n that for f = 0.17 a n d 0.23 t h e R H C S t h e o r y g i v e s a s i g n i f i c a n t l y b e t t e r fit to
e x p e r i m e n t a l v a l u e s t h a n t h e M G t h e o r y . F o r f = 0 . 2 9 d i s c r e p a n c i e s a l s o start to
a p p e a r b e t w e e n t h e R H C S t h e o r y a n d t h e m e a s u r e m e n t s . In s u m m a r y , o u r
k n o w l e d g e o f t h e p a r a m e t e r χ h a s a l l o w e d u s t o d e r i v e a n e w effective m e d i u m
t h e o r y for C0-AI2O3 c o m p o s i t e s . T h i s t h e o r y is a c c u r a t e o v e r a l a r g e r r a n g e o f
filling factors t h a n t h e p r e v i o u s l y u s e d M G t h e o r y .
ι 1——
ι 1——
j—
ι—
ι—
ι—
ι—
ι—
ι—
ι—
ι—
ι—
ι—
ι—
ι—
ι 1—
BM-bounds
= 1
0,01 - ></ ~~
ε
2
0.005 — s' y —
Theory
0
1 1 1——
ι I11111111I I I I Iι
1 1.05 1.1 1.15 1.2
ε.
Fig. 1 2 . B e r g m a n - M i l t o n b o u n d s for a n i s o t r o p i c d i s p e r s i o n o f
A l C > 3 - c o a t e d a l u m i n i u m s p h e r e s i n air. T h e c o m p u t a t i o n
2
refers to λ = 2 0 0 μ ι η , f = 0 . 0 1 5 a n d Ω = 0 . 3 5 . T h e m a r k s o n the
A
bounds indicate values pertinent to the structural parameter χ
g o i n g from z e r o to u n i t y b y steps o f 0.1. T h e e x p e r i m e n t a l
v a l u e w i t h e r r o r b a r s for and the theoretical value calculated
f r o m t h e effective m e d i u m t h e o r y for fractal s t r u c t u r e s a r e a l s o
shown. (From Ref. 102).
V. MATERIALS WITH LARGE INHOMOGENEITIES
S o far w e h a v e o n l y c o n s i d e r e d t w o - c o m p o n e n t m a t e r i a l s , w h e r e t h e s i z e o f t h e
i n c l u s i o n s o f t h e c o m p o n e n t s a r e m u c h s m a l l e r t h a n t h e w a v e l e n g t h o f light.
T h i s a l l o w e d u s to treat t h e o p t i c a l p r o p e r t i e s o f t h e c o m p o s i t e s i n t h e q u a s i s t a t i c
a p p r o x i m a t i o n . I n this s e c t i o n w e g o b e y o n d this a p p r o x i m a t i o n a n d t r e a t
absorption and scattering b y composite media where the inhomogeneities are
comparable to or larger than the wavelength.
τ 1—ι—ι—ι 1 1—ι—ι—ι—r-rr
10
- r=o.i2
> '
5
<
C
2
s
1 = 0.23
§j r=o.i9
S - X. A=0.25
Si v > \
ce Λ \ *- „
Li. - —
ο ε2
H '
OC
< I I
CL 3 EXP
Œ ~ C o - A I 20 3 MG THEORY
Ζ N RHCS THEORY
S
- " V
- \S. f = 0.29
2- \ ^ ^ ^ ^ f* = 0.25
\ ^ \ fA=0.33
I I I I I I I I I I I I I I I
0.4 0.6 0.8 1 2
WAVELENGTH (μπι)
Fig. 1 3 . I m a g i n a r y p a r t o f t h e effective d i e l e c t r i c p e r m e a b i l i t y as a
f u n c t i o n o f w a v e l e n g t h for C0-AI2O3 c o a t i n g s . D o t t e d c u r v e s
denote experimental results, dashed curves denote computa-
tions b y t h e M a x w e l l G a r n e t t t h e o r y a n d full lines d e n o t e c o m -
putations b y the R a n d o m H a r d Coated Spheres theory. T h e
filling factors o f c o b a l t , f, o f c o b a l t p a r t i c l e s , f*, a n d o f o x i d e
c o a t e d c o b a l t p a r t i c l e s , f , a r e g i v e n in t h e inset. T h e v o l u m e
A
fraction o f m e t a l in t h e o x i d e c o a t e d p a r t i c l e s w a s p u t e q u a l to
0.75. ( F r o m Ref. 9 1 ) .
O u r definition o f an effective m e d i u m required that the R a n d o m U n i t Cell, w h e n

e m b e d d e d in t h e effective m e d i u m , s h o u l d n o t b e d e t e c t a b l e b y e l e c t r o m a g n e t i c
r a d i a t i o n . T h i s l e d to t h e c r i t e r i o n that t h e s c a t t e r i n g a m p l i t u d e S ( 0 ) s h o u l d b e
z e r o . H o w e v e r , o n e c o u l d j u s t as w e l l d e m a n d that t h e b a c k s c a t t e r i n g a m p l i t u d e
S(K) s h o u l d b e z e r o . T h u s a m o r e r i g o r o u s definition o f a n e f f e c t i v e m e d i u m is
S (0) = S (π) = 0 , (49)
w h e r e t h e s c a t t e r i n g is f r o m a R U C e m b e d d e d in the e f f e c t i v e m e d i u m . E q u a t i o n
(49) is satisfied as l o n g as o n l y t h e e l e c t r i c d i p o l e t e r m in t h e L o r e n z - M i e
e x p a n s i o n is t a k e n i n t o a c c o u n t , or, e q u i v a l e n t l y , as l o n g as t h e q u a s i s t a t i c
approximation holds.
T h e l i m i t s o f v a l i d i t y o f t h e s i m p l e effective m e d i u m t h e o r i e s t r e a t e d in S e c . I l l
c a n b e a s s e s s e d b y c o m p u t i n g the c o n t r i b u t i o n o f t h e h i g h e r o r7d1e4r t e r m s o f t h e
L o r e n z - M i e e x p a n s i o n to t h e effective d i e l e c t r i c p e r m e a b i l i t y . ' These large-size
l i m i t s d e p e n d o n t h e filling factor, t h e w a v e l e n g t h a n d o n t h e d i e l e c t r i c p e r m e a -
bilities o f t h e c o n s t i t u e n t m a t e r i a l s , a n d n o g e n e r a l r u l e s c a n b e g i v e n . H o w e v e r ,
for t h e c a s e o f m e t a l - i n s u l a t o r c o m p o s i t e s it a p p e a r s that t h e d i a m e t e r o f t h e m e t a l
p a r t i c l e s s h o u l d b e71less
4 t h a n ~ λ / 2 0 in o r d e r that t h e effective m e d i u m t h e o r i e s
remain accurate. '
W h e n t h e p a r t i c l e s i z e is s o l a r g e that E q . (49) is n o l o n g e r v a l i19 d o n e h a s to r e s o r t

to e x t e n d e d e f f e c t i v e m e d i u m t h e o r i e s , as s h o w n b y B o h r e n . These theories
e m p l o y t w o e f f e c t i v e q u a n t i t i e s , n a m e l y t h e effective d i e l e c t r i c p e r m e a b i l i t y
d i s c u s s e d in p r e v i o u s s e c t i o n s a n d an effective m a g n e t i c p e r m e a b i l i t y , μ. R i g o -
r o u s r e s u l t s19for ε a n d μ a r e k n o w n o n l y in the l i m i t o f s m a l l filling f a c t o r s w h e r e
we obtain
3f
(εμ>ν2 = ι - i A S(0) (50)
2 (k )3
efl
and
3f
εΐ/2.μΐ/2 .ΐ= A (51)
2(V)3 S(tc) .
H e r e w e h a v e a s s u m e d s p h e r i c a l p a r t i c l e s o f r a d i u s a. F r o m t h e s e e q u a t i o n s
e x p r e s s i o n s for ε a n d μ m a y b e o b t a i n e d . T h e e x t e n s i o n o f t h e t h e o r y to h i g h e r
filling factors r e m a i n s a n o b j e c t for future r e s e a r c h . A l s o E q s . ( 5 0 ) a n d (51) w e r e

d e r i v e d b y a s s u m i n g n o r m a l l y i n c i d e n t light o n t o a s l a b o 1 f9t h e c o m p o s i t e , a n d
their a p p l i c a b i l i t y at o b l i q u e i n c i d e n c e is still in q u e s t i o n .
T h e effective d i e l e c t r i c a n d m a g n e t i c p e r m e a b i l i t i e s o b t a i n e d f r o m e x t e n d e d
effective m e d i u m t h e o r i e s c a n n o w b e i n s e r t e d i n t o t h e e x p r e s s i o n s for thin film
o p t i c s in S e c . II. In this w a y t h e t r a n s m i t t a n c e a n d r e f l e c t a n c e c a n b e c a l c u l a t e d , at
l e a s t for n o r m a l l y i n c i d e n t light. T h e e x t e n d e d effective m e d i u m t h e o r i e s h a v e s o
far n o t b e e n u s e d v e r y m u c h . A d e t a i l e d t r e a t m e n t o f t h e l o n g - w a v e l e n g t h l i m i t
w a s g i v e n in Ref. 1 0 5 . T h e m a i n a r e a o f a p p l i c a t i o n c o n c e r n s t h e far infrared
a b s o r p t i o n o f m e t4 a l 19
p a0
1r t i c3
0l 7
e s6, w-h e1r e 0in m a n y c a s e s t h e m a g n e t i c d i p o l e t e r m s a r e
very i m p o r t a n t . ' ' H o w e v e r , the fact that ε a n d μ a r e i n d e p e n d e n t
q u a n t i t i e s h a s s e l d o m b e e n a p p r e c i a t e d ; in m a n y c a s e s o n l y t h e p r o d u c t ε · μ h a s
been studied.
T h e p r o b l e m o f o b t a i n i n g r i g o r o u s b o u n d s to t h e effective p h y s i c a l p r o p e r t i e s o f a
c o m p o s i t e b e y o n d t h e q u a s i s t a t i c limit h a s b e e n little e x p l o r e d . T h e o n l y w o r k h a s
b e e n a g e n e r a l i z a t i o n o f t h e W i1 e8
n0e r b o u n d s to m a t e r i a l s w i t h i n h o m o g e n e i t i e s
c o m p a r a b l e to t h e w a v e l e n g t h . However, no bou 1n8d0s o n t h e effective m a g n e t i c
p e r m e a b i l i t y w e r e g i v e n . T h e t r e a t1m e01n9t 8
0o f A s p n e s h a s b e e n a p p l i e d to
experiments on pressed p o w d e r s . '
A m a j o r s h o r t c o m i n g o f e x t e n d e d effective m e d1 i u1
950t h e o r i e s is t h a t t h e y c a n n o t
m
distinguish between scattering and a b s o r p t i o n . ' In r e a l i t y , for m a t e r i a l s w h e r e
t h e c o m p o n e n t p a r t i c l e s a r e sufficiently l a r g e , diffuse s c a t t e r i n g o f l i g h t p l a y s a
m a j o r r o l e . In a d d i t i o n to the d i r e c t l y t r a n s m i t t e d a n d s p e c u l a r l y r e f l e c t e d l i g h t
f r o m a s l a b o f the c o m p o s i t e , significant a m o u n t s o f diffusely r e f l e c t e d a n d
t r a n s m i t t e d light c a n b e p r e s e n t a l s o . T h i s s i t u a t i o n d e m a n d s a t h o r o u g h l y
different t h e o r e t i c a l a p p r o a c h a n d e v e n the f o r m u l a s o f thin film o p t i c s in S e c . II
c a n n o l o n g e r b e u s e d . In o r d e r to treat s c a t t e r i n g m e d i a o r m a t e r i a l s w h e r e b o t h
s c a t t e r i n g a n d a b s o r p t i o n 2a r2 e02i m p o r t a n t w e h a v e to c o n s i d e r m u l t i p l e s c a t t e r i n g o r
r a d i a t i v e transfer t h e o r y . " In t h e g e n e r a l c a s e this t h e o r y is v e r y c o m p l e x a n d
r e s u l t s h a v e to b e o b t a i n e d b y n u m e r i c a l c a l c u l a t i o n s . A v e r y useful t a b u l a t2 i0
on of
results from multiple scattering theory has b e e n published b y van de H u l s t . If
i n f o r m a t i o n o n the a n g u l a r d i s t r i b u t i o n o f the s c a t t e r e d l i g h t is n o t n e c e s s a r y ,
i m p o r t a n t s i m p l i f i c a t i o n s c a n b e m a d e . T h i s s i t u a t i o n is p r e s e n t w h e n m e a s u r e -
ments o f the optical properties of composite materials are performed b y an
i n t e g r a t i n g s p h e r e . I n this c a s e t h e s p e c u l a r a n d diffuse c o m p o n e n t s o f t h e
r e f l e c t a n c e , a n d the d i r e c t a n d diffuse t r a n s m i t t a n c e a r e e a s i l y m e a s u r e d . T h e s e
four q u a n t i t i e s c a n b e c a 2 l c u11
l a t1
e2d0b y -a 1 s i m1p l i f i e d m u l t i p l e s c a t t e r i n g t h e o r y , t h e s o
c a l l e d four-flux t h e o r y . ' 1 2 1 A n a n a l y t i c a l s o l u t i o n o f this t h e o r y h a s r e c e n t l y
b e e n g i v e n b y M a h e u et a l .
C o n s i d e r n o w a s l a b o f t h i c k n e s s d w h i c h c o n t a i n s a d i l u t e d i s p e r s i o n o f particles.
In t h e four-flux t h e o r y t h e r a d i a t i o n field is m o d e l e d as c o n s i s t i n g o f four parts: a
c o l l i m a t e d b e a m o f i n t e n s i t y I ( z ) a n d a diffuse b e a m o f i n t e n s i t y I ^ ( z ) p r o p a g a t i n g
c
to n e g a t i v e z, a n d a c o l l i m a t e d b e a m J ( z ) a n d a diffuse b e a m J ( z ) p r o p a g a t i n g to
1 2 1 c d
p o s i t i v e z. T h e g e o m e t r y is s h o w n in F i g . 1 4 . T h e differential e q u a t i o n s for the
intensities a r e
Film
Incident
light
Jc
Jd
ζ =d 2 =0
Fig. 14. G e o m e t r y a n d t h e v a r i o u s fluxes that a p p e a r i n t h e four-flux
t h e o r y . ( F r o m Ref. 1 1 4 ) .
dlc/dz = (k+s)I , (52)

c
d j / d z = - (k+s)J , (53)
c c
sI
d l / d z = r|kl + ri(l-p )sl - ' Pc c " ( ^ P c M o (54)
d d d d
d j / d z = - r|kj - n(l-p )sj + " ( l - p ) s l + (l-p )sl + p sj . (55)
d d d d d d c c c c
H e r e k is t h e a b s o r p t i o n coefficient, s is the s c a t t e r i n g coefficient, p a n d p a r e the
c d
ratios o f f o r w a r d to total s c a t t e r i n g for t h e c o l l i m a t e d a n d diffuse b e a m s , r e s p e c t i -
v e l y , a n d η is a p a r a m e t e r that d e t e r m i n e s t h e a v e r a g e p a t h l e n g t h t r a v e l l e d b y t 1 h e2 1
diffuse b e a m s as c o m p a r e d to the c o l l i m a t e d o n e s . A s d i s c u s s e d b y M a h e u e t a l .
t h e coefficients k, s a n d p c a n b e o b t a i n e d f r o m s i n g l e s c a t t e r i n g c a l c u l a t i o n s b y
c
L o r e n z - M i e t h e o r y for the c a s e o f s p h e r i c a l p a r t i c l e s . F o r t h e o t h e r p a r a m e t e r s ,
r i g o r o u s results a r e k n o w n o n l y for e x t r e m e c a s e s . T h e p a r a1m2e1t e r η is u n i t y for a
c o l l i m a t e d b e a m a n d t w o for a s e m i - i s o t r o p i c diffuse 21 b e a m . T h e forward
s c a t t e r i n g ratio p h a s b e e n c a l c u l a t e d b y I s h i m a r u for t h e c a s e o f i s o t r o p i c
d
i n c i d e n t light. T h e o t h e r e x t r e m e c a s e , i.e., 1v2e 1r y a n i s o t r o p i c i n c i d e n t light, w o u l d
l e a d to p = p , as a s s u m e d b y M a h e u et a l .
c d
T h e s e t o f e q u a t i o n s ( 5 2 ) - ( 5 5 ) c a n b e s o l v e d in o r d e r to o b t a i n t h e t r a n s m i t t a n c e
a n d r e f l e c t a n c e for a s l a b o f the c o m p o s i t e m a t e r i a l . T h e c a l c u l a t i o n s a r e e l e m e n -
tary, a l t h o u g h r a t h1e2 r 1i n v o l v e d , s o that o n l y the results o f t h e c a l c u l a t i o n s a r e
presented b e l o w . T h e , total t r a n s m i t t a n c e is the s u m o f t h e d i r e c t c o m p o n e n t
T a n d t h e diffuse c o m p o n e n t T , i.e.
c d
Τ = T + T , (56)
1 21 c d
where
2
: ( l - r c)2e x p ( - ( k - f - s ) d)
(57)
l-r e x p ( - 2 ( k + s ) d)
c
and
Td ( l - r ) (2
c l - r ) e x p ( - ( k + s ) d)
d
" (Ai - ( k + s ) ) ( l - r 2 e x p ( - 2 ( k + s ) d)) D '
c
Ν
)
H e r e r a n d r a r e the reflection coefficients at the s l a b b o u n d a r i e s for c o l l i m a t e d
c d
a n d i n t e r n1a2l 1diffuse i n c i d e n t r a d i a t i o n , r e s p e c t i v e l y . T h e p a r a m e t e r s in E q . ( 5 8 ) are
given b y
Ν = Aj [ r A - A
d 3 2 + r c ( r dA 2- A 3) ] cosh (Ajd) +
+ [(A -r A ) (A +A r ) - (A -r A ) (A +A r )]
5 d 4 3 2c 4 d 5 2 3c
• sinh (A]d) + A ] [ ( A - r A ) exp [(k+s)d] +
2 d 3
+ r ( A - r A ) exp (-(k+s)d)], (59)
c 3 d 2
2
D = A j ( r - l ) cosh (Ajd) + [ r ( A - r A ) + r A
d d 5 d 4 d 5 - A 4] sinh (Ajd), (60)
2
A! = η [ k + 2 ( 1 ^ ^ / 2 , )
A
2= s [r|kp + n s ( l - p ) + p ( k + s ) ] ,
c d c (62)
A
3= s ( l - p ) (k+s) (η-1),
c (63)
A
4= η (k + ( l - p ) s ) ,
d (64)
A s
5 = η (1-Pd) - ( )
S i m i l a r l y the total r e f l e c t a n c e is the s u m o f the s p e c u l a r c o m p o n e n t 1 ^ a n d the

diffuse c o m p o n e n t R , i.e.
d
R = R + R . (66)
c d
T h e components are given by
2
T + r ( l - r2) e x p ( - 2 ( k + s ) d) )
c c 6 5
^ ~ c i-r exp(-2(k+s)d)
c
and
( l - r ) 2( l - r ) e x2p ( - ( k + s ) d ) M
d c (68)
[ A | - ( k + s ) ] [1 - r e x p (-2(k+s) d) ] D '
c
where
M [A + A r - r
A
r 3 2 c d ( A 2+ A 3r c) ] +
+ [ A j ( A r - A ) c o s h (Α ά) + (A (A -A r ) +
2d 3 λ 2 5 4d
+ A
3( A 5r d- A 4) ) sinh (Ajd)] exp [(k+s)d] +
+ r
c[A| ( A r - A ) cosh ( A ^ ) + ( A ( A - A r ) +
3d 2 3 5 4d
+ A
2( A 5r d- A 4) ) sinh ( A j d ) ] e x p [-(k+s)d] (69)
w i t h t h e o t h e r p a r a m e t e r s as g i v e n a b o v e . I f t h e p a r t i c l e s a r e t r a n s p a r e n t ( k = 0 )
t h e s o l u t i o n c a n n o t b e o b t a i n e d d i r e c t l y from t h e a b o v e r e s u l t s , b u t 1 m2o1d i f i e d
e x p r e s s i o n s c o n v e n i e n t for c a l c u l a t i o n s w e r e g i v e n b y M a h e u e t . a l . The
coefficients s, k a n d p c a n b e d i r e c t l y o b t a i n e d f r o m L o r e n z - M i e c a l c u l a t i o n s for a
c
single particle and are the fundamental material parameters o f the composite.
H o w e v e r , it s h o u l d b e e m p h a s i z e d t h a t t h e u s e o f L o r e n z - M i e t h e o r y for this
p u r p o s e p r e s u p p o s e s a d i l u t e m i x t u r e o f p a r t i c l e s in a m a t r i x . T h u s t h e four-flux
t h e o r y in its p r e s e n t f o r m u l a t i o n s h o u l d b e v a l i d for l o w filling f a c t o r s o f t h e
s c a t t e r i n g c o m p o n e n t o n l y . T h e e x t e n s i o n o f m u l t i p l e s c a t t e r i n g t h e o r y1 3to1 h i g h
filling factors is a c o m p l e x p r o b l e m b u t s o m e p r o g r e s s h a s b e e n m a d e .
141
T h e four-flux t h e o r y h a s b e e n20c o m p a r e d to t h e r i g o r o u s m u l t i p l e s c a t t e r i n g
calculations of van de H u l s t . G o o d a g r e e m e n t w a s f o u n d if p h y s i c a l l y r e a l i s t i c
v a l u e s o f t h e p a r a m e t e r s η a n d p w e r e u s e d . T h u s t h e four flux t h e o r y is suffi-
d
c i e n t l y a c c u r a t e s o that it c a n b e u s e d for d e t a i l e d c o m p a r i s o n s w i t h s p e c t r o -
121
photometric integrating sphere measurements. Further simplifications of the
t h e o r y a r e p o s1 s5i b1l e to o b t a i n t w o - f l u x t h e o r i e s s u c h as t h e w e l l - k n o w n K u b e l k a -
Munk model. H o w e v e r , two-flux m o d e l s d o n o t treat t h e d i r e c t a n d diffuse
c o m p o n e n t s s e p a r a t e l y a n d t h u s a r e n o t as a c c u r a t e as t h e four-flux m o d e l s .
O n e c a n e n v i s a g e n u m e r o u s a p p l i c a t i o n s for this k i n d o f t h e o r y . I n p a r t i c u l a r it
c a n b e u s e d to p r e d i c t t h e o p t i c a l p r o p e r t i e s o f h e t e r o g e n e o u s m a t e r i a l s c o n s i s t i n g
o f p a r t i c l e1
s d1 i1s8
p61
e r s e d in a m a t r i x . S o m 19e 1e x a m p l e s o f this k i n d1 o2f1m 202a t e r i a l a r e p a i n t
c o a t i n g s , 1"32 p i g m e n t e d p o l y m e r s , Christiansen f i l t e r s , " and fibrous
materials. S u c h m a t e r i a l s a r e o f i n t e r e s t for i m p r o v i n g e n e r g y efficiency in
c e r t a i n c a s e s . F o r e x a m p l e , p9a1 i n8t1
s a r e a p p l i e d as s e l e c t i v e a n d n o n - s e l e c t i v e
1 10 9 1
absorbers o f solar r a d i a t i o n , ' p i g m e n t e d p o l y m e r s a r e o f i n t e r e s t in r a d i a t i v e
c o o l i n g , '1 0 2r e f r a c t i v e i n d e x m a t c h i n g m a y b e u s e d in o r d e r to o b t a i n t h e r m o -
c h r o m1 i s m21 21 2a n d v o l t a g e - i n d u c e d s w i t c h i n g b e t w e e n c l e a r a n d diffusely s c a t t e r i n g
s t a t e s ' 1in 32w i n d o w s , a n d fibrous m a t e r i a l s a r e c o m m o n l y u s e d for t h e r m a l
insulation.
In F i g . 15 w e s h o w c a l c u l a t i o n s o f total t r a n s m i t t a n c e a n d r e f l e c t a n c e for a c o m -
p o s i t e c o n s i s t i n g o f T i 0 s p h e r e s o f d i a m e t e r 0.23 μιη d i s p e r s e d in p o l y e t h y l e n e .
2
W e u s e d t h e four-flux t h e o r y w i t h η = 1 a n d P d = P - T h e p a r a m e t e r s s, k a n d p w e3r4e
c c
o b t a i n e d f r o m a L o r e n z - M i e c a l c u l a t i o n w h i c h14u2s e d p u b l i s h e d o p t i c a l c o n s t a n t s
for T1O2 a n d m e a s u r e d , as w e l l as p u b l i s h e d , a b s o r p t i o n coefficients o f
p o l y e t h y l e n e . T h e refractive i n d e x o f p o l y e t h y l e n e w a s t a k e n t o b e 1.51. T h e
c o m p o s i t e h a s a v e r y h i g h r e f l e c t a n c e in t h e v i s i b l e a n d n e a r i n f r a r e d w a v e l e n g t h
r a n g e a n d a h i g h t r a n s m i t t a n c e further o u t in t h e infrared, p a r t i c u l a r l y a r o u n d
10 μιτι. T h i s m a k e s t h e foil s u i t a b l e for r a d i a t i v e c o o l i n g p u r p o s e s . T h e
a b s o r p t i o n o f s o l a r r a d i a t i o n is l o w a n d t h e h i g h t r a n s m i t t a n c e in t h e a t m o s p h e r i c
w i n d o w r e g i o n a r o u n d 1 0 μιη g i v e s r i s e to r a d i a t i v e c o o l i n g o f a n u n d e r l y i n g
e m i s s i v e m a t e r i a l . C a l c u l a t i o n s for a T i C ^ - p o l y e t h y l e n e c o m p o s i t e w i t h f = 0 . 0 6 5 a r e
in g o o d a g r e e m e n t w i t h e x p e r i m e n t a l r e s u l t s in t h e v i s i b l e a n d n e a r i n f r a r e d
s p e c t r a l r e g i o n s , as s e e n in Fig. 1 5 . F u r t h e r d a t a are g i v e n in t h e c h a p t e r o n
M a t e r i a l s for R a d i a t i v e C o o l i n g to L o w T e m p e r a t u r e s .
1.0 ρ — ' '·'<'[— 1 1Ι1 —ιΙ—

ΙΤ
8 : : Ti0
: 2- Polyethylene
; ; f =0.065
:
Theory
* ° · " f x v
Exp.
• 0.6 - / \ \
* 04 I ι
1.0
-
υ 0.8
c
0.6
/!
/'i
Λ \ -
0.2
ι
\ :
I ,,,Α i\JK'
0.5 2 5 10 20
Wavelength (μιτι)
Fig. 1 5 . T o t a l t r a n s m i t t a n c e a n d r e f l e c t a n c e as a f u n c t i o n o f w a v e -
l e n g t h for a c o m p o s i t e c o n s i s t i n g o f T1O2 p a r t i c l e s o f 0.23 μ ι η
m e d i a n d i a m e t e r in p o l y e t h y l e n e . D a s h e d c u r v e s d e n o t e
experimental data and continuous curves denote calculations
c a r r i e d o u t b y the four-flux t h e o r y w i t h η = 1 a n d p = p . T h e
d c
filling factor o f T1O2 w a s e q u a l to 0.065 a n d t h e t h i c k n e s s o f
t h e foil w a s 1 0 0 μιη. ( F r o m Ref. 1 1 9 ) .
O f c o u r s e , m u l t i p l e s c a t t e r i n g t h e o r y h a s m a n y o t h e r a22 pplications. These include

s c a t t e r i n g f r o m g e o l o g i c a l m a t e r i a l s ( r e m o t e s e n s i n g ) , a t m o s p h21eric scattering,
s c a t t e r i n g i n s e a w a t e r , a n d s c a t t e r i n g from b i o l o g i c a l m a t e r i a l s .
VI. CONCLUDING REMARKS
I n this r e v i e w w e h a v e c o n s i d e r e d t h e t h e o r e t i c a l d e s c r i p t i o n o f t h e o p t i c a l p r o -
p e r t i e s o f i n h o m o g e n e o u s m a t e r i a l s . T h e u s e o f effective m e d i u m t h e o r i e s for
m a t e r i a l s w i t h s m a l l i n c l u s i o n s o f the c o m p o n e n t s is b y n o w w e l l e s t a b l i s h e d .
T h i s d e s c r i p t i o n is v e r y often u s e d to d e s c r i b e the o p t i c a l p r o p e r t i e s o f c o m p o s i t e
films, for e x a m p l e s e l e c t i v e s o l a r a b s o r b i n g c o a t i n g s . T h e r i g o r o u s B e r g m a n -
Milton bounds, on the other hand, are a m o r e recent development and have not
y e t b e e n s o w i d e l y u s e d for c o m p a r i s o n w i t h e x p e r i m e n t s . P a r t l y , this is d u e to an
insufficient u n d e r s t a n d i n g o f t h e r e l a t i o n b e t w e e n m i c r o s t r u c t u r e a n d specific
areas within the Bergman-Milton bounds.
A n i m p o r t a n t c h a l l e n g e for future r e s e a r c h is to classify t h e a r e a w i t h i n t h e

B e r g m a n - M i l t o n b o u n d s in t e r m s o f specific a s p e c t s o f t h e m i c r o s t r u c t u r e s . T h e
first a t t e m p t s to d o this e m p l o y e d c a l c u l a t i o n s o f t h e s t r u c t u r a l p a r a m e t e r x , w h i c h
i n c l u d e s c o n t r i b u t i o n s f r o m p a i r a n d t h r e e - p o i n t c o r r e l a t i o n effects, for different
m o d e l m i c r o s t r u c t u r e s . T h e f o r m u l a t i o n o f n e w effective m e d i u m t h e o r i e s
t a k i n g at least t h e s e effects i n t o a c c o u n t a p p e a r s to b e n e c e s s a r y i n o r d e r to o b t a i n a
d e t a i l e d u n d e r s t a n d i n g o f o p t i c a l data.
T h e o p t i c a l p r o p e r t i e s o f m a t e r i a l s w i t h i n h o m o g e n e i t i e s w i t h s i z e s > λ h a v e to b e
d e s c r i b e d b y m u l t i p l e s c a t t e r i n g t h e o r y . W e t r e a t e d a s i m p l i f i e d four-flux t h e o r y
w h i c h is v e r y useful for c o m p a r i s o n s w i t h s p e c t r o p h o t o m e t r i c m e a s u r e m e n t s .
T h i s k i n d o f t h e o r y h a s n o t b e e n w i d e l y u s e d for t h e d e s c r i p t i o n o f c o a t i n g s a n d
o p t i c a l m a t e r i a l s , a n d further t h e o r e t i c a l a d v a n c e s a r e d e s i r a b l e . I n p a r t i c u l a r , t h e
t h e o r y s h o u l d b e e x t e n d e d to the c a s e o f d e n s e d i s p e r s i o n s o f s c a t t e r i n g p a r t i c l e s .
T h e optical properties o f such materials are not well understood at the present
time.
I n h o m o g e n e o u s m a t e r i a l s a r e v e r y i m p o r t a n t for v a r i o u s a p p l i c a t i o n s r e l a t e d to
e n e r g y efficiency. M a n y s e l e c t i v e solar a b s o r b e r s c o n s i s t o f v e r y s m a l l m e t a l
p a r t i c l e s in a n o x i d e m a t r i x . T h e o p t i c a l p r o p e r t i e s c a n g e n e r a l l y b e a c c u r a t e l y
d e s c r i b e d b y effective m e d i u m m o d e l s , b u t in specific c a s e s s c a t t e r i n g b y r o u g h
s u r f a c e s is a l s o o f m a j o r i m p o r t a n c e . T r a n s p a r e n t h e a t - r e f l e c t i n g m e t a l c o a t i n g s
o f t e n h a v e a n i n h o m o g e n e o u s n e t w o r k s t r u c t u r e w h i c h d e m a n d s effective
m e d i u m t h e o r i e s o r e x t e n s i o n s o f t h e m . T h e d e v e l o p m e n t o f a four-flux t h e o r y
for m a t e r i a l s w i t h l a r g e p a r t i c l e s is c o n s i d e r e d to b e o f g r e a t i m p o r t a n c e for m a n y
t e c h n o l o g i c a l m a t e r i a l s . A s e x a m p l e s w e m a y cite p a i n t s , p i g m e n t e d p o l y m e r s
a n d f i b r o u s i n s u l a t i o n m a t e r i a l s , w h i c h all h a v e i m p o r t a n t a p p l i c a t i o n s in e n e r g y
technology.
Acknowledgement: This work was financially supported b y grants from the

National E n e r g y Administration of Sweden, the S w e d i s h Natural Science
Research Council and the National Swedish Board of Technical Development.
P a r t o f t h e w o r k r e v i e w e d in this p a p e r w a s p e r f o r m e d w i t h Prof. C . G . G r a n q v i s t ,
w h o is t h a n k e d for a fruitful c o l l a b o r a t i o n a n d v a l u a b l e d i s c u s s i o n s .
REFERENCES
1. F o r a r e c e n t r e v i e w s e e , for e x a m p l e , W . F . B o g a e r t s a n d C M . L a m p e r t , J .
Mater. Sci. 18, 2847 (1983). A bibliography was published b y G.A. Niklasson
and C.G. Granqvist, J. Mater. Sci. 18, 3475 (1983).
2. R . B . Pettit, J . N . S w e e t a n d R . R . S o w e l l , in MiCon 82: Optimization of
Processing, Properties and Service Performance Through Microstructural
Control, A S T M S T P 7 9 2 , e d i t e d b y H . A b r a m s , E . C l a r k , J . H o o d a n d B . S e t h
( A S T M , P h i l a d e l p h i a , 1 9 8 2 ) , p . 2 6 3 ; J . N . S w e e t , R . B . Pettit a n d M B .
Chamberlain, Solar Energy Mater. 1 0 , 251 (1984).
3. P.M. Driver and P.G. M c C o r m i c k , Solar Energy Mater. 6, 159 (1982).
4. G . B . Smith, R.C. M c P h e d r a n and G.H. Derrick, Appl. Phys. A 3 6 , 193 (1985).
5. Â . A n d e r s s o n , O . H u n d e r i a n d C . G . G r a n q v i s t , J. A p p l . P h y s . 5 L 7 5 4 ( 1 9 8 0 ) .
6. R . A . B u h r m a n a n d H . G . C r a i g h e a d , in Solar Materials Science, e d i t e d b y L . E .
M u r r ( A c a d e m i c , N e w Y o r k , 1 9 8 0 ) , p. 2 7 7 .
7. G.A. Niklasson and C.G. Granqvist, J. Appl. Phys. 5 5 , 3382 (1984).
8. J . A . T h o r n t o n , in MiCon 82: Optimization of Processing, Properties and
Service Performance Through Microstructural Control, A S T M STP 792,
edited b y H. Abrams, E. Clark, J. H o o d and B . Seth ( A S T M , Philadelphia,
1982).
9. S.W. Moore, Proc. Soc. Photo-Opt. Instrum. Engr. 5 0 2 , 68 (1984).
10. C . G . G r a n q v i s t a n d T . S . E r i k s s o n , this b o o k .
11. G.B. Smith, G.A. Niklasson, J.S.E.M. Svensson and C.G. Granqvist, J. Appl.
P h y s . 5 9 , 5 7 1 (1986).
12. R . L a n d a u e r , A I P C o n f . P r o c . 4 0 , 2 (1978).
13. D.E. Aspnes, Thin Solid Films 8 9 , 249 (1982).
14. G . A . N i k l a s s o n a n d C . G . G r a n q v i s t , in Contribution of Cluster Physics to
Materials Science and Technology, edited by J. Davenas and P.M. Rabette
( M a r t i n u s Nijhoff, D o r d r e c h t , 1 9 8 6 ) , p. 5 3 9 .
15. O. Wiener, Abh. Sachs. Akad. Wiss. Leipzig, Math.-Naturwiss. Kl. 32, 509
(1912).
16. Z . H a s h i n a n d S. S h t r i k m a n , J . A p p l . P h y s . 3 3 , 3 1 2 5 ( 1 9 6 2 ) .
17. D.J. Bergman, Ann. Phys. (N.Y.) 138, 78 (1982).
18. G . W . M i l t o n , J . A p p l . P h y s . 5 2 , 5 2 8 6 , 5 2 9 4 (1981).
19. C F . B o h r e n , J. A t m o s . S c i . 4 3 , 4 6 8 ( 1 9 8 6 ) .
20. H . C v a n d e H u l s t , Multiple Light Scattering. Tables, Formulas and
Applications ( A c a d e m i c , N e w Y o r k , 1 9 8 0 ) , V o l s . 1 a n d 2.
21. A . I s h i m a r u , Wave Propagation and Scattering in Random Media
( A c a d e m i c , N e w Y o r k , 1 9 7 8 ) , V o l s . 1 a n d 2.
22. W . G . E g a n a n d T . W . H i l g e m a n , Optical Properties of Inhomogeneous
Materials (Academic, N e w York, 1979).
23. G . A . N i k l a s s o n , J . A p p l . P h y s . 6 2 , 2 5 8 (1987).
24. F . L a d o a n d S. T o r q u a t o , P h y s . R e v . Β 3 3 , 3 3 7 0 ( 1 9 8 6 ) ; S. T o r q u a t o a n d F .
L a d o , P h y s . R e v . Β 3 3 , 6 4 2 8 (1986).
25. J . D . B e a s l e y a n d S. T o r q u a t o , J. A p p l . P h y s . 6 0 , 3 5 7 6 ( 1 9 8 6 ) .
26. B.U. Felderhof, Physica 1 2 6 A , 430 (1984).
27. S. T o r q u a t o a n d G . Stell, J . C h e m . P h y s . 79, 1 5 0 5 ( 1 9 8 3 ) ; S. T o r q u a t o , J . C h e m .
P h y s . 8 4 , 6 3 4 5 (1986).
28. A . H j o r t s b e r g , A p p l . O p t . 2 0 , 1 2 5 4 (1981).
29. J . D . J a c k s o n , Classical Electrodynamics (Wiley, N e w York, 1975).
30. M . B o r n a n d E . W o l f , Principles of Optics, s i x t h e d i t i o n , ( P e r g a m o n , O x f o r d ,

1 9 8 0 ) ; O . S . H e a v e n s , Optical Properties of Thin Solid Films (Butterworth,
London, 1955).
31. V . A r k a d i e v , J . P h y s . (U.S.S.R.) 9 , 3 7 3 ( 1 9 4 5 ) .
32. P. G r o s s e , Freie Elektronen in Festkorpern (Springer, Berlin, 1979).
33. D . E . G r a y , e d i t o r , American Institute of Physics Handbook ( M c G r a w Hill,
N e w Y o r k , 1 9 6 3 ) ; W . G . D r i s c o l l a n d W . V a u g h a n , e d i t o r s , Handbook of
Optics ( M c G r a w - H i l l , N e w Y o r k , 1 9 7 8 ) ; E . D . P a l i k , e d i t o r , Handbook of
Optical Constants of Solids ( A c a d e m i c , N e w Y o r k , 1 9 8 5 ) .
34. J . H . W e a v e r , C . K r a f k a , D . W . L y n c h a n d E . E . K o c h , Optical Properties of
Metals, Pts. I and II, Physics Data No. 18 ( F a c h i n f o r m a t i o n s z e n t r u m E n e r g i e ,
Physik, Mathematik, Karlsruhe, 1981).
35. D.J. B e r g m a n , P h y s . R e v . Lett. 4 4 , 1 2 8 5 (1980); P h y s . R e v . Β 2 3 , 3 0 5 8 ( 1 9 8 1 ) .
36. G . W . M i l t o n , A p p l . P h y s . Lett. 3Z, 3 0 0 (1980).
37. G . W . M i l t o n a n d R . C . M c P h e d r a n , in Macroscopic Properties of Disordered
Media, e d i t e d b y R. B u r r i d g e , S. C h i l d r e s s a n d G . P a p a n i c o l a o u , L e c t u r e
N o t e s in P h y s i c s , V o l . 1 5 4 ( S p r i n g e r , B e r l i n , 1 9 8 2 ) , p. 1 8 3 .
38. D . J . B e r g m a n , P h y s . R e p . 4 3 , 3 7 7 (1978).
39. R.C. McPhedran and G.W. Milton, Appl. Phys. A 26, 207 (1981).
40. G . W . M i l t o n , A p p l . P h y s . A 2 6 , 1 2 5 (1981).
41. K. Golden, J. Mech. Phys. Solids 3 4 , 333 (1986).
42. D.J. Bergman, T A U P 1313-85, unpublished.
43. G . B . S m i t h , J . P h y s . D 1 0 , L 3 9 (1977); A p p l . P h y s . Lett. 3 5 , 6 6 8 ( 1 9 7 9 ) .
44. W . L a m b , D . M . W o o d a n d N . W . Ashcroft, P h y s . R e v . Β 2 1 , 2 2 4 8 ( 1 9 8 0 ) .
45. G . A . N i k l a s s o n , C . G . G r a n q v i s t a n d O. H u n d e r i , A p p l . O p t . 2 0 , 2 6 ( 1 9 8 1 ) .
46. C . F . B o h r e n a n d D . P . G i l r a , J . C o l l o i d Interface S c i . 7 2 , 2 1 5 ( 1 9 7 9 ) .
47. H . C . v a n d e H u l s t , Light Scattering by Small Particles ( D o v e r , N e w Y o r k ,
1981).
48. R . J . Elliot, J . A . K r u m h a n s l a n d P . L . L e a t h , R e v . M o d . P h y s . 4 6 , 4 6 5 ( 1 9 7 4 ) .
49. D . S t r o u d a n d F.P. P a n , P h y s . R e v . Β 17, 1 6 0 2 ( 1 9 7 8 ) .
50. M . K e r k e r , The Scattering of Light and Other Electromagnetic Radiation
(Academic, N e w York, 1969); C.F. Bohren and D.R. Huffman, Absorption
and Scattering of Light by Small Particles (Wiley, N e w York, 1983).
51. J . C . M a x w e l l G a r n e t t , P h i l o s . T r a n s . R. S o c . ( L o n d o n ) 2 0 3 , 3 8 5 ( 1 9 0 4 ) ; 2 0 5 , 2 3 7
(1906).
52. W.T. Perrins, R.C. McPhedran and D.R. McKenzie, Thin Solid Films 57, 321
(1979).
53. R . C . M c P h e d r a n a n d D . R . M c K e n z i e , P r o c . R . S o c . ( L o n d o n ) 3 5 9 , 4 5 (1978).
54. W . T . D o y l e , J . A p p l . P h y s . 4 9 , 7 9 5 (1978).
55. D . R . M c K e n z i e , R . C . M c P h e d r a n a n d G . H . D e r r i c k , P r o c . R. S o c . ( L o n d o n )
3 6 2 , 2 1 1 (1978).
56. D.A.G. Bruggeman, Ann. Phys. (Leipzig) 24, 636 (1935).
57. P. S h e n g , P h y s . R e v . Lett. 4 5 , 6 0 ( 1 9 8 0 ) .
58. T. H a n a i , K o l l o i d Z . 17L 2 3 (1960).
59. C. G r o s s e , J. C h i m . P h y s . 7 6 , 1 5 3 (1979); C. G r o s s e a n d J . - L . Greffe, J . C h i m .
P h y s . 7 6 , 3 0 5 (1979).
60. C. B o n e d a n d J. P e y r e l a s s e , J . P h y s . D 1 6 , 1 7 7 7 ( 1 9 8 3 ) ; C o l l o i d P o l y m . S c i .
261, 600 (1983).
61. U.J. Gibson, H.G. Craighead and R.A. Buhrman, Phys. Rev. Β 2 5 , 1449 (1982).
62. U . J . G i b s o n a n d R . A . B u h r m a n , P h y s . R e v . Β 2Z, 5 0 4 6 ( 1 9 8 3 ) .
63. M . O k u y a m a , K. F u r u s a w a a n d Y . H a m a k a w a , S o l a r E n e r g y 2 2 , 4 7 9 ( 1 9 7 9 ) .
64. J . Perrin, B . D e s p a x a n d E . K a y , P h y s . R e v . B 3 2 , 7 1 9 ( 1 9 8 5 ) ; E . K a y , Z. P h y s . D
3 , 2 5 1 (1986).
65. L . M a r t i n u , S o l a r E n e r g y M a t e r . 1 5 , 21 ( 1 9 8 7 ) .
66. R . W . C o h e n , G . D . C o d y , M . D . C o u t t s a n d B . A b e l e s , P h y s . R e v . B 8, 3 6 8 9
( 1 9 7 3 ) ; E . B . P r i e s t l e y , B . A b e l e s a n d R . W . C o h e n , P h y s . R e v . B 1 2 , 2 1 2 1 (1975).
67. J.C.C. F a n a n d P . M . Z a v r a c k y , A p p l . P h y s . Lett. 2 9 , 4 7 8 ( 1 9 7 6 ) .
68. J . I . G i t t l e m a n , B . A b e l e s , P. Z a n z u c c h i a n d Y . A r i e , T h i n S o l i d F i l m s 4 5 , 9
(1977).
69. C . G . G r a n q v i s t , J . A p p l . P h y s . 5 0 , 2 9 1 6 (1979).
70. S. B e r t h i e r , K . D r i s s - K h o d j a a n d J . Lafait, J . P h y s . (Paris) 4 8 , 6 0 1 ( 1 9 8 7 ) .
71. S. B e r t h i e r , K . D r i s s - K h o d j a a n d J . Lafait, E u r o p h y s . Lett. 4 , 1 4 1 5 ( 1 9 8 7 ) .
72. P. A p e l l , O. H u n d e r i a n d R . M o n r e a l , P h y s . S c r i p t a 3 4 , 3 4 8 ( 1 9 8 6 ) .
73. S. T o r q u a t o , J . Stat. P h y s . 4 5 , 8 4 3 (1986); P h y s . R e v . B 3 5 , 5 3 8 5 ( 1 9 8 7 ) .
74. S. T o r q u a t o a n d G . Stell, J . C h e m . P h y s . 7 7 , 2 0 7 1 (1982); 7 8 , 3 2 6 2 ( 1 9 8 3 ) .
75. M . Beran, N u o v o C i m e n t o 3 8 , 771 (1965).
76. B . U . Felderhof, J . P h y s . C 1 5 , 3 9 4 3 , 3 9 5 3 ( 1 9 8 2 ) .
77. B . B . M a n d e l b r o t , The Fractal Geometry of Nature ( F r e e m a n , N e w Y o r k ,
1983).
78. J . E . M a r t i n , J . P h y s . A 1 8 , L 2 0 7 (1985).
79. A . J . K a t z a n d A . H . T h o m p s o n , P h y s . R e v . Lett. 5 4 , 1 3 2 5 ( 1 9 8 5 ) .
80. M . V . B e r r y a n d I. P e r c i v a l , O p t . A c t a 3 3 , 5 7 7 ( 1 9 8 6 ) ; P M , H u i a n d D . S t r o u d ,
P h y s . R e v . Β 3 3 , 2 1 6 3 (1986).
81. S. T o r q u a t o a n d G . Stell, Lett. A p p l . E n g . Sci. 2 3 , 3 7 5 , 3 8 5 ( 1 9 8 5 ) .
82. S. T o r q u a t o , J . C h e m . P h y s . 8 3 , 4 7 7 6 (1985).
83. M . N . Miller. J . M a t h . P h y s . 1 0 , 1 9 8 8 (1969); 1 2 , 1 0 5 7 (1971).
84. Y . K a n t o r a n d D . J . B e r g m a n , J. P h y s . C 1 5 , 2 0 3 3 (1982).
85. A . L i e b s c h a n d B.N.J. P e r s s o n , J . P h y s . C 1 6 , 5 3 7 5 (1983); A . L i e b s c h a n d P . V .
Gonzalez, Phys. Rev. Β 2 9 , 6907 (1984).
86. M . G o m e z a n d L . F o n e s c a , T h i n S o l i d F i l m s 1 2 5 , 2 4 3 ( 1 9 8 5 ) ; M . G o m e z , L.
F o n e s c a , G . R o d r i g u e z , A . V e l a z q u e z a n d L. C r u z , P h y s . R e v . Β 3 2 , 3 4 2 9
(1985).
87. R . G . B a r r e r a , G . M o n s i v a i s a n d W . L . M o c h a n , P h y s . R e v . Β 3 8 , 5 3 7 1 (1988).
88. V . A . D a v i s a n d L . S c h w a r t z , P h y s . R e v . B 3 L 5 1 5 5 (1985); P h y s . R e v . Β 3 3 ,
6 6 2 7 (1986).
89. B . U . F e l d e r h o f a n d R . B . J o n e s , Z. P h y s . B . 6 2 , 4 3 , 2 1 5 , 2 2 5 , 2 3 1 ( 1 9 8 6 ) .
90. S. T o r q u a t o , J . A p p l . P h y s . 5 8 , 3 7 9 0 (1985).
91. G . A . N i k l a s s o n , S o l a r E n e r g y M a t e r . 17, 2 1 7 ( 1 9 8 8 ) .
92. C.G. Granqvist and R.A. Buhrman, J. Appl. Phys. 47, 2200 (1976).
93. S.R. F o r r e s t a n d T . A . W i t t e n , Jr., J . P h y s . A 1 2 , L I 09 ( 1 9 7 9 ) .
94. T. F a r e s t a m a n d G . A . N i k l a s s o n , J . P h y s . C o n d . M a t t e r 1, 2 4 5 1 ( 1 9 8 9 ) .
95. W.T. Doyle, Phys. Rev. I l l , 1067 (1958).
96. J . E u l e r , Z . P h y s . 13Z, 3 1 8 (1954).
97. A . G . M a t h e w s o n a n d H.P. M y e r s , P h y s . S c r i p t a 4 , 2 9 1 ( 1 9 7 1 ) .
98. H . G . H a g e m a n n , W . G u d a t a n d C. K u n z , D E S Y R e p o r t S R - 7 4 / 7 ( 1 9 7 4 ) .
99. T . S . E r i k s s o n , A . H j o r t s b e r g , G . A . N i k l a s s o n a n d C . G . G r a n q v i s t , A p p l . Opt.
2 0 , 2 7 4 2 (1981).
100. J . T . C o x , G. H a s s a n d J . B . R a m s e y , J . P h y s . (Paris) 2 5 , 2 5 0 (1964).
101. C . G . G r a n q v i s t , R . A . B u h r m a n , J . W y n s a n d A . J . S i e v e r s , P h y s . R e v . Lett. 3Z,
6 2 5 (1976).
102. G . A . N i k l a s s o n , S. Y a t s u y a a n d C . G . G r a n q v i s t , S o l i d S t a t e C o m m u n . 5 9 , 5 7 9
(1986).
103. C . G . G r a n q v i s t , Z . P h y s . Β 3 0 , 2 9 (1978).
104. W . A . Curtin and N . W . Ashcroft, Phys. Rev. B 3 L 3 2 8 7 (1985).
105. A. Wachniewski and H.B. McClung, Phys. Rev. Β 3 3 , 8053 (1986).
106. L . G e n z e l a n d U . K r e i b i g , Z. P h y s . Β 3 7 , 9 3 ( 1 9 8 0 ) .
107. P. C h y l e k a n d V . S r i v a s t a v a , P h y s . R e v . Β 2 7 , 5 0 9 8 ( 1 9 8 3 ) .
108. D . E . A s p n e s , P h y s . R e v . Β 2 5 , 1 3 5 8 (1982).
109. W . G . Egan and D.E. Aspnes, Phys. Rev. Β 26, 5313 (1982).
110. J . K . B e a s l e y , J . T . A t k i n s a n d F . W . B i l l m e y e r , J r . , in Electromagnetic
Scattering, edited b y R.L. Powell and R.S. Stein (Gordon and Breach, N e w
Y o r k , 1 9 6 7 ) , p. 7 6 5 .
111. P.S. Mudgett and L.W. Richards, Appl. Opt. 1 0 , 1485 (1971).
112. B . M a h e u , J . N . L e t u o l o u z a n a n d G . G o u s e b e t , A p p l . O p t . 2 3 , 3 3 5 3 (1984);
B. M a h e u and G. Gousebet, Appl. Opt. 2 5 , 1122 (1986).
113. G . H . G o e d e c k e , J . O p t . S o c . A m . 6 7 , 1 3 3 9 (1977).
114. G . A . N i k l a s s o n , A p p l . O p t . 2 6 , 4 0 3 4 (1987).
115. P. K u b e l k a a n d F . M u n k , Z. T e c h n . P h y s . H a , 4 6 4 ( 1 9 3 1 ) .
116. L.W. Richards, J. Paint Technol. 4 2 , 276 (1970).
117. T . K u n i m o t o , H . M . S h a f e y a n d T . T e r a m o t o , Bull. J S M E 2 2 , 1 5 8 7 ( 1 9 7 9 ) .
118. T . K u n i m o t o , Y . T s u b o i , S. I w a s h i t a a n d H . M . S h a f e y , in Solar World
Congress: Proc. Int. Solar Energy Soc. Congr. Perth 14-19 Aug. 1983, e d i t e d b y
S.V. S z o k o l a y ( P e r g a m o n , O x f o r d 1 9 8 4 ) , V o l . 3, p. 1 9 4 3 .
119. G.A. Niklasson and T.S. Eriksson, Proc. Soc. Photo-Opt. Instrum. Engr. 1016,
8 9 (1989).
120. A.M. Andersson, G.A. Niklasson and C G . Granqvist, Appl.Opt. 2 6 , 2164
(1987).
121. H . G . C r a i g h e a d , J . C h e n g a n d S. H a c k w o o d , A p p l . P h y s . Lett. 4 0 , 2 2 (1982).
122. F . v a n K o n y n e n b u r g , S. M a r s l a n d a n d J . M c C o y , P r o c . S o c . P h o t o - O p t .
I n s t r u m . E n g r . 8 2 3 , 143 (1987); S o l a r E n e r g y M a t e r . 1 9 , 2 7 ( 1 9 8 9 ) .
123. T.W. T o n g and C L . Tien, J. Thermal Insul. 4, 27 (1980).
124. D.R. Smith and E.V. Loewenstein, Appl. Opt. 14, 1335 (1975).
Chapter 3
TRANSPARENT INSULATION MATERIALS
W. Platzer and V. Wittwer
F r a u n h o f e r I n s t i t u t fur S o l a r e E n e r g i e s y s t e m e
Oltmannsstr. 22
D-7800 Freiburg, Germany
ABSTRACT
Transparent or translucent insulation materials (TIM's) represent a n e w class of

m a t e r i a l s w i t h a h i g h p o t e n t i a l for i n c r e a s i n g the efficiency o f s o l a r t h e r m a l
c o n v e r s i o n s y s t e m s . A l a r g e n u m b e r o f m a t e r i a l s h a v e b e e n s u b j e c t e d to t h e o r e -
tical a n d e x p e r i m e n t a l i n v e s t i g a t i o n , as d i s c u s s e d in this c h a p t e r . T h e
applications of TIM's include w i n d o w s , industrial glazings, high temperature
collectors, integrated storage collectors, seasonal heat storage systems, a n d
transparently insulated buildings.
I. INTRODUCTION
If o n e a n a l y s e s the e n e r g y c o n s u m p t i o n in i n d u s t r i a l i z e d c o u n t r i e s , o n e finds that

a b o u t 4 0 % o f t h e p r i m a r y e n e r g y is u s e d to p r o d u c e l o w t e m p e r a t u r e t h e r m a l
e n e r g y for h e a t i n g in d w e l l i n g s a n d i n d u s t r i a l b u i l d i n g s , d o m e s t i c h o t w a t e r a n d
l o w t e m p e r a t u r e i n d u s t r i a l p r o c e s s h e a t . T h i s i n d i c a t e s t h e g r e a t p o t e n t i a l for
t h e r m a l s o l a r e n e r g y u s e , a n d u t i l i s a t i o n s h o u l d b e p o s s i b l e e v e n in t h e C e n t r a l
European climate.
T h e r m a l s o l a r e n e r g y is u s e d in p a s s i v e s y s t e m s s u c h as g r e e n h o u s e s o r w i n d o w s .
In t h e a c t i v e s y s t e m s field, d e v e l o p m e n t s h a v e r e s u l t e d in r e l i a b l e c o l l e c t o r
s y s t e m s for s w i m m i n g p o o l s a n d d o m e s t i c h o t w a t e r . T h e m o s t r e c e n t w o r k in
b o t h a r e a s is o n h i g h l y efficient c o l l e c t o r s y s t e m s for p r o c e s s h e a t a n d n e w s y s t e m s
l i k e t r a n s p a r e n t l y i n s u l a t e d w a l l s w h i c h a r e d i s c u s s e d later.
T h e f u n d a m e n t a l p h y s i c a l p r i n c i p l e w h i c h is u s e d in all o f t h e s e a p p l i c a t i o n s is
t h e w a v e l e n g t h difference b e t w e e n t h e s o l a r r a d i a t i o n a b s o r b e d b y a d a r k s u r f a c e ,
w h i c h m a y b e a n a b s o r b e r o r a p e r t u r e to a r o o m , a n d t h e t h e r m a l r a d i a t i o n w h i c h
is e m i t t e d b y t h e h e a t e d a b s o r b e r o r r o o m . T h i s d i f f e r e n c e a l l o w s t h e u t i l i s a t i o n o f
selective cover layers m a d e of so-called transparent insulation materials (TIM's)
w h i c h a r e t r a n s p a r e n t for t h e s o l a r r a d i a t i o n a n d o p a q u e for t h e t h e r m a l r a d i a -
44
Transparent Insulation Materials 45
tion. A s a result, t h e I R - r a d i a t i o n l o s s e s o f t h e h e a t e d s y s t e m a r e r e d u c e d a n d the

s y s t e m is m o r e e f f e c t i v e t h a n o n e w i t h o u t a c o v e r . O f c o u r s e t h e r e a r e o t h e r h e a t
l o s s m e c h a n i s m s , b u t all o f t h e m a r e l e s s i m p o r t a n t . T h e m o s t p r o m i n e n t
c a n d i d a t e for s u c h a s e l e c t i v e c o v e r is a g l a s s p a n e , w h i c h fulfils t h e p h y s i c a l
r e q u i r e m e n t s q u i t e w e l l . T h e r e f o r e a g l a s s p a n e m a y b e r e g a r d e d as t h e s i m p l e s t
t y p e o f t r a n s p a r e n t i n s u l a t i o n m a t e r i a l . A s s h o w n later, a l a r g e n u m b e r o f
different T I M ' s a r e p o s s i b l e , v a r y i n1g in their p h y s i c a l c h a r a c t e r i s t i c d a t a a n d
s u i t a b l e for different a p p l i c a t i o n s . F r o m t h e p h y s i c a l p o i n t o f v i e w , h i g h
transmittance of solar radiation and l o w thermal conductivity w o u l d b e the best
combination, but other aspects are also important. High transmittance can cause
a n o v e r h e a t i n g p r o b l e m in g r e e n h o u s e s for e x a m p l e . S c a t t e r e d l i g h t m i g h t b e
b e t t e r t h a n d i r e c t l i g h t for d a y l i g h t i n g a p p l i c a t i o n s . E c o n o m i c a s p e c t s m a y b e
a n o t h e r r e a s o n to u s e different m a t e r i a l s in s y s t e m s for different a p p l i c a t i o n s .
If o n e l o o k s at t h e e n e r g y efficiency o f a t h e r m a l s y s t e m t h e r e a r e t w o critical
characteristics: the function o f the solar input w h i c h can b e absorbed b y the system
- depending on the solar transmittance o f the cover and the absorptance o f the
a b s o r b e r - a n d t h e p o r t i o n o f t h e h e a t p r o d u c e d in t h e s y s t e m w h i c h c a n b e s t o r e d
and used - depending mainly on the thermal insulation of the system (U-value).
For large energy gains one always needs a high irradiation level and a high
τα - product, w h e r e τ denotes the transmittance of the collector cover and α the
a b s o r p t a n c e o f t h e a b s o r b e r p l a t e , b u t t h e i n f l u e n c e o f t h e U - v a l u e is s t r o n g l y
d e p e n d e n t o n t h e t e m p e r a t u r e l e v e l o f the s y s t e m in c o m p a r i s o n t o t h e s u r r o u n -
d i n g s a n d t h e s t o r a g e t i m e . In s y s t e m s o n e t h e r e f o r e h a s to o p t i m i z e t h e T I M for
different applications.
T h e p r i n c i p l e c h a r a c t e r i s t i c s o f t h e n e w t y p e o f T I M w i l l b e d e m o n s t r a t e d in t h e
following example. A scientist has a black absorber insulated on the backside, an
air g a p o f 1 0 c m in front o f t h e a b s o r b e r a n d a c e r t a i n a m o u n t o f g l a s s sufficent to
c a s t a 5 m m t h i c k p a n e . H i s a i m is to o p t i m i s e t h e c o l l e c t o r for different a p p l i c a -
t i o n s b y v a r y i n g t h e s p a t i a l d i s t r i b u t i o n o f this a m o u n t o f g l a s s as s h o w n in F i g . 1.
P r o b a b l y h e w i l l start w i t h t h e s i n g l e g l a z e d c o l l e c t o r , w i l l g o o n to d o u b l e a n d
triple g l a z i n g , b u t t h e n h e w i l l s t o p for a m o m e n t , b e c a u s e h e finds t h a t o n t h e
o n e h a n d the thermal insulation gets better and better but o n the other h a n d the
t r a n s m i t t a n c e g e t s w o r s e . E v e n if h e u s e d e x p e n s i v e a n t i r e f l e c t i o n c o a t i n g s o r
l o w - r e f r a c t i v e - i n d e x m a t e r i a l s , at s o m e p o i n t t h e r e w o u l d b e a l i m i t in t h e f e a s i b l e
n u m b e r o f l a y e r s for s u c h a s y s t e m .
T o o v e r c o m e t h e s e r e f l e c t i o n p r o b l e m s , t h e s c i e n t i s t h a s to c h a n g e t h e g e o m e t r y .
B y r o t a t i n g t h e g l a s s b y 9 0 ° , h e n o l o n g e r h a s reflection l o s s e s , a n d for n o n -
s c a t t e r i n g a n d n o n - a b s o r b i n g m a t e r i a l s t h e t r a n s m i t t a n c e w i l l b e c l o s e to 1.0.
H o w e v e r , h e h a s to d o this v e r y carefully. I f his s t r u c t u r e is o p e n , h e w i l l g e t
l o s s e s d u e to c o n v e c t i o n a n d , w h a t m i g h t b e e v e n m o r e d e t r i m e n t a l , t h e r e w i l l b e
o n l y l o w d a m p i n g o f t h e t h e r m a l r a d i a t i o n . B y c o n t r a s t , if h e u s e s h o n e y c o m b
s t r u c t u r e s o r c a p i l l a r i e s w i t h a l a r g e a s p e c t ratio, h e w i l l g e t a c o v e r w i t h a h i g h
t r a n s m i t t a n c e a n d a l o w t h e r m a l c o n d u c t a n c e . A s a result, h e w i l l m e a s u r e that
n o w t h e t h e r m a l c o n d u c t i v i t y in t h e air, o f t h e m a t e r i a l (2g4l -a s s ) , a n d t h e t h e r m a l
radiation losses will b e of the same order o f m a g n i t u d e .
A r e t h e r e a n y further p o s s i b i l i t i e s to i m p r o v e t h e c h a r a c t e r i s t i c s o f t h e m a t e r i a l ?
F r o m the theoretical point of view, a h o m o g e n e o u s distribution of the 5 m m glass
a c r o s s t h e total v o l u m e o f 1 0 c m s h o u l d b e t h e b e s t . I n d e e d t h e r e e x i s t s s u c h a
m a t e r i a l w i t h n e a r l y i d e a l c h a r a c t e r i s t i c s ; it is c a l l e d a n a e r o g e l . T h e m a t e r i a l is
p r o d u c e d b y a s p e c i a l d r y i n g p r o c e s s from sol-gel g l a s s . It is a n o p e n p o r o u s
structure with typically 5 % v o l u m e occupied b y glass. T h e pore diameters are
w e l l b e l o w t h e w a v e l e n g t h s o f v i s i b l e light, a n d t h e r e f o r e o n e f i n d s o n l y a s m a l l
a m o u n t o f R a y l e i g h s c a t t e r i n g at s h o r t w a v e l e n g t h s . T h e t h e r m a l c o n d u c t i v i t y o f
t h e g a s is r e d u c e d as t h e m e a n free p a t h o f t h e m o l e c u l e s is l a r g e r t h a n t h e p o r e
s i z e , a n d e v e n t h e s o l i d s t a t e c o n d u c t i v i t y is d i m i n i s h e d b y t h e s t r u c t u r e o f t h e
m a t e r i a l in c o m p a r i s o n to g l a s s . In F i g . 1 t h e different m a t e r i a l s a r e s h o w n
schematically and the m a i n heat loss m e c h a n i s m s are indicated.
T a b l e 1 s h o w s t h e e x p e c t e d c h a r a c t e r i s t i c d a t a for p u r e g l a s s as t h e b a s e m a t e r i a l
and illustrates the principal potential o f optimizing a T I M b y varying o n l y the
spatial distribution of one material. Clearly the heat insulation can b e i m p r o v e d
b y a factor - 4 0 w i t h o u t c h a n g i n g t h e t r a n s m i t t a n c e v e r y m u c h .
In p r a c t i c a l a p p l i c a t i o n s , n o t o n l y t h e efficiency b u t a l s o t h e s i m p l i c i t y o f c o n s t -
r u c t i o n , t h e l o n g t e r m stability, a n d t h e cost a r e v e r y i m p o r t a n t . B e s i d e s g l a s s ,
m a n y p l a s t i c m a t e r i a l s c a n b e u s e d in a s i m i l a r w a y a n d , a s s h o w n l a t e r , in m o s t
r e a l s y s t e m s a c o m b i n a t i o n w i t h s p e c t r a l l y s e l e c t i v e s u r f a c e s , air g a p s , different g a s
fillings o r e v e n v a c u u m a r e u s e d .
T a b l e 1. Ideal values o f transmittance and thermal insulation

for a n a r r a n g e m e n t i n v o l v i n g p u r e g l a s s .
Configuration 1 pane 2 panes 3 panes honeycomb aerogel
Diffuse t r a n s -
mittance, i f : 0.85 0.77 0.71 0.95 0.77
d i
U-value: ( W / m 2 K ) 8 4 2.7 0.8 0.2
IL GENERIC TYPES OF TRANSPARENT INSULATION

MATERIALS
A l t h o u g h t h e r e is a m u l t i t u d e o f v e r y different m a t e r i a l t y p e s , a c l a s s i f i c a t i o n
shall b e a t t e m p t e d b e l o w . E a c h class o r t y p e t h e n s h o u l d b e d e s c r i b e d , at l e a s t
approximately, b y a theoretical model. T h e r e are m a n y criteria which could b e
u s e d for a c l a s s i f i c a t i o n s u c h as p r o d u c t i o n p r o c e s s , b a s e m a t e r i a l s , e n v i r o n m e n t a l
h a z a r d a s s o c i a t e d w i t h t h e m a t e r i a l u s e a n d p r o d u c t i o n , fire r e s i s t a n c e o r m e c h a -
n i c a l stability. T h e s e criteria a r e c e r t a i n l y i m p o r t a n t for t h e a p p l i c a t i o n , b u t for
the basic physics they are secondary. A physical criterion could b e the thermal
emittance of the material, which m e a n s a division into low-emitting and high-
e m i t t i n g m a t e r i a l s . T h i s w i l l b e a n i m p o r t a n t p o i n t w h e n t h e c o m b i n a t i o n o f the
m a t e r i a l s w i t h s p e c t r a l l y s e l e c t i v e a b s o r b e r s w i l l b e d i s c u s s e d . W i t h r e s p e c t to
o p t i c a l q u a l i t i e s o n e m a y a l s o classify t h e m a t e r i a l s a c c o r d i n g to t h e o p t i c a l p a t h o f
10 cm TIM Absorber
5mm
IR-radiation
> convection
IR-radiation
> convection
IR-radiation
~ air conduction
air conduction
> IR-radiation
m
air conduction
~ IR-radiation
a
-solid state conduction
air conduction
-solid state conduction
~ IR-radiation
Fig. 1. Sequential refinement of structures m a d e from the s a m e

amount o f glass, and main heat loss mechanisms.
a n i n c o m i n g b e a m : C l e a r g l a s s e s for i n s t a n c e c a n b e s e e n t h r o u g h , b u t diffusing
structures can not. Also there are structures which preserve the incidence angle
b u t still d o n o t a l l o w a c l e a r v i e w . B o t h criteria a r e p h y s i c a l l y m e a n i n g f u l , b u t
t h e r e is a c o n t i n u m o f m a t e r i a l s b e t w e e n t h e e x t r e m e c a s e s , a s is m a d e o b v i o u s b y
t h e e m i t t a n c e . H o w e v e r , m i x e d t y p e s a l s o e x i s t w i t h r e s p e c t t o their o p t i c a l
b e h a v i o u r . A h o n e y c o m b s t r u c t u r e p r o d u c e d f r o m w e a k l y s c a t t e r i n g p l a s t i c foils
d o e s n o t fully p r e s e r v e t h e i n c i d e n c e a n g l e for t h e t r a n s m i t t e d b e a m , b u t a l s o h a s
a s m a l l diffusing c o m p o n e n t . A classification a c c o r d i n g t o t h e g e o m e t r i c s t r u c t u r e
o f t h e m a t e r i a l s h a s p r o v e n t o b e r a t h e r useful. F o u r g e n e r i c t y p e s a r e p r o p o s e d ,
w h i c h s h o w different p h y s i c a l b e h a v i o u r a n d i n c l u d e m o s t r e a l m a t e r i a l s . They
a r e s h o w n in F i g . 2.
obsorber-paraUel
ο Multiple glazing
ο Plastic films
ο | R - r e f l e c t i v e glass
absorber-vertical
ο parallel slats
ο honeycombs
ο capillaries
cavity structure
ο duct plates
ο foam
(quasi-) homogeneous
ο glass fibers
ο aerogel
Fig. 2. Generic types of transparent insulation materials.
T h e first t y p e is t h e w e l l - k n o w n absorber-parallel cover with multiple glazings or

p l a s t i c s h e e t s , w h i c h m a y b e clear b u t a l s o diffusing. H i g h o p t i c a l reflection l o s s e s
prohibit the use of a large n u m b e r o f layers. T h e glass panes or plastic sheets have
d e f i n e d t e m p e r a t u r e s ( a p p r o x i m a t e l y c o n s t a n t ) b u t b e c a u s e o f c o n v e c t i o n in t h e
intervening gaps, a one-dimensional temperature distribution cannot b e given.
T h e absorber-vertical structures include h o n e y c o m b and capillary materials with

different c r o s s - s e c t i o n a l g e o m e t r i e s as w e l l as slit s t r u c t u r e s (plastic s h e e t s
s t r e t c h e d p a r a l l e l a c r o s s t h e c o l l e c t o r ) . A s t h e i n c o m i n g b e a m is r e f l e c t e d a n d
t r a n s m i t t e d b y t h e s t r u c t u r e w a l l s t o w a r d s the a b s o r b e r , o p t i c a l l o s s e s m a y b e v e r y
small, and only s o m e scattering and absorption within the sheets reduce the
overall transmittance. For clear sheets with low extinction, the transmission
p r o p e r t i e s a r e n e a r l y i n d e p e n d e n t o f t h e m a t e r i a l t h i c k n e s s . T h e r e f o r e v e r y thick
s a m p l e s m a y b e u s e d . C o n t r a r y to t h e first t y p e , t h e a b s o r b e r - p a r a l l e l s t r u c t u r e s ,
w h e r e c o n v e c t i o n is v e r y often p r e s e n t in p r a c t i c e , c o n v e c t i o n m a y b e effectively
s u p p r e s s e d w h e n t h e a s p e c t ratio (cell l e n g t h d i v i d e d b y cell w i d t h ) is c h o s e n w e l l .
If b o t h t y p e s a r e c o m b i n e d , o n e g e t s a cavity structure, r e p r e s e n t e d in r e a l i t y b y
t r a n s p a r e n t m u l t i p l e d u c t plates o r t r a n s p a r e n t f o a m w i t h b u b b l e s i z e s o f s o m e
millimetres. F r o m the optical viewpoint, these materials h a v e approximately the
s a m e t r a n s m i t t a n c e as a n e q u i v a l e n t m u l t i p l e s h e e t c o v e r , a s t h e r e f l e c t i o n is the
dominant loss, but they h a v e the advantage o f effectively suppressing the

convection.
Quasi-homogeneous layers are characterised by properties similar to those m e n -

tioned above, but they stem from other physical m e c h a n i s m s , n a m e l y scattering
a n d a b s o r p t i o n . A e r o g e l , a m i c r o p o r o u s "silicate f o a m " , b e l o n g s to this class.
B e c a u s e o f p o r e s w i t h s i z e s o f s o m e 1 0 0 Â , l i g h t is s c a t t e r e d w i t h i5 n 6t h e m a t e r i a l in
a n a l o g y w i t h t h e w e l l - k n o w n R a y l e i g h s c a t t e r i n g o f t h e b l u e s k y . ' G l a s s fibre
m a t e r i a l s d o n o t h a v e this h o m o g e n e i t y , as s i n g l e fibres c a n b e s e e n , b u t t h e y c a n
b e treated and analysed with similar methods.
F o r e a c h o f t h e four g e n e r i c t y p e s , t h e o r e t i c a l a p p r o a c h e s e x i s t w h i c h a r e c a p a b l e o f
a s a t i s f a c t o r y d e s c r i p t i o n o f t h e b a s i c features o f t h e m a t e r i a l s . O f c o u r s e transition
m a t e r i a l s e x i s t w h i c h c a n n o t b e strictly classified. F o l d e d o r V - c o r r u g a t e d foils a r e
s u c h e x a m p l e s . I f t h e c o r r u g a t i o n a n g l e is s m a l l , t h e c o v e r b e h a v e s e s s e n t i a l l y
l i k e a n a b s o r b e r - v e r t i c a l m a t e r i a l ; if t h e a n g l e is l a r g e , it b e h a v e s n e a r l y l i k e an
a b s o r b e r - p a r a l l e l c o v e r . A l s o h o n e y c o m b s t r u c t u r e s w i t h cells n o t v e r t i c a l l y
oriented with respect to the absorber are produced, which provide a transition
b e t w e e n t h e a b s o r b e r - p a r a l l e l a n d t h e c a v i t y s t r u c t u r e type. N e v e r t h e l e s s , t h e
g e n e r i c t y p e s p r o v i d e a useful a p p r o x i m a t i o n o f real m a t e r i a l s a n d a n u n d e r -
s t a n d i n g o f t h e s e t y p e s is n e c e s s a r y b e f o r e the m o r e c o m p l e x m a t e r i a l s m a y b e
tackled.
ΙΠ. THEORETICAL MODELS
T h e a i m o f a t h e o r e t i c a l d i s c r i p t i o n o f a T I M is to g i v e p o s s i b i l i t i e s to o p t i m i s e the
physical behaviour o f the materials. T h e choice o f base material, the geometrical
structure o f the T I M and fundamental physical b o u n d a r y conditions influence
heat transport processes and solar transmittance. Therefore these parameters
h a v e to b e i n c l u d e d in t h e m o d e l s . H o w e v e r , m o d e l s a r e b o u n d to i d e a l i s e a n d to
d e s c r i b e p h y s i c a l r e a l i t y o n l y to a c e r t a i n l e v e l o f s o p h i s t i c a t i o n . T h e o r e t i c a l
c a l c u l a t i o n s h a v e t h e a d v a n t a g e o f y i e l d i n g c o n t i n u o u s f u n c t i o n s for i m p o r t a n t
parameters, whereas experiments can only give single data points b e c a u s e the
n u m b e r o f e x p e r i m e n t s is l i m i t e d .
F o r T I M ' s c e r t a i n l y t h e h e a t r e s i s t a n c e R o r its i n v e r s e , t h e h e a t c o n d u c t a n c e
Λ = 1 / R , a n d t h e s o l a r t r a n s m i t t a n c e τ a r e the m o s t i m p o r t a n t p h y s i c a l v a l u e s . If
s y s t e m s as a w h o l e a r e o f interest, t h e n t h e h e a t transfer coefficients, h , b e t w e e n
t
s u r f a c e s a n d air a l s o h a v e to b e c o n s i d e r e d s i n c e t h e y i n f l u e n c e t h e h e a t l o s s e s
( U - v a l u e s ) a n d the s o l a r g a i n s ( c h a r a c t e r i s e d b y t h e total e n e r g y t r a n s m i t t a n c e g o f
t h e s y s t e m , w h i c h is a l s o c a l l e d t h e effective t r a n s m i t t a n c e a b s o r p t a n c e p r o d u c t
( x a ) in t h e s o l a r c o l l e c t o r field (Ref. 7 ) ) . A b s o r b e d s o l a r r a d i a t i o n w i t h i n t h e
e
m a t e r i a l m a y f l o w to different e x t e n t s to the a m b i e n t a n d to t h e c o l l e c t o r , d e p e n -
d i n g for i n s t a n c e o n t h e e m i t t a n c e o f t h e a b s o r b e r o r t h e w i n d v e l o c i t y a t t h e o u t e r
surface. A s t h e r e a r e s e v e r a l c l a s s e s o f m a t e r i a l s , a c c o r d i n g l y different m o d e l s
e x i s t for c a l c u l a t i n g h e a t transfer a n d t r a n s m i t t a n c e .
T h e first s y s t e m to b e c o n s i d e r e d is a m u l t i p l e c o v e r (e.g., d o u b l e g l a z i n g ) . I f t h e
t r a n s m i t t a n c e a n d t h e r e f l e c t a n c e v a l u e s for t h e front a n d b a c k s i d e s o f e a c h s i n g l e
layer are given, then several methods allow the overall properties, including the
a b s o r p t i o n , for m u l t i p l e l a y e r s8to b e c a l c u l a t e d . W e can m e n t i o n t h9e n e t flux
m e t h o d o f S i e g e l a1n0d H o w e l l , t h e e m b e d d i n g m e t h o d o f E d w a r d s a n d a m a t r i x
method of Rubin. O f course, the equations of these computational methods are
v a l i d o n l y for s p e c i f i e d v a l u e s o f i n c i d e n c e a n g l e φ, p o l a r i s a t i o n , a n d w a v e l e n g t h .
H o w e v e r , a p p r o x i m a t i o n s m a y b e tried for i n t e g r a t e d q u a n t i t i e s i f t h e a c c u r a c y
d o e s n o t n e e d to b e t o o h i g h a n d t h e n u m b e r o f l a y e r s is s m a l l ( < 3 ) . F o r d i e l e c t r i c
layers, the properties m a y b e calculated easily from the index o f refraction and the
a b s o r p t i o n coefficient (e.g., Ref. 1 1 ) . I f t h e l a y e r s a r e n o t c l e a r , b u t at l e a s t p a r t l y
diffusive, t h e i n p u t for t h e m u l t i p l e c o v e r m o d e l n e e d s12t h e b i d i r e c t i o n a l e n t i t i e s
τ(φί , φ ι ) , etc., a n d a m a t r i x c a l c u l a t i o n h a s to b e u s e d .
η ο υ
Radiation heat 1 t3r a n s p o r t is e a s i l y c a l c u l a t e d w i t h i n a m u l t i p l e g l a z i n g b y a f o r m -
ula of Pfluger. T h e h e a t transfer, i n c l u d i n g t h e c o u p l e d c o n v e1 c4t i v e a n d i n f r a r e d
r a d i a t i o n t r a n s p o r t , w a s first d e s c r i b e d b y H o l l a n d s a n d W r i g h t . I f the a b s o r p -
tion w i t h i n the different l a y e r s is k n o w n , t h e g - v a l u e m a y a l s o b e c a l c u l a t e d .
T h e m e t h o d s for m u l t i p l e c o v e r m a t e r i a l s a r e d e v e l o p e d , a n d t h e c h o i c e o f
m e t h o d and degree of sophistication depend on the question considered.
For thicker materials, w h e r e an appreciable temperature distribution within the

layer m a y be noticed, other models should be used. A relatively easy method
e x i s t s for "grey" a b s o r b i n g a n d s c a t t e r i n g l a y e r s (like a e r o g e l a n d fibre i n s u l a t i o n ) ,
w h e n the spectral dependence can be ignored. T h e IR-radiation transport m a y be
a c c u r a t e l y d e s8
c r15
i b e d b y m e t h o d s d e v e l o p e d for h e a t t r a n s p o r t in g a s e s a n d stellar
atmospheres. ' I s o t r o p i c s c a t t e r i n g is e a s y to h a n d l e e v e n w i t h a n a l y t i c a l
m e t h o d s . H o w e v e r , i f t h e p h a s e - f u n c t i o n o f t h e s c a t t e r i n g p a r t i c l e is a n i s o t r o p i c ,
e i t h e r an a p p r o x i m a t e r e1s c16 7a l i n g m a y b e tried o r o n e m u s t r e s o r t to n u m e r i c a l o r
Monte Carlo m e t h o d s . '
H o w e v e r t h e s p e c t r a l v a r i a t i o n s i n e x t i n c t i o n , w h i c h is t h e s u m o f a b s o r p t i o n a n d
s c a t t e r i n g , m a y c a u s e p r o b l e m s . T h e q u e s t i o n o f t h e "true"1 168 equivalent extinction
coefficient for "grey" m o d e l s is still u n d e r d i s c u s s i o n . '
W h e n t h e l a y e r is n o t a h o m o g e n e o u s m a t e r i a l , b u t a g e o m e t r i c a l s t r u c t u r e w i t h
vertical walls like a h o n e y c o m b , the angular variation of emission and transmis-
s i o n w i t h i n t h e s t r u c t u r e is i m p o r t a n t . T h e I R - r a d i a t i o n t r a n s p o r t c a n b e c a l 1c u1
l7
a2-9
0
ted v e r y w e l l f r o m a m o d e l s i m i l a r to the o n e u s e d for s o l a r t r a n s m i t t a n c21e , ' '
w h e r e t h e a n g u l a r v a r i a t i o n o f e m i t t a n c e is e x p l i c i t l y t a k e n i n t o a c c o u n t . The
I R - t r a n s m i t t a n c e is n e e d e d22 as i n p u t for t h e r e f o r m u l a t e d r a d i a t i o n t r a n s p o r t
equation of a thick l a y e r . T h e coupling b e t w e e n the conduction within sheet
a n d air a n d t h e r a d i2 a3t i o n t r a n s p o r t c a n b e s o l v e d b y a n a n a l y t i c a l m e t h o d
d e v e l o p e d b y C e s s for h o m o g e n e o u s m17 edia, w h e r e an effective volumetric
a b s o r p t i o n coefficient h a s b e e n d e f i n e d .
T h e a g r e e m e n t b e t w e e n e x p e r i m e n t a l d a t a a n d t h e o r e t i c a l c a l c u l a t i o n s is r e m a r k -
a b l y g o o d , as s h o w n in F i g . 3. I f solar r a d i a t i o n is p r e s e n t , v o l u m e t r i c h e a t i n g o f
t h e m a t e r i a l s b y a b s o r p t i o n also has to b e c o n s i d e r e d . T h i s c a n b e d o n e , at l e a s t
a p p r o x i m a t e l y , w i t h t h e m e t h o d s m e n t i o n e d , so t h e s e c o n d a r y h e a t g a i n f r o m
solar absorption also m a y b e calculated.
/Heattransport within honeycombs \

\ Experiment and theory /
2.5 η — 7
1
^ 2.0- ^
UO-f- 1 1 1 1 .
1.0 1.5 2 2.0 2.5
Λ β ρχ[W/m K]
Fig. 3. Comparison between experimental and theoretical

v a l u e s o f t h e h e a t c o n d u c t a n c e for different h o n e y c o m b
m a t e r i a l s w i t h a s p e c t ratios b e t w e e n 5 a n d 2 2 .
A p r o b l e m for m o s t c a l c u l a t i o n s is t h e c h o i c e o f p r o p e r i n p u t d a t a . T h e g e o m e t r i c
s t r u c t u r e o f real m a t e r i a l s is v e r y often far f r o m r e g u l a r , a n d in p a r t i c u l a r h o n e y -
c o m b s m a y h a v e varying sheet thicknesses and aspect ratios. Also, getting reliable
I R - a b s o r p t i o n d a t a for m a t e r i a l s l i k e a e r o g e l , w h i c h c a n h a v e v e r y different s p e c t -
ral b a n d s , is difficult. B e c a u s e o f t h e s e p r o b l e m s , it is n o t y e t c l e a r w h e n n o n -
s p e c t r a l c a l c u l a t i o n s w i t h a v e r a g e d i n p u t d a t a a r e sufficient a n d w h e n e x a c t
s p e c t r a l c a l c u l a t i o n s a r e n e c e s s a r y . R e s u l t s for h o n e y c o m b s a n d a e r o g e l s i n d i c a t e
t h a t t h e first m a t e r i a l t y p e is r a t h e r w e l l d e s c r i b e d b y t h e s i m p l1e r178m e t h o d , w h e r e a s
n o n - s p e c t r a l m e t h o d s often p r o d u c e l a r g e e r r o r s for a e r o g e l s . '
IV. EXPERIMENTAL CHARACTERIZATION
S e v e r a l b a s i c e x p e r i m e n t a l s e t - u p s for m e a s u r i n g t h e f u n d a m e n t a l p h y s i c a l
v a l u e s a r e d e s c r i b e d in t h e f o l l o w i n g s e c t i o n . O t h e r e x p e r i m e n t s , y i e l d i n g s p e c t r a l
i n f o r m a t i o n , s c a t t e r i n g p h a s e f u n c t i o n s etc., a r e 24
s o m e t i m e s n e c e s s a r y to fully
u n d e r s t a n d a m a t e r i a l l i k e a e r o g e l for e x a m p l e , b u t a d i s c u s s i o n o f t h e s e a s p e c t s
w o u l d g o b e y o n d t h e s c o p e o f this c h a p t e r .
A. Measurement of Solar Transmittance and Reflectance

F o r s o l a r e n e r g y a p p l i c a t i o n s , it is n o t n e c e s s a r y to b e a b l e to s e e c l e a r l y t h r o u g h a
c o l l e c t o r c o v e r . I n s t e a d , all o f t h e t r a n s m i t t e d l i g h t r e a c h i n g t h e a b s o r b e r is o f
r e l e v a n c e , e v e n w h e n this l i g h t h a s b e e n s c a t t e r e d o r r e f l e c t e d . T h e r e f o r e t h e
d i r e c t - h e m i s p h e r i c a l o r diffuse t r a n s m i t t a n c e x ^ f (φ, ρ ) , d e p e n d i n g o n t h e
i n c i d e n c e a n g l e s φ ( p o l a r ) a n d ρ ( a z i m u t h ) , is i m p o r t a n t . V e r y often a n a z i m u t h a l
d e p e n d e n c e d o e s n o t e x i s t (e.g., for u s u a l g l a z i n g s ) o r is n e g l i g i b l e (for m o s t
honeycombs).
Diffuse t r a n s m i t t a n c e c a n b e m e a s u r e d b y a n i n t e g r a t i n g s p h e r e , for w h i c h t h e
l i g h t e n t e r i n g f r o m all d i r e c t i o n s c o n t r i b u t e s to a h o m o g e n e o u s r a d i a n c e2 o75f t-h e2
sphere walls (apart from certain spots) because of multiple r e f l e c t i o n s . Small
s p h e r e s for s p e c t r o m e t e r s c o m m o n l y u s e a d o u b l e - b e a m g e o m e t r y , w h e r e a s l a r g e
s p h e r e s s u i t a b l e for T I M ' s a r e s i n g l e - b e a m d e v i c e s , as s h o w n in F i g . 4 . H e r e a
detector measures the radiance of a selected part of the sphere wall, w h e r e no
direct light from the entrance port should be incident. M e a s u r e m e n t s with and
w i t h o u t t h e s a m p l e in front o f t h e e n t r a n c e p o r t g i v e a r a w v a l u e for t h e t r a n s -
m i t t a n c e , w h i c h h a s to b e c o r r e c t e d b e c a u s e the s e n s i t i v i t y o f t h e s p h e r e c h a n g e s
s o m e w h a t d e p e n d i n g o n the r e f l e c t a n c e o f the s a m p l e . A c o l l i m a t e d b e a m o f
diameter d irradiates a s a m p l e with dimension D , having a structure with typical
d i m e n s i o n δ (say t h e b u b b l e d i a m e t e r o f a n a c r y l i c f o a m o r the cell w i d t h o f a
h o n e y c o m b ) . T h e r a d i a t i o n t r a v e r s e s t h e s a m p l e a n d hits t h e s p h e r1e 27 en20t r28
9
ance
p o r t w i t h d i a m e t e r a. N o w t w o different set-ups a r e c o n c e i v a b l e : ' ' ' E i t h e r
t h e b e a m d i a m e t e r is m u c h s m a l l e r t h a n t h e e n t r a n c e p o r t a n d t h e s a m p l e ( D ~ a
» d » δ ) , or a l a r g e s a m p l e is h o m o g e n e o u s l y i r r a d i a t e d ( D « d » a » δ ) . A s the
sample
4\
halogen-metal
lamp light beam
chopper
diffusor rotating disk
'sandblasted
1 1
{ quartz I 0.123 -3 I j
V reterence Z _ _ signal y
integrating sphere
with pyroelectric detector
Fig. 4 . E x p e r i m e n t a l s e t - u p for a n a n g l e - d e p e n d e n t t r a n s m i t t a n c e
m e a s u r e m e n t using an integrating sphere. T h e configuration
uses a single-beam and large area illumination.
s p h e r e d i a m e t e r h a s to b e m u c h l a r g e r t h a n t h e d i a m e t e r o f t h e e n t r a n c e p o r t , to
k e e p t h e c o r r e c t i o n s s m a l l , t h e first s e t - u p calls for v e r y l a r g e s p h e r e s , w h e r e a s for
the second set-up the requirements on radiation h o m o g e n e i t y and intensity m a y
b e difficult t o m e e t . It is i m p o r t a n t for b o t h d e s i g n s t o h a v e a s t r o n g r a d i a t i o n
s o u r c e for p a r a l l e l l i g h t ( l a m p w i t h c o l l i m a t o r ) , w i t h a s p e c t r a l i n t e n s i t y distri-
b u t i o n c l o s e to that o f t h e terrestrial s o l a r s p e c t r u m , a n d a s p e c t r a l l y n o n - s e l e c t i v e
d e t e c t o r for t h e r e g i o n 0.3 to 2.5 μπι. P y r o e l e c t r i c d e t e c t o r s offer t h e b e s t s e n s i t i v -
ity, b u t t h e r m o p i l e s m a y b e a l s o u s e d i f t h e p o w e r o f t h e i l l u m i n a t i o n is l a r g e
e n o u g h . T h e c o a t i n g o f t h e i n t e g r a t i n g s p h e r e s h o u l d b e a diffusing o n e w i t h
h i g h r e f l e c t a n c e in t h e w h o l e r e l e v a n t w a v e l e n g t h r e g i o n . F o r v e r y l a r g e s p h e r e s ,
i n n e r c o30a t i n g s o f H a l o n ( p r e s s e d P o l y t e t r a f l u o r e t h y l e n e p o w d e r , P T F E ) is t h e b e s t
c h o i c e , b u t is difficult t o a p p l y . F o r t h e s a m e r e a s o n , s m o k e d M g O is p r e f e r a b l e
o n l y for s m a l l s p h e r e s . B a S Ô - p o w d e r - b a s e d p a i n t s a r e r e l a t i v e l y e a s y to a p p l y ,
4
but a binder other than water should b e used because o f the strong absorption
b a n d s o f w a t e r in t h e n e a r infrared.
R e f l e c t a n c e m e a s u r e m e n t s in p r i n c i p l e c a n a l s o b e m a d e w i t h a n i n t e g r a t i n g
s p h e r e , w i t h a n a d d i t i o n a l s a m p l e p o r t in t h e r e a r p a r t o f t h e s p h e r e . T h e light
e n t e r s t h e front e n t r a n c e p o r t a n d is r e f l e c t e d f r o m a r e f e r e n c e s u r f a c e o r f r o m t h e
s a m p l e i n t o t h e s p h e r e . F o r e a c h i n c i d e n c e a n g l e o n e n e e d s a s e p a r a t e o p e n i n g for
t h e i n c o m i n g light. A further p r o b l e m s t e m s f r o m t h e s c a t t e r e d l i g h t in t h i c k
samples: radiation, although scattered or reflected b a c k towards the sphere, m a y
n o t r e t u r n t h r o u g h t h e s a m p l e port. L a r g e s a m p l e p o r t s a n d s m a l l b e a m
d i a m e t e r s a r e u s u a l l y n e c e s s a r y , s o that t h e lost p a r t o f t h e r a d i a t i o n is n o t t o o
l a r g e . A s a c o n s e q u e n c e t h e m e a s u3 r1e d r e f l e c t a n c e for t h i c k s c a t t e r i n g s a m p l e s is
often s m a l l e r t h a n t h e t r u e v a l u e .
B. Measurement of Heat Transport
F o r t h e m e a s u r e m e n t o f total h e a t t r a n s p o r t w i t h i n T I M ' s , in p r i n c i p l e a n y h o t -
p l a t e a p p a r a t u s for d e t e r m i n a t i o n o f U - v a l u e s c a n b e u s e d , as d e s c r i b e d in t h e
standards (ISO, D I N 4757 (German Industrial Standard)). Since the materials are
p a r t i a l l y t r a n s p a r e n t to I R - r a d i a t i o n , t h e e m i s s i v i t y o f the s u r f a c e s in t h e
apparatus should b e k n o w n and be interchangeable.
T o d e t e r m i n e c o n v e c t i o n p r o p e r t i e s o f t h e s a m p l e s for v a r y i n g i n c l i n a t i o n , t h e
w h o l e apparatus should b e rotatable b y 180 degrees. T h e 180° position (hot plate
o n t o p o f a h o r i z o n t a l m a t e r i a l ) is u s e d to d e t e r m i n e t h e h e a t t r a n s p o r t w i t h o u t
c o n v e c t i o n . T h e d i f f e r e n c e for a n y o t h e r p o s i t i o n to this v a l u e g i v e s t h e c o n v e c -
tive p a r t o f t h e h e a t t r a n s p o r t a n d m a y b e e x p r e s s e d in t e r m s o f t h e N u s s e l t
n u m b e r N u . F o r e x a c t a n d fast m e a s u r e m e n t , a h o t - p l a t e a p p a r a t u s w i t h h e a t flux
m e t e r s o n b o t h p l a t e s is a d v a n t a g e o u s (e.g., Ref. 1 3 ) . U s u a l l y r e s u l t s a r e s h o w n as
a f u n c t i o n o f the d i m e n s i o n l e s s R a y l e i g h n u m b e r R a , w h i c h i n c o r p o r a t e s
thickness and temperature difference across the material.
F i g u r e 5 s h o w s t h e N u s s e l t n u m b e r s for 10 c m s q u a r e h o n e y c o m b s w i t h a s p e c t
r a t i o s ( t h i c k n e s s d i v i d e d b y cell w i d t h ) 5 a n d 1 0 a n d i n c l i n a t i o n 4 5 ° . O n e c a n s e e
t h a t for t h e s e c o n d s a m p l e , c o n v e c t i o n is n e g l i g i b l e for s o l a r t h e r m a l a p p l i c a t i o n
( b e l o w a t e m p e r a t u r e difference b e t w e e n t h e h o t a n d t h e c o l d s i d e , Δ Τ , o f 1 0 0 ° C ) .
It s h o u l d b e n o t e d , h o w e v e r , t h a t this o b s e r v a t i o n is v a l i d o n l y for t h e m a t e r i a l
t h i c k n e s s 10 c m . F o r t h i c k e r m a t e r i a l s , t h e R a n u m b e r i n c r e a s e s r a p i d l y , w h e r e a s
for 5 c m t h i c k n e s s , for e x a m p l e , an a s p e c t r a t i o o f 6 to 8 m a y b e e n o u g h t o s u p p r e s s
c o n v e c t i o n . R e s u l t s s h o w a l s o t h a t t h e m a x i m u m o f t h e N u s s e l t n u m b e r for
c o n s t a n t R a is b e t w e e n 3 0 ° a n d 4 5 ° i n c l i n a t i o n a n g l e (Fig. 6 ) .
/ Convection in quadratic honeycombs

\ Influence 0ofm
caspect ratio
VSsT^ · aspect A=5 ° aspect A=10
9.0-
Z3
u 7.0- τ /
ί 5.0- J
% /
W
W
-
ëy
2 3.0- f
1.0 ,1 * i , ,
0.0 2.0 4.0 6.0 8.0 10.0e
Rayleigh number Ra *10
Fig. 5. Convection suppression o f square h o n e y c o m b materials (10 cm
t h i c k n e s s ) w i t h a s p e c t ratios o f 5 a n d 10 e x p r e s s e d b y N u s s e l t
number (Nu = 1 means no convection).
W h e n t h e h e a t t r a n s p o r t o f a c o l l e c t o r t y p e s y s t e m is m e a s u r e d , c o n v e c t i o n is
p r e s e n t n o t o n l y w i t h i n t h e m a t e r i a l s b u t a l s o in t h e air g a p s . T h e m a i n i m p a c t o f
i n t r o d u c i n g air g a p s in s y s t e m s w i t h a l o w e m i s s i v e s u r f a c e is to r e d u c3e 3 2t3h e
radiation-conduction coupling b e t w e e n the absorber surface and T I M . * Figure
7 s h o w s m e a s u r e d a n d c a l c u l a t e d U - v a l u e s for a set-up w i t h a 10 c m h o n e y c o m b
m a t e r i a l , a v a r i a b l e air g a p , a n d a s p e c t r a l l y s e l e c t i v e a b s o r b e r h a v i n g a h e m i s p h e -
rical e m i t t a n c e , ε^, o f 0.08. N o c o n v e c t i o n is p r e s e n t in t h e s y s t e m . A s a c o m p a -
r i s o n , t h e d a s h e d l i n e s h o w s t h e h y p o t h e t i c a l a d d i t i v e U - v a l u e if n o c o u p l i n g
e x i s t e d . F o r h i g h - e m i s s i v e p l a t e s (i.e., > 0 . 7 0 ) this is a g o o d a p p r o x i m a t i o n .
If c o n v e c t i o n is p r e s e n t in t h e air g a p , as is u s u a l for i n c l i n e d c o l l e c t o r s , t h e
d e c o u p l i n g effect o f the air g a p is d e c r e a s e d b u t still a p p r e c i a b l e (Fig. 8 ) .
/ Convection in quadratic honeycombs \

\ Dependence on inclination J
aspect a = 5
10.0η
• Ro
L° 1 . 8 E +60 • Ro
x=. 3 . 3 Ε +β0 χ Ρα^-4.βΕ+_0β
8.0- /"""{ Τ
6
· ° - ; - - · - " " 1 j
21
4.0 -
i — ! — ·
2.0- ^ ^ - 1 ,
0 . 0 -j—Ι—Ι—1—1—1—1—Ι—Ι—ι—Ι—Ι—ι—Ι—Ι—ι—Ι—Ι
0 15 30 45 60 75 90
Honeycomb inclination β [degree]
Fig. 6. D e p e n d e n c e of convection within the h o n e y c o m b s on the
i n c l i n a t i o n o f t h e a b s o r b e r s y s t e m ( a s p e c t r a t i o 5, m a t e r i a l
t h i c k n e s s 10 c m ) .
f Coupled heattransport for selective absorber \
\ Air gap without convection J
mean temperature T
M= 37 °C
• measured data D COUPLE
1 .50
1 .25
I
£ 1 .00 Η
0.75 -ί·
I
0.50
o.o 0.5 1.0 1.5 2.0 2.5 3.0
gap width d [cm]
Fig. 7. H e a t t r a n s m i t t a n c e coefficient for a s p e c t r a l l y s e l e c t i v e a b s o r b e r
s y s t e m w i t h 10 c m h o n e y c o m b a n d v a r i a b l e air g a p ( n o
convection). Dashed lower curve represents a calculation
neglecting the radiation-conduction coupling.
)
/ Selective Collector
\ with and without air gap
• 0 cm airgap (exp) 9_i?]!_(theo.r.)
• 2 cm airgap (exp) 2 cmftheôr.)
1.6
1 . 4:
ι 1-2- r""'
i 1.0-
0.6 -j 1 1 -» Γ
30 50 70 90 110 130
absorber temperature [°Ql
Fig. 8. U-values of spectrally selective h o n e y c o m b collectors with and
w i t h o u t air g a p . T h e i n c l i n a t i o n is 4 5 ° a n d c o n v e c t i o n is
present.
C Total Energy Transmittance
B e c a u s e o f s o l a r a b s o r p t i o n in m o s t T I M ' s , s o l a r i r r a d i a n c e will r e s u l t in a
t e m p e r a t u r e r i s e w i t h i n t h e m a t e r i a l s . T h i s l e a d s to a s u p e r p o s i t i o n o f a h e a t flux
q , t o w a r d s t h e a b s o r b e r , w h i c h is p r o p o r t i o n a l , at least to a first a p p r o x i m a t i o n , to
n
t h e i r r a d i a n c e I. T h e r e f o r e t h e total e n e r g y t r a n s m i t t a n c e g, d e f i n e d b y
β( φ ) = (τα)(φ) + ς
ί / Ιη = ( τ α ) θ, (1)
is t h e r e l e v a n t p a r a m e t e r for t h e r m a l s y s t e m s . O f c o u r s e , q j d e p e n d s o n t h e h e a t
n
r e s i s t a n c e s f r o m t h e T I M to t h e a b s o r b e r a n d t h e e n v i r o n m e n t , b u t a l s o o n t h e
a b s o r b e r reflectivity a n d o n t e m p e r a t u r e l e v e l s . S t r i c t l y s p e a k i n g , t h e g - v a l u e is a
system parameter, and not a material parameter like the solar transmittance.
r i o w e v e r , c a l c u l a t i o n s s h o w t h a t t h e latter s y s t e m p a r a m e t e r s a r e o f m i n o r influ-
e n c e , a n d c o r r e c t i o n s for t h e1first
27
0 o n e s c a n b e i n t r o d u c e d i f a m e a s u r e m e n t o f g for
d e f i n e d c o n d i t i o n s is d o n e . ' O n l y a f e w direct m e a s u r e m e n t m e t h o d s , all o f
which are calorimetric, are known. While two of them employ constructions
s u c h as w a t e r o r air c o l l e c t o r s , a n d t h e fluid t e m p e r a t u r e d i f f e r e n c e b e t w e e n inlet
and outlet together with the flow rate are measured, the absorber o f the apparatus
at t h e I n s t i t u t e for S o l a r E n e r g y S y s t e m s ( I S E ) in F r e3 i4burg, on the other hand, uses
h e a t flux m e t e r s m o u n t e d o n a c o o l e d c o p p e r p l a t e . T h e a d v a n t a g e s o f this
d e v i c e l i e in a r e l a t i v e l y fast r e s p o n s e , a g o o d a c c u r a c y , a n d t h e p o s s i b i l i t y o f
m e a s u r i n g w i t h different i n c i d e n c e a n g l e s .
I n p r i n c i p l e , t h e m e a s u r e m e n t is a n a l o g o u s t o a n e f f i c i e n c y d e t e r m i n a t i o n o f a
solar collector: T h e ambient temperature T , the absorber temperature T b , and
a as
t h e i r r a d i a t i o n I a r e n e e d e d as w e l l as t h e n e t h e a t g a i n q
n t oef t h e a b s o r b e r . T h e
collector equation
q
n t =e g I - U ( T a - bT a)s (2)
t h e n c a n b e u s e d to d e t e r m i n e g, if t h e U - v a l u e o f t h e T I M - c o v e r is k n o w n . T h i s
can b e m e a s u r e d with the s a m e apparatus without irradiation. O n e advantage of
t h e I S E - d e v i c e c e r t a i n l y is t h e d i r e c t d e t e r m i n a t i o n o f T t > a n d o f q
a s n t wei t h h e a t
flux m e t e r s , w h e r e a s e l s e w h e r e the u s u a l h e a t r e m o v a l f a c t o r F R ( s e e R e f . 7 ) h a s to
b e t a k e n i n t o a c c o u n t . T h e total e n e r g y t r a n s m i t t a n c e for diffuse i s o t r o p i c irradia-
tion, gdif, c a n a l s o b e d e t e r m i n e d b y i n t e g r a t i n g n u m e r i c a l l y o v e r t h e a n g u l a r d e -
p e n d e n t g(<|>). R e s u l t s a p p r o p r i a t e for T I M ' s h a v e b e c o m e a v a i l a b l e n o w ; for t h e s e
g is g i v e n u n d e r n o r m a l i s e d c o n d i t i o n s w i t h m a x i m u m a b s o r p t a n c e ( a ) e q u a l to
u n i t y , a m b i e n t t e m p e r a t u r e ( T ) o f 2 6 ° C , a b s o r b e r t e m2p e r a t u r e ( T ^ ) o f 3 0 ° C ,
a 2 34 as
i n t e r n a l h e a t transfer coefficient (hj) o f 6.5 ± 0.5 W / m K , a n d e x t e r n a l h e a t t r a n s -
rfer coefficient ( h ) o f 8 ± 1 W / m K . R e p r e s e n t a t i v e d a t a a r e g i v e n in T a b l e 2.
a
Still, t h e r e is n o t e n o u g h d a t a w i t h t h e d e s i r e d a c c u r a c y to d e t e r m i n e t h e effective
s c a t t e r i n g p a r t o f t h e e x t i n c t i o n for different b a s e m a t e r i a l s , e.g. for t h e h o n e y c o m b
design. O n l y with additional work, and with theoretical models, can the impact o f
a m a t e r i a l c h a n g e o n t h e total e n e r g y t r a n s m i t t a n c e b e j u d g e d , a n d t h e r e f o r e t h e
i m p a c t o n t h e l a y o u t o f a s o l a r s y s t e m . A n e x a m p l e for t h e m a x i m u m d i f f e r e n c e
b e t w e e n s o l a r a n d total e n e r g y t r a n s m i t t a n c e is g i v e n in F i g . 9, w h e r e b o t h p r o p e r -
ties a r e p l o t t e d as f u n c t i o n s o f the i n c i d e n c e a n g l e . T h e d i f f e r e n c e for diffuse
i r r a d i a t i o n is a n 8 p e r c e n t c h a n g e in t r a n s m i t t a n c e .
Table 2 S o l a r a n d total e n e r g y t r a n s m i t t a n c e for diffuse i r r a d i a t i o n o f

different t y p e s o f m a t e r i a l s .
T
Material Thickness dif gdif
(cm)
Floatglass
"~~0.3 U.74±~o7o3 ÔJ9±~0703
P M M A pane 0.3 0.77 ± 0.03 0.81 ± 0.03
P M M A foam 1.5 0.55 ± 0.03 0.57 ± 0.02
Aerogel granules
between P M M A 0.3/2.0/0.3 0.37 ± 0 . 0 3 0.42 ± 0.03
PC honeycombs 10.0 0.78 ± 0.03 0.82 ± 0.05
P M M A capillaries 9.8 0.74 ± 0.03 0.77 ± 0.05
f Influence of solar absorption on transmittance

y PC-honeycomb with selective absorber
total energy solar
1.0 π
0.8- ^^"""'--^^^
0 0.6- \ \
1 4 \ \
ë °· ~ \ \
0.2- \ \
2
0 . 0 —I—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—r ^
0 15 30 45 60 75 90
incidence angle [degree]
Fig. 9. C o m p a r i s o n o f c a l c u l a t e d s o l a r a n d total e n e r g y t r a n s m i t t a n c e
for 1 0 c m h o n e y c o m b . A b s o r p t i o n , b u t n o s c a t t e r i n g in t h e
p l a s t i c s h e e t s , is a s s u m e d .
V. AVAILABLE MATERIALS AND REAL TRANSPARENT

COVER SYSTEMS
A l a r g e n u m b e r o f different m a t e r i a l s a n d s y s t e m s h a v e b e e n t e s t e d o n a l a b o r a -
t o r y s c a l e in t h e last y e a r s , b u t o n l y a f e w s y s t e m s a r e a v a i l a b l e o n t h e m a r k e t . In
t h e f o l l o w i n g s e c t i o n s s o m e o f t h e s e w i l l b e e x a m i n e d in m o r e detail.
A. Multiple Glazing with L o w Refractive Index Materials
F o r flat p l a t e s o l a r c o l l e c t o r s w o r k i n g w i t h o u t s t o r a g e in t h e m e d i u m t e m p e r a t u r e
r a n g e ( Δ Τ « 5 0 ° C ) , a h i g h g - v a l u e a n d t h e r e f o r e a l a r g e s o l a r t r a n s m i t t a n c e is v e r y
i m p o r t a n t , w h e r e a s a l o w U - v a l u e is n o t s o m e a n i n g f u l . F o r t h e s e a p p l i c a t i o n s , a
s p e c t r a l l y s e l e c t i v e a b s o r b e r h a s b e e n u s e d in m o s t c a s e s , t o g e t h e r w i t h a h i g h l y
t r a n s p a r e n t i n s u l a t i o n m a t e r i a l to s u p p r e s s c o n v e c t i o n .
P a r a l l e l P T F E (Teflon) slats a n d h o n e y c o m b s y s t e m s w e r e i n v e s t i g a t e d in
Australia and Canada, and Swedish companies have installed large area collector
fields w i t h different a r r a n g e m e n t s o f T e f l o n foils in t h e g a p b e t w e e n t h e a b s o r b e r
a n d t h e c o v e r g l a s s . C h a r a c t e r i s t i c d a t a o f s u c h s y s t e m s a r e s h o w n in T a b l e 3 ,
w h i c h i l l u s t r a t e s diffuse s o l a r t r a n s m i t t a n c e a n d U - v a l u e s for a n u m b e r o f
different s y s t e m s .
In a p p l i c a t i o n s , t h e cost o f t h e s y s t e m s is a n i m p o r t a n t p o i n t . T h e first field tests

w i t h l a r g e a r e a c o l l e c t o r s in S w e d e n i n d i c a t e t h a t for district h e a t i n g s y3s5t e m s w i t h
s e a s o n a l s t o r a g e a s i n g l e T e f l o n film is t h e b e s t o p t i o n at t h e m o m e n t . A
comparison b e t w e e n h o n e y c o m b s and parallel 3 6 structures s h o w s that the
slat
r e s u l t s c o u l d b e v e r y s i m i l a r for b o t h s y s t e m s .
Table 3. Characteristic data o f collector cover systems with P T F E

sheets between absorber and cover glass. T h e configuration
h a d £h » 0.23 a n d Δ Τ ~ 5 5 ° C ( e x c e p t i n g t h e U - v a l u e m a r k e d b y
a n a s t e r i s k , for w h i c h « 0.9).
Sheet type: Single Double V-corrugated Honeycomb None

T :
dif 0.82 0.75 0.83 0.81 0.85
U - v a l u2e : 2.9 2.5 2.75 2.0* 3.7
(W/m K)
B. H o n e y c o m b and Capillary Structures
F o r s y s t e m s w h i c h a r e w o r k i n g at h i g h e r t e m p e r a t u r e s o r w i t h i n t e r n a l s t o r a g e , a
l o w U - v a l u e b e c o m e s m o r e a n d m o r e i m p o r t a n t . O f c o u r s e a h i g h g - v a l u e is
a l w a y s g o o d . F o r real s y s t e m s o n e h a s to o p t i m i z e t h e m a t e r i a l a g a i n . F o r t h e s e
a p p l i c a t i o n s , I R - o p a q u e h o n e y c o m b a n d c a p i l l a r y s t r u c t u r e s37w e r e d e v e l o p e d ; t h e y
suppress the convection and IR-radiation very e f f e c t i v e l y . For l o w tempera-
tures, e v e n a s p e c t r a l l y s e l e c t i v e c o a t i n g is n o l o n g e r n e c e s s a r y .
A s u p p r e s s i o n o f I R - r a d i a t i o n is m u c h h a r d e r to a c h i e v e t h a n a p r e v e n t i o n o f
c o n v e c t i o n . T h e m a t e r i a l s o p t i m i s a t i o n p r o c e s s t h e r e f o r e is a q u e s t i o n o f h o w
l a r g e a n a s p e c t r a t i o h a s to b e c h o s e n a n d h o w the t h i c k n e s s o f t h e s h e e t s s h o u l d
b e a d a p t e d to g e t g o o d d a m p i n g for the I R - r a d i a t i o n o n t h e o n e h a n d a n d n o t t o o
h i g h a b s o r p t i o n a n d s c a t t e r i n g for t h e i n c o m i n g s o l a r r a d i a t i o n o n t h e o t h e r h a n d .
In m o s t o f t h e s e s y s t e m s , c o n v e c t i o n in t h e s t r u c t u r e is n o l o n g e r a p r o b l e m .
T w o t y p e s o f m a t e r i a l s a r e a v a i l a b l2e in l a r g e q u a n t i t i e s o n the m a r k e t : a s q u a r e
h o n e y c o m b m a t e r i a l (3.5 χ 3.5 m m cell size) m a d e from p o l y c a r b o n a t e , a n d
c a p i l l a r y m a t e r i a l s m a d e from different p l a s t i c s w i t h v a r i o u s c a p i l l a r y d i a m e t e r s .
T y p i c a l t h i c k n e s s e s o f the plastic l a y e r s in b o t h c a s e s is 2 0 to 5 0 μιη. In p r i n c i p l e ,
t h e m a t e r i a l s c a n b e o p t i m i z e d for a s p e c i a l a p p l i c a t i o n . In T a b l e 4 t y p i c a l c h a r a c -
teristic d a t a a r e g i v e n for a n u m b e r o f t h e s e m a t e r i a l s w i t h o u t a n a d d i t i o n a l c o v e r
g l a s s , r e q u i r e d for a real a p p l i c a t i o n . T h e r m a l d a t a w e r e m e a s u r e d w i t h b l a c k
a b s o r b e r s (ε^ « 0.9) o n b o t h sides. T h e m a t e r i a l h a d a m e a n t e m p e r a t u r e ( T
m )e o f a n
10°C.
T h e d a t a s h o w t h e h i g h p o t e n t i a l o f t h e s e m a t e r i a l s for h i g h t e m p e r a t u r e o r
s t o r a g e s y s t e m s . F u r t h e r i m p r o v e m e n t s m i g h t b e p o s s i b l e in t h e future, m a i n l y
in t r a n s m i t t a n c e as a r e s u l t o f b e t t e r p r o d u c t i o n t e c h n o l o g i e s , b u t a l s o in U - v a l u e s
which could b e lowered b y optimisation o f the geometry.
Table 4. Characteristic data of h o n e y c o m b and capillary structures. The

configurations had ΔΤ « 10°C and T = 10°C.
m ne a
Sample: Honeycomb. Honeycomb. Capillaries. Capillaries.

5 c m thick 10 cm thick 10 c m thick 10 c m thick
Polycarbonate Polycarbonate Polycarbonate PMMA
x
d :i f 0.85 0.78 0.73 0.80
A(W/m2K): 2 1.07 0.98 0.91
C Homogeneous Materials (Aerogels)
A s s t a t e d in t h e i n t r o d u c t i o n , a h o m o g e n e o u s m a t e r i a l d i s t r i b u t i o n w o u l d b e t h e
optimal o n e from the physical point of view. This brings us to aerogels, which
h a v e b e e n k n o w n for m o r e t h a n 5 0 y e a r s . T h e first a p p l i c a t i o n s in t h e o p t i c a l
field w e r e w i t h e x p e r i m e n t s in C e r e n k o v c o u n t e r s in e l e m e n t a r y p a r t i c l e p h y s i c s .
T h e u t i l i z a t i o n o f t h e s e t r a n s p a r e n t a n d w e l l i n s u l a t i n g m a t e r i a l s in w i n d o w a n d
c o v e r s y s t e m s s t a r t e d a b o u t 10 y e a r s a g o . Y e t still o n l y t w o different t y p e s o f
a e r o g e l s a r e a v a i l a b l e o n a s m a l l s c a l e for tests. O n e t y p e c o m e s as tiles o f t y p i c a l l y
2 c m t h i c k n e s s a n d d i m e n s i o n s o f u p to 6 0 χ 6 0 c m , w h i c h a r e h i g h l y t r a n s p a r e n t
a n d c a n b e u s e d in w i n d o w s . T h e o t h e r t y p e c o m e s as g r a n u l e s o f v a r i a b l e
d i a m e t e r ( t y p i c a l l y 1 to 10 m m ) , w h i c h s h o u l d b e m u c h c h e a p e r in p r o d u c t i o n a n d
w h i c h c a n b e filled i n t o t h e g a p b e t w e e n p a n e s in a d o u b l e g l a z i n g , for e x a m p l e .
T h i s latter m a t e r i a l as y e t s h o w s s t r o n g s c a t t e r i n g b u t it c o u l d b e u s e d in c o l l e c t o r s
a n d f a c a d e s for e x a m p l e , as w i l l b e d i s c u s s e d later. T a b l e 5 s h o w s c h a r a c t e r i s t i c
d a t a o f a d o u b l e g l a z e d w i n d o w w i t h different a e r o g e l fillings. I n p r i n c i p l e ,
s y s t e m s u s i n g tiles o r g r a n u l e s c a n b e i m p r o v e d b y e v a c u a t i o n o r s p e c i a l g a s
fillings.
T a b l e 5. C h a r a c t e r i s t i c d a t a o f a e r o g e l s a m p l e s b e t w e e n p a n e s in a
double glazing. T h e configurations had ΔΤ « 10°C and
Sample: Tiles Granules with diameters:

6-8 m m 4-6 m m 3-4 m m <2 mm
:
*dif 2 0.57 0.43 0.42 0.40 0.22
Λ ( W / m K ) : 0.95 1.15 1.13 1.03 0.98
VI. APPLICATIONS OF TRANSPARENT INSULATION

MATERIALS
A. Fiat P l a t e C o l l e c t o r s for P r o c e s s H e a t (90 t o 1 5 0 ° C )
Flat plate collectors can b e tremendously improved b y using transparent insula-

tion m a t e r i a l s a s t h e front c o v e r . A r e a s o n a b l e c r i t e r i o n for t h e c o m2 parison of
p r o c e s s h e a t c o l l e c t o r s is t h e efficiency a t a n i r r a d i a t i o n o f 8 0 0 W / m a n d a t e m p e -
r a t u r e d i f f e r e n c e o f Δ Τ = 1 0 0 ° C . U n d e r t h e s e c o n d i t i o n s , a c o n v e n t i o n a l flat p l a t e
c o l l e c t o r w i t h a s p e c t r a l l y s e l e c t i v e a b s o r b e r a n d s i n g l e g l a z i n g h a s a n efficiency o f
a p p r o x i m a t e l y 2 0 % o n l y , w h e r e a s v a c u u m t u b e c o l l e c t o r s r e a c h a b o u t 5 0 %.
U s i n g a 1 0 c m h o n e y c o m b s t r u c t u r e m a d e o f p o l y c a r b o n a t e ,2t h e front c o v e r l o s s e s
o f a flat p l a t e c o l l e c t o r c a n b e r e d u c e d t o as little as 0.9 38 W / m K (at Δ Τ = 1 0 0 ° C ) . 2
Such a collector has been developed recently at I S E . A c o l l e c t o r field o f 6 0 m
area has been tested in combination with a transmembrane water desalination
u n i t o n t h e C a n a r y I s l a n d s s i n c e M a y 1 9 8 8 . F i g u r e 10 s h o w s a c o m p a r i s o n o f d a t a
for flat p l a t e , v a c u u m t u b e , a n d flat p l a t e h o n e y c o m b c o l l e c t o r s .
A c c o r d i n g t o c a l c u l a t i o n s , still further i m p r o v e m e n t s o f o p t i m i z e d flat p l a t e

c o l l e c t o r s w i t h T I M ' s a r e p o s s i b l e , s o that t h e y w i l l e v e n o u t p e r f o r m v a c u u m t u b e
c o l l e c t o r s i n t h e future.
ο σ ο ο ο ο σ ο ο ο ο
(%)
D9JD jeqjosqD uo pasDq
il:
LI I I I I VIA f
Aouapijp
Temperature difference between cover and absorber,

divided by irradiation I (Km2/kW)
Fig. 1 0 . Efficiency c u r v e s for s o l a r c o l l e c t o r s o f different d e s i g n s .

1 = s p e c t r a l l y s e l e c t i v e flat p l a t e
2 = spectrally selective with h o n e y c o m b
3 = vacuum tube
B. Integrated Storage Collectors for D o m e s t i c Hot W a t e r
A n i n t e g r a t e d s t o r a g e c o l l e c t o r ( I S C ) c o n s i s t s o f a flat s t o r a g e t a n k w h o s e u p p e r
s u r f a c e a c t s as a n a b s o r b e r a n d is s u p p l i e d w i t h t r a n s p a r e n t i n s u l a t i o n . A typical
d e s i g n is s h o w n in F i g u r e l l . 39 T h e t a n k is c o n s t r u c t e d to w i t h s t a n d w a t e r
pressure from the mains. T h e advantages over a conventional solar domestic hot
water ( D H W ) system are
- compact construction, only one single device,

- n o heat exchanger, no p u m p , n o control system,
- n o anti-freeze fluid.
T h e s e a d v a n t a g e s c a n h e l p to b r i n g d o w n t h e c o s t s o f s o l a r d o m e s t i c h o t w a t e r
s y s t e m s . U p to n o w , i n t e g r a t e d s t o r a g e c o l l e c t o r s w i t h s i m p l e s i n g l e o r d o u b l e
g l a z i n g c o u l d b e u s e d s u c c e s s f u l l y in w a r m c l i m a t e s o n l y . U n d e r C e n t r a l
E u r o p e a n w i n t e r w e a t h e r c o n d i t i o n s , f r e e z i n g o c c u r s if s i m p l e g l a z i n g is u s e d .
T h e s e difficulties c a n b e o v e r c o m e , h o w e v e r , b y u s i n g t r a n s p a r e n t i n s u l a t i o n
m a t e r i a l s as t h e c o v e r s o f I S C ' s . T h r o u g h e x t e n s i v e c o m p u t e r s i m u l a t i o n s , it h a s
b e e n s h o w n that for I S C ' s t h e r e is n o d a n g e r o f freezing in C e n t r a l E u r o p e a n
weather.
type I type 2
Fig. 1 1 . Cross-sections of two types o f integrated storage collectors
designed to operate under mains pressure.
1 = glass cover
2 = transparent insulation
3 = water outlet
4 = opaque insulation
5 = water tank
6 = w a t e r inlet
T h r e e p r o t o t y p e s o f i n t e g r a t e d s t o r a g e c o l l e c t o r s w i t h T I M ( g = 0.6 a n d 1.7 W / m 2K
o v e r a l l h e a t l o s s coefficient w i t h r e s p e c t to a b s o r b e r a r e a ) h a v e b e e n c o n s t r u c t e d at
I S E a n d a r e c u r r e n t l y u n d e r i n v e s t i g a t i o n . I n a c o m p u t e r - c o n t r o l l e d test r o u t i n e ,
4 0 l i t r e s / m 2o f h o t w a t e r a r e w i t h d r a w n e v e r y d a y f r o m t h e i n t e g r a t e d s t o r a g e
c o l l e c t o r . T h e p r o t o t y p e s a r e c h a r a c t e r i z e d in t e r m s o f s y s t e m e f f i c i e n c y a n d s o l a r
fraction. T h e s y s t e m efficiency is t h e y e a r l y a c c u m u l a t e d h e a t g a i n (i.e., t h e e n e r g y
c o n t e n t o f t a p p e d w a t e r at t h e t e m p e r a t u r e l e v e l o f t h e s t o r a g e o f t h e s o l a r s y s t e m
minus the energy content of the cold mains water) divided b y the yearly accumu-
l a t e d s o l a r r a d i a t i o n e n e r g y o n t h e c o l l e c t o r a r e a , a n d t h e s o l a r fraction is t h e
yearly accumulated heat gain minus storage losses divided b y the yearly accumu-
l a t e d h e a t d e m a n d (i.e., t h e e n e r g y c o n t e n t o f t a p p e d w a r m w a t e r d e l i v e r e d b y the
s o l a r s y s t e m as w e l l as h e a t e d u p b y a n a u x i l i a r y h e a t e r m i n u s t h e e n e r g y c o n t e n t
o f t h e c o l d m a i n s w a t e r ) . D u r i n g n i n e m o n t h s o f o p e r a t i o n ( f r o m N o v e m b e r '86
to J u l y ' 8 7 ) t h e m e a s u r e d s y s t e m efficiency w a s 3 1 % at a s o l a r fraction o f 5 2 %
(Fig. 1 2 ) . M o r e details o f t h e test r e s u l t s a r e d e s c r i b e d b y S c h m i d t e t . a l . 40 T h e
efficiencies r e p o r t e d in F i g . 12 a r e c o n s i d e r a b l y h i g h e r t h a n t h o s e o f c o n v e n t i o n a l
s o l a r D H W s y s t e m s w i t h flat p l a t e c o l l e c t o r s u n d e r C e n t r a l E u r o p e a n w e a t h e r
conditions.
%
00 "Τ : S : : : i : 1
I ! i S : 1
i 1 L—. yeorly solar fraction
j yearly efficiency
8 0 ~~ΤΊΤ~Π Γ"
i \ L-^f i i I I
40 Lv£ L J i j i
I/ x ! i i I i
2o _ /1 j i_Sî__i i
/ ! I „!__ j I—
7 ~~T !"*" "T ~ T ι 1
ο 1 ι ι ! . . I
0i 1 1 1 1 1 1 1
0 1 2 3 4 5 6 7 8
specific wafer withdrawal
Fig. 12. Y e a r l y s o l a r fraction a n d y e a r l y efficiency o f an I S C
( t y p e 2 ) as a function o f the specific w a t e r w i t h d r a w a l .
C House Heating with Transparently Insulated Collector-Storage Walls
A n e w concept of external transparent insulation o f massive house walls c o m -

bines the advantages of conventional opaque insulation (reduction o f heat losses)
w i t h t h o s e o f a s o l a r c o l l e c t o r s y s t e m ( c o n v e r s i o n o f s o l a r r a d i a t i o n i n t o useful
h e a t ) . It is t h e r e f o r e p r a c t i c a l n o t o n l y in c o l d a n d s u n n y c l i m a t e s , b u t a l s o in
northern climates. O n l y the special properties o f g o o d T I M ' s allow an application

o f this p r i n c i p l e u n d e r t h e latter c o n d i t i o n s .
T h e w o r k i n g p r i n c i p l e is s h o w n i n F i g . 1 3 . A l a y e r o f t r a n s p a r e n t i n s u l a t i o n is
m o u n t e d on the facade o f a building. T h e surface of the wall has the properties of
a n a b s o r b e r , s o t h e i n c o m i n g r a d i a t i o n is c o n v e r t e d i n t o t h e r m a l e n e r g y .
D e p e n d i n g o n the relation o f the U-values o f the wall and the transparent cover,
m o r e o r l e s s e n e r g y w i l l f l o w i n t o t h e b u i l d i n g , t h u s c o n4t r4i1
2b u t i n g useful heat. A
s t e a d y - s t a t e m o d e l w a s d e v e l o p e d b y G o e t z4
b e4r3
4g e r e t . a l . ' a n d h a s b e e n c o m p a r e d
with experimental and numerical r e s u l t s . '
insulation
\ absorber H wa
rrincir. temperature
a
9P
airqai
exterior ground ~ ' interior
Fig. 13. P r i n c i p l e for t r a n s p a r e n t i n s u l a t i o n o f m a s s i v e h o u s e w a l l s .
T h e t h e o r y d e s c r i b e s m o n t h l y , o r e v e n w e e k l y , m e a n v a l u e s v e r y w e l l a n d is
s t r a i g h t f o r w a r d as l o n g as n o s w i t c h i n g c o n t r o l o f t h e s y s t e m p r o d u c e s n o n - l i n e a r
t h e r m a l b e h a v i o u r . T h e n e t h e a t flux d e n s i t y ( q ) o f t h e s y s t e m to t h e o u t s i d e is
w
g i v e n b y t h e total U - v a l u e ( U ) a n d t h e efficiency (ηο), w h e r e U
t o t t t oa c c o u n t s for
t h e U - v a l u e s o f the w a l l c o n s t r u c t i o n (U u)
wa a n d o f t h e T I M - c o v e r (UjiM-cover)
a c c o r d i n g to
U _1 U _1 + U
tot = wall TIM-c -1 (3)
T h e f o r m u l a for q
wis t h e r e f o r e
u T T 1
q (4)
w= t o t < i " a ) " Ή0
with
u
g wall
(5)
' Uwall + U T .Ic M
or 'v e
w h e r e I is t h e s o l a r i r r a d i a t i o n i n t e n s i t y as b e f o r e .
Although the intrinsic storage capacity of the collector wall distributes the solar
gains over an extended period o f time, producing high comfort conditions, some-
t i m e s t h e e x c e s s i v e s o l a r g a i n s a r e n e i t h e r n e c e s s a r y in o r d e r t o k e e p t h e t e m p e r a -
t u r e at t h e r e q u i r e d c o m f o r t l e v e l n o r c a n t h e y b e s t o r e d w i t h i n t h e t h e r m a l m a s s
o f t h e b u i l d i n g l o n g e n o u g h . T h e s e p a r t s o f t h e s o l a r g a i n s a r e t h e n l o s t a g a i n to
the surroundings without having reduced the auxiliary heating d e m a n d . U n d e r
t h e s e c o n d i t i o n s , t h e u t i l i z a t i o n o f t h e s o l a r g a i n s is b e l o w o n e . T h e u t i l i z a t i o n
factor c a n o n l y b e d e t e r m i n e d b y e x p e r i m e n t s o r n u m e r i c a l s i m u l a t i o n s . It is
n o r m a l l y l a r g e r t h a n for d i r e c t - g a i n s y s t e m s , w h e r e v e r y often h o t air h a s to b e
v e n t e d . T h e useful m o n t h l y e x c e s s s o l a r g a i n Q i ( r e p r e s e n t e d b y t h e s e c o n d p a r t
s o
o f E q . 4 , i.e., rjo I) is l i m i t e d b y t h e m o n t h l y r e m a i n i n g h e a t l o a d LH o f t h e h o u s e .
T h e r e f o r e t h e i d e a l l i n e a r r e l a t i o n in E q . (4) c h a n g e s in r e a l i t y w h e n Q i a p p r o -
s o
a c h e s t h e o r d e r o f m a g n i t u d e o f L ^ , as a p p a r e n t f r o m F i g . 1 4 . It c a n a l s o b e s h o w n
that, for a v a i l a b l e m a t e r i a l s , t h e s y s t e m w o r k s v e r y w e l l for all o r i e n t a t i o n s e x c e p t
f a c i n g n o r t h (in t h e n o r t h e r n h e m i s p h e r e ) .
(utilizability of excess solar gains ^

• fu=1 ° fu<1
g
-
1Ό
Ο
λ.
Ό ~~~j£ZZZ ζζ ^ζζζζζζζ - - - - - - Β
(0
Ο
Ά
I
1
-1 —j 1
I •
0.0 0.2 0.4 2 0.6

Solar irradiation per degree day [kWiym Kd]
Fig. 14. Excess solar load ratio (integrated positive net heat flow into a
b u i l d i n g d i v i d e d b y its r e m a i n i n g h e a t l o a d ) v s . i r r a d i a t i o n
energy divided by degree days (monthly values).
Single points: simulation results;
continuous line: analytical result using Eq. (4).
E x p e r i m e n t a l r e s u l t s for a w e s t f a c a d e o f a h o u s e in F r e i b u r g , G e r m a n y , h a v e b e e n
c o l l e c t e d s i n c e 1 9 8 3 . A l t h o u g h t h e h o u s e is s h a d e d b y n e i g h b o u r i n g h o u s e s a n d
trees, a comparison o f the T I M - s y s t e m with a conventional o p a q u e insulation and

t h e w a l l a l o n e s h o w s t h e r e m a r k a b l e p o t e n t i a l for e n e r g y s a v i n g s b y u s e o f n o v e l
c o l l e c t o r - s t o r a g e w a l l s (Fig. 1 5 ) .
no i n s u l a t i o n opaque i n s u l a t i o n t r a n s p a r e n t i2n s u l a t i o n
u= 1 W/nTK u= 0 . 5 6 W/nfK u= 0 . 5 6 W/m K
Ζ,Ο-1 1 j 1 Heat energy demand

f o r three months
= no i n s u l a t i o n
2
4 2 . 2 KWh/m 100%
Baza opaque i n s u l a t .
2
2 3 . 8 KWh/nf 50%
transp.insulat.
2
Jan Feb Mar 3 . 9 KWh/rn 10%
Fig. 1 5 . D a i l y a v e r a g e d h e a t f l o w s for a t r a n s p a r e n t l y i n s u l a t e d
wall, an equivalent opaque-insulated wall, and a wall
without insulation.
( W e s t f a c a d e o f a h o u s e in F r e i b u r g ; e x p e r i m e n t a l r e s u l t s
for J a n u a r y - M a r c h 1 9 8 5 ) .
Wall: 36 c m brick.
T h e h e a t e n e r g y d e m a n d is t h e i n t e g r a t e d h e a t f l o w o v e r
3 months.
O n e p r o b l e m , w h i c h a l m o s t c e r t a i n l y a r i s e s , is o v e r h e a t i n g in t h e s u m m e r . A s
t h e c o l l e c t o r w a l l is an efficient s y s t e m , e x c e s s h e a t w i l l b e p r o d u c e d c o n s t a n t l y in
the s u m m e r . S o m e t i m e s this p r o b l e m c a n b e s o l v e d b y p a s s i v e s h a d o w i n g , e.g.,
w i t h o v e r h a n g s or b y n a t u r a l v e n t i n g o f e x c e s s h e a t at t h e a b s o r b e r , b u t in m o s t
c a s e s a n a c t i v e s y s t e m is n e e d e d . T h e r e f o r e a n a u t o m a t i c roller b l i n d s y s t e m ,
c o n t r o l l e d b y a m i c r o c o m p u t e r s y s t e m , w a s i n t e g r a t e d in t h e test f a c a d e . D u r i n g
s u m m e r t h e r o l l e r b l i n d is c l o s e d . A t t h e b e g i n n i n g o f t h e h e a t i n g s e a s o n , 4t h40
5e
o u t d o o r t e m p e r a t u r e d e c r e a s e s a n d t h e roller b l i n d o p e n s d u r i n g t h e d a y . '
S i n c e 1 9 8 8 , s e v e r a l b u i l d i n g s o f different t y p e s h a v e b e e n e q u i p p e d w i t h T I M -
s y s t e m s a n d m e a s u r e m e n t s a r e t a k e n to c h e c k t h e p e r f o r m a n c e o f t h e s e s y s t e m s
i n t e g r a t e d in real h o u s e s w i t h i n h a b i t a n t s .
VIL CONCLUSION AND OUTLOOK
T h e e x p e r i m e n t a l , t h e o r e t i c a l a n d p r a c t i c a l w o r k o v e r t h e last f e w y e a r s h a s l e d to
a basic understanding of TIM's. The 2 materials n o w available reach heat trans-
m i t t a n c e c o e f f i c i e n t s b e l o w 1.0 W / m K w i t h t r a n s m i s s i o n v a l u e s o f 0.7. T h e
t h e o r e t i c a l m o d e l s h a v e p r o v e n t h e i r v a l i d i t y a n d c a n b e u s e d in s i m u l a t i o n a n d
o p t i m i z a t i o n p r o g r a m s . F u r t h e r i m p r o v e m e n t s , p r i n c i p a l l y in s y s t e m s b u t a l s o in
materials, can be expected.
T h e first a p p l i c a t i o n s o f T I M ' s , e.g., for flat p l a t e c o l l e c t o r s , h a v e s h o w n t h a t an

i n c r e a s e in efficiency c a n b e a c h i e v e d . In o t h e r fields, e.g., h o u s e h e a t i n g a n d
storage, completely n e w concepts are m a d e possible.
O n e m a i n g o a l for t h e future w i l l b e to i m p r o v e t h e s y s t e m s a n d r e d u c e c o s t , t h u s
e n a b l i n g t h e s t o r a g e o f h e a t f r o m s u m m e r to w i n t e r .
Initial c a l c u l a t i o n s s h o w t h e l a r g e p o t e n t i a l o f t r a n s p a r e n t l y i n s u l a t e d e n e r g y
s t o r a g e s y s t e m s (Fig. 1 6 ) . F u r t h e r i m p r o v e m e n t s o f s u c h s y s t e m 4s 86c o-u l4d h e l p to
s o l v e t h e s t o r a g e p r o b l e m in l a r g e s o l a r h e a t i n g i n s t a l l a t i o n s .
CD
"Ό
°1 ι ι 1 1 1 1 1—'
0 200 400 600 800 1000 1200 M00
TIME, days
Fig. 16. S i m u l a t i o n r e s u l t s for l a r g e t r a n s p a r e n t l y i n s u l a t e d s t o r a g e
t a n k s w i t h o3u t u s e r (no w a t e r w i t h d r a w a l ) .
A = 200 m 3
Β = 30000 m
Horizontal T I M cover.
REFERENCES
1. V . W i t t w e r , W . P l a t z e r , A . P f l u g e r , W . S t a h l a n d A . G o e t z b e r g e r , in Proc.
ISES Solar World Forum, M o n t r e a l , V o l . 2 , p . 1 1 1 4 ( 1 9 8 5 ) .
2. G . F r a n c i a , in Proc. U.N. Conf. on New Sources of Energy, E / C o n f .
3 5 / S / 7 1 (1961).
3. K . G . T . H o l l a n d s , S o l a r E n e r g y 9 , 1 5 9 (1965).
4. H . T a b o r , S o l a r E n e r g y 1 2 , 5 4 9 (1969).
5. A.J. Hunt, Lawrence Berkeley Laboratory Report LBL-15756
(University of California, 1983).
6. M . R u b i n a n d C M . L a m p e r t , S o l a r E n e r g y M a t e r . 7, 3 9 3 ( 1 9 8 3 ) .
7. J . A . D u f f i e a n d W . A . B e c k m a n , Solar Engineering of Thermal Processes
(Wiley, N e w York, 1980).
8. R . S i e g e l a n d J . R . H o w e l l , Thermal Radiation Heat Transfer, second
edition (McGraw-Hill, N e w York, 1981).
9. D . K . E d w a r d s , S o l a r E n e r g y 1 2 , 4 0 1 (1977).
10. M . R u b i n , Int. J . E n e r g y R e s . 6, 123 (1982).
11. M . B o r n , Optik - Ein Lehrbuch, third edition (Springer, Berlin, 1981).
12. K. Papamichael and F. Winkelmann, Lawrence Berkeley Laboratory
Report LBL-20543 (1986).
13. A . Pfluger, D i p l o m a r b e i t , U n i v e r s i t y o f F r e i b u r g , G e r m a n y ( 1 9 8 4 ) .
14. K.G.T. Hollands and J.L. Wright, Solar Energy 3 L 211 (1983).
15. M . G . Kaganer, Opt. Spektrosk. 2 6 , 4 4 3 (1969).
16. R. Caps, Ph.D. Thesis, University o f W u r z b u r g , G e r m a n y (1985).
17. W . Platzer, Ph.D. Thesis, University of Freiburg, G e r m a n y (1988).
18. A. Pfluger, Ph.D. Thesis, University o f Freiburg, G e r m a n y (1988).
19. K . G . T . H o l l a n d s , K . N . M a r s h a l l a n d R . K . W e d e l , S o l a r E n e r g y 2L
231 (1978).
20. W . P l a t z e r , S o l a r E n e r g y M a t e r . 1 6 , 2 7 5 (1987).
21. M . Rubin, Solar Energy Mater. 6, 375 (1982).
22. D . K . E d w a r d s a n d R . D . T o b i n , J . H e a t T r a n s f e r ( 1 9 6 7 ) , p. 1 3 2 .
23. R . D . C e s s , A d v . H e a t T r a n s f e r 1 , 1 (1964).
24. J . F r i c k e , e d i t o r , Aerogels, Springer Proc. Phys. Vol. 6 (Springer,
Berlin, 1986).
25. R . U l b r i c h t , E l e k t r . T e c h n . Z . 2 6 , 5 1 2 (1905).
26. R . U l b r i c h t , Elektr. T e c h n . Z . 2 8 , 7 7 7 (1907).
27. J.A. Jacquez and H.F. Kuppelheim, J. Opt. Soc. A m . 4 5 , 4 6 0 (1955).
28. J . G . S y m o n s , J . S o l a r E n e r g y E n g r . 1 0 4 , 2 5 1 (1982).
29. J.G. Symons, E.A. Christie and M.K. Peck, Appl. Opt. 2 1 , 2827 (1982).
30. V . R . W e i d n e r a n d J . J . H s i a , J. O p t . S o c . A m . Z L 8 5 6 ( 1 9 8 1 ) .
31. E . K r o c h m a n n a n d J . K r o c h m a n n , P a p e r p r e s e n t e d at t h e C I E 2 0 t h s e s s i o n ,
1983.
32. K . G . T . H o l l a n d s , G . D . R a i t h b y a n d F . B . R u s s e l l , Int. J . H e a t M a s s
T r a n s f e r 2Z, 2 1 1 9 (1984).
33. K.G.T. Hollands and K. Iynkaran, Solar Energy 3 4 , 309 (1985).
34. B. Jacobs, Diplomarbeit, University of Freiburg, G e r m a n y (1989).
35. B . K a r l s s o n , in Proc. North Sun 1988 ( S w e d i s h C o u n c i l for B u i l d i n g
R e s e a r c h , S w e d e n , 1 9 8 8 ) , p. 5 1 3 .
36. J . G . S y m o n s , J . S o l a r E n e r g y E n g r . 1 0 4 , 2 5 1 (1982).
37. V . W i t t w e r , W . S t a h l a n d A . Pfluger, S o l a r E n e r g y M a t e r . Π , 1 9 9 ( 1 9 8 4 ) .
38. M . R o m m e l a n d V . W i t t w e r , in Advances in Solar Energy Technology,
e d i t e d b y W . H . B l o s s a n d F . Pfisterer ( P e r g a m o n , O x f o r d , 1 9 8 8 ) , p . 6 4 1 .
39. A. Goetzberger and M. R o m m e l , Solar Energy 3 9 , 211 (1987).
40. C . S c h m i d t , A . G o e t z b e r g e r a n d M . R o m m e l , in Advances in Solar Energy
Technology, e d i t e d b y W . H . B l o s s a n d F . Pfisterer ( P e r g a m o n , O x f o r d ,
1988), p. 9 3 5 .
41. A. Goetzberger, J. Schmid and V. Wittwer, Arcus L 3 2 (1984).

42. A . G o e t z b e r g e r , J . S c h m i d a n d V . W i t t w e r , Int. J . S o l a r E n e r g y 2 , 2 8 9 ( 1 9 8 4 ) .
43. W . P l a t z e r , in Advances in Solar Energy Technology, edited b y W . H . Bloss
a n d F . Pfisterer ( P e r g a m o n , O x f o r d , 1 9 8 8 ) , p. 3 4 9 8 .
44. P . O . B r a u n , J . S c h m i d a n d E . B o l l i n , in Proc. 7th Int. Sonnenforum,
Frankfurt (DGS-Sonnenenergie V e r l a g s - G m b H , 1990), p. 5 4 4 .
45. A. Goetzberger and K.A. Gertis, Technical Report BMFT-03E-8411-A (1987).
46. A . G o e t z b e r g e r , Int. J . S o l a r E n e r g y 2 , 5 2 1 ( 1 9 8 4 ) .
47. A. Goetzberger and M. R o m m e l , Solar Energy 3 9 , 211 (1987).
48. M . R o m m e l , V . W i t t w e r a n d A . G o e t z b e r g e r , in Advances in Solar Energy
Technology, e d i t e d b y W . H . B l o s s a n d F . Pfisterer ( P e r g a m o n , O x f o r d , 1 9 8 8 ) ,
p. 1553.
Chapter 4
SELECTIVELY SOLAR-ABSORBING SURFACE COATINGS:

OPTICAL PROPERTIES AND DEGRADATION.
G.A. N i k l a s s o n a n d C . G . G r a n q v i s t
Physics Department
ABSTRACT
T h e m o s t critical p a r t o f a n e n e r g y - e f f i c i e n t s o l a r c o l l e c t o r is t h e a b s o r b e r s u r f a c e ,
w h i c h should b e spectrally selective and exhibit high solar absorptance and low
t h e r m a l e m i t t a n c e . T h i s c h a p t e r i n t r o d u c e s different d e s i g n p r i n c i p l e s for
a c h i e v i n g s p e c t r a l s e l e c t i v i t y , r e p o r t s r a d i a t i v e p r o p e r t i e s for s e v e r a l a v a i l a b l e
solar absorber surfaces, discusses theoretical modelling, and reviews recent w o r k
a i m e d at u n d e r s t a n d i n g their d e g r a d a t i o n at e l e v a t e d t e m p e r a t u r e .
I. INTRODUCTION
A n energy-efficient solar collector should absorb incident solar radiation, convert

it to t h e r m a l e n e r g y , a n d d e l i v e r t h e t h e r m a l e n e r g y to a h e a t - t r a n s f e r m e d i u m
w i t h m i n i m u m l o s s at e a c h s t e p . F i g u r e 1 s e r v e s a s a c o n v e n i e n t i n t r o d u c t i o n to
t h e d e s i g n o f a flat-plate s o l a r c o l l e c t o r a n d o u t l i n e s t h e m o s t s a l i e n t c o m p o n e n t s .
The collector comprises a thermally well-insulated arrangement w h o s e upward-
f a c i n g s i d e is t r a n s p a r e n t s o that s o l a r r a d i a t i o n can p e n e t r a t e to a n a b s o r b i n g
s u r f a c e , w i t h carefully t a i l o r e d p r o p e r t i e s , in c o n t a c t w i t h a h e a t - t r a n s f e r m e d i u m
s u c h as w a t e r o r air. T h e r m a l l o s s e s a r e d i m i n i s h e d b y p l a c i n g t h e a b s o r b e r
s u r f a c e b e l o w a c o v e r g l a s s . E v e n s m a l l e r l o s s e s c a n b e o b t a i n e d b y u s e o f trans-
p a r e n t i n s u l a t i o n m a t e r i a l s o f the k i n d d i s c u s s e d in t h e p r e v i o u s c h a p t e r . In
p r i n c i p l e , t h e e n e r g y efficiency o f t h e c o l l e c t o r c a n b e b o o s t e d b y s u r f a c e c o a t e d
g l a s s : a n t i r e f l e c t i o n c o a t i n g s as w e l l as infrared-reflecting c o a t i n g s a r e o f interest.
S u c h c o a t i n g s a r e d i s c u s s e d in t h e f o l l o w i n g c h a p t e r . It s h o u l d b e s t r e s s e d that Fig.
1 refers to the c o m m o n l y u s e d fixed flat-plate c o l l e c t o r . M o s t o f t h e t r e a t m e n t
b e l o w w i l l b e d o n e w i t h s u c h c o l l e c t o r s in m i n d , b u t w e a l s o i n c l u d e s o m e dis-
c u s s i o n o f a b s o r b e r s u r f a c e s d e s i g n e d for h i g h - t e m p e r a t u r e a p p l i c a t i o n s p r i m a r i l y
in e v a c u a t e d t u b u l a r c o l l e c t o r s . S o l a r c o l l e c t o r c o n s t r u c t i o n s w i t h s o l a r r e f l e c t i n g
a n d t r a c k i n g facilities a r e in e x i s t e n c e as w e l l .
70
Selectively Solar-absorbing Surface Coatings 71
Antireflection coating
Cover glass
Infrared reflecting coating
Thermal insulation
Transparent thermal insulation
Absorber surface
Absorber
Heat - transfer fluid
1.
Fig. 1. P r i n c i p l e d e s i g n o f a flat-plate s o l a r c o l l e c t o r . M o s t p r a c t i c a l
collectors, though, do not use antireflection coatings, infrared
reflecting coatings, or transparent thermal insulation materi-
als. T h e different c o m p o n e n t s a r e n o t t o s c a l e . ( F r o m R é f . 1 ) .
T h e r e q u i r e m e n t s for e n e r g y efficiency c a n b e i n t r o d u c e d w i t h r e f e r e n c e to t h e
"natural" r a d i a t i o n in o u r s u r r o u n d i n g s . T h e p e r t i n e n t r a d i a t i v e p r o p e r t i e s a r e
s h o w n i n F i g . 2 . T h e s o l i d c u r v e r e p r o d u c e s a t y p i c a l s p e c t r u m for s o l a r i 2 rradiance
at t h e g r o u n d . S p e c i f i c a l l y , the c u r v e g i v e s t h e air m a s s ( A M ) 2 s p e c t r u m , c o r r e -
s p o n d i n g to c l e a r w e a t h e r w i t h t h e s u n 3 0 ° a b o v e t h e h o r i z o n . It is s e e n that s o l a r
r a d i a t i o n c o m e s at w a v e l e n g t h s s u c h that λ < 3 μιη. T h e a b s o r b e r s u r f a c e o f t h e
s o l a r c o l l e c t i o n d e v i c e m u s t a b s o r b this e n e r g y . T h e s u r f a c e t h e n h e a t s u p a n d
e m i t s t h e r m a l r a d i a t i o n . T h e d a s h e d c u r v e s in F i g . 2 i n d i c a t e b l a c k b o d y s p e c t r a
for t h r e e t e m p e r a t u r e s ; t h e e m i t t e d e n e r g y is n e g l i g i b l e at λ < 3 μπ\ for a t e m p e r a -
ture o f τ < 100°C. T h e losses associated with thermal emission should b e avoided
in o r d e r to g a i n e n e r g y efficiency. T h i s c a n b e a c c o m p l i s h e d in t w o different w a y s .
T h e first o n e r e l i e s o n a c o v e r g l a s s w i t h a c o a t i n g t h a t reflects at λ > 3 μπι s o that
t h e r a d i a t i o n e m i t t e d f r o m t h e a b s o r b e r s u r f a c e is b r o u g h t b a c k t o this s a m e
s u r f a c e . A s e c o n d , a n d m o r e c o m m o n l y u s e d , w a y to d i m i n i s h t h e h e a t l o s s e s is
1 1 11
Γ Ί — ι—ι J ΙJ ι "ι 111
'I I τ' — ι Iι I "I I Ij I ~
•?riX>- I I Solar -
h AM2 Blackbody
:
§ lh ' \ ^300°C
0.5- / / V^/20(TC-
I ; / \ />- - V 0 0
*
ω o 0.2
u / . ι.... 1ι ν Vr>i
j
2 r r5r r û 10
ι '
î ^<ir
'''I
20 J
OB Wavelength
1 (urn)
Fig. 2 . S p e c t r a for c h a r a c t e r i s t i c s o l a r i r r a d i a n c e a n d for b l a c k b o d y

radiation pertaining to three temperatures.
to h a v e a n a b s o r b e r s u r f a c e w h o s e t h e r m a l e m i t t a n c e i s l o w . T h e s e a r e t h e
s e l e c t i v e l y s o l a r - a b s o r b i n g surfaces t o b e d i s c u s s e d i n this c h a p t e r . T h e y a r e
characterized b y a l o w reflectance at λ < X a n d a high reflectance at λ > X , w h e r e
c c
X « 3 μιη for τ < 100°C. A t increased operating temperatures, X should b e
c c
d i s p l a c e d t o w a r d s a l o w e r v a l u e , a n d at τ = 3 0 0 ° C it is a d e q u a t e t o p u t X « 2 μ ι η .
c
Q u a l i t a t i v e p e r f o r m a n c e criteria c a n b e f o r m u l a t e d b y u s e o f t h e n o r m a l s o l a r
absorptance ( A i ) a n d the hemispherical thermal emittance ( E h ) . T h e s e para-
s o t e r m
meters are defined b y
A i = 1 dX 0 (λ) ( 1 - R (λ, 0 ) ) / J d λ rf ( λ ) , (1)

s o sl o sol
π/2
Etherm (Ό = J dX J d(sin2 Θ) 0 (λ, θ ) ) / J άΧ 0

t hm(λ,
e τ)r (1-R t hm(λ,
e τ),r (2)
0 -5
therm = q λ [exp ( c /(λτ)], (3)
2
w h e r e 0 i is t h e s o l a r i r r a d i a n c e (for e x a m p l e t h e A M 2 s p e c t r u m ) , R (λ, θ) is16t h e
so
r e f l e-c t a2n c e as a function o f w2 a v e l e n g t h a n d i n c i d e n c e a n g l e , c\ = 3 . 7 8 1 4 χ Ι Ο "
W m , a n d C2 = 1.4388 χ 1 0 ~ m K . C l e a r l y , t h e d e s i r e d s p e c t r a l s e l e c t i v i t y i m p l i e s
that A i s h o u l d b e c l o s e t o u n i t y a n d that E h should b e minimized.
s o t e mr
Coatings a n d surface treatments with high A i a n d l o w E h
s o t e mrw e r e s u b j e c t to
intense research a n d development in m a n y laboratories around the world during
t h e 1 9 7 0 ' s a n d e a r l y 1 9 8 0 ' s . T h i s w o r k13h a s b e e n r e v i e w e d i n c o n s i d e r a b l e detail i n
Refs. 3 - 1 2 . A n a n n o t a t e d b i b l i o g r a p y , c o v e r i n g t h e p e r i o d 1 9 5 5 - 1 9 8 1 , w a s p u b l i s -
h e d i n 1 9 8 3 . It lists 5 6 5 scientific p a p e r s , i n c l u d i n g s t u d i e s o f a l m o s t 2 8 0 different
c o a t i n g s o r s u r f a c e t r e a t m e n t s . R a t h e r t h a n r e v i e w i n g this v a s t , a n d s o m e w h a t
stale, field o n c e a g a i n , this c h a p t e r f o c u s e s o n c e r t a i n k e y i s s u e s a n d o n t h e latest
d e v e l o p m e n t s . W e first c o n s i d e r d e s i g n p r i n c i p l e s for o b t a i n i n g s p e c t r a l selec-
tivity, a n d d a t a f o r s e v e r a l s o l a r c o l l e c t o r surfaces u s e d in p r a c t i c e . S u b s e q u e n t l y
w e d i s c u s s t h e o r e t i c a l m o d e l s for t h e o p t i c a l p r o p e r t i e s a n d c u r r e n t i d e a s c o n c e r -
n i n g d e g r a d a t i o n at e l e v a t e d t e m p e r a t u r e . T h e t r e a t m e n t o f d e g r a d a t i o n c o v e r s
t h e latest a d v a n c e s for this t e c h n i c a l l y i m p o r t a n t s u b j e c t a n d is c a r r i e d o u t i n
detail for s o m e p r a c t i c a l l y useful s o l a r c o l l e c t o r s u r f a c e s .
II. SELECTIVELY SOLAR-ABSORBING SURFACES: DESIGN AND

DATA
A. Principles
It is p o s s i b l e t o e x p l o i t s e v e r a l different d e s i g n p r i n c i p l e s a n d p h y s i c a l m e c h a -
n i s m s i n o r d e r to c r e a t e a s e l e c t i v e l y s o l a r - a b s o r b i n g surface. S i x o f t h e s e a r e
s h o w n s c h e m a t i c a l l y i n F i g . 3 . T h e m o s t s t r a i g h t f o r w a r d o n e is t o u s e a m a t e r i a l
w h o s e intrinsic radiative properties h a v e t h e d e s i r e d k i n d o f s p e c t r a l s1e4l e c t i v i t y .
G e n e r a l l y s p e a k i n g , this a p p r o a c h h a s n o t b e e n v e r y fruitful, b u t w o r k o n ZrB2
Intrinsic Metal
selective material -Dielectric
Substrate Metal
_ 2um
Antireflection coating
Silicon
Metal
Metal
, Dielectric
SnO: 2F,...
Metal
Dielectric
Substrate
wmm*\ Black enamel
Substrate
Fig. 3. S c h e m a t i c d e s i g n s o f six different c o a t i n g s a n d s u r f a c e

t r e a t m e n t s for s e l e c t i v e a b s o r p t i o n o f s o l a r e n e r g y .
(From Réf. 1).
a n d o n s o m e o t h e r c o m p o u n d s i n d i c a t e s that i n t r i n s i c a l l y s e l e c t i v e m a t e r i a l s d o
exist.
Semiconductor-metal tandems can give the desired spectral selectivity b y absor-

b i n g s h o r t - w a v e l e n g t h r a d i a t i o n in a s e m i c o n d u c t o r w h o s e b a n d g a p is ~ 0.6 e V
a n d h a v i n g l o w t h e r m a l e m i t t a n c e as a r e s u l t o f t h e u n d e r l y i n g m e t a l . T h e useful
s e m i c o n d u c t o r s h a v e u n d e s i r a b l y l a r g e refractive i n d i c e s , w h i c h t e n d s t o y i e l d
h i g h reflection l o s s e s . H e n c e it is n e c e s s a r y to antireflect t h e s u r f a c e s in t h e r a n g e
o f s o l a r radiation. A w e l l k n o w n w o r k 1 ' 15 6 in this c a t e g o r y is c e n t e r e d o n S i - b a s e d
designs prepared b y chemical vapour deposition.
Multilayer absorbers c a n b e t a i l o r e d s o that t h e y b e c o m e efficient s e l e c t i v e

a b s o r b e r s o f s o l a r r a d i a t i o n . It is c o m p a r a t i v e l y e a s y t o c o m p u t e their o p t i c a l
p e r f o r m a n c e , w h i c h facilitates o p t i m i z a t i o n o f the d e s i g n . O n e i n t e r e s t i n g
e x a m p l e is AI2O3/M0/AI2O3, w h i c h w a s o r i g i n a l l y d e v e l o p e d for t h e U . S . s p a c e
p r o g r a m m e . 17 T h i s t y p e o f surface h a s b e e n p r o d u c e d b y l a r g e - a r e a s p u t t e r i n g
t e c h n o l o g y . 18
Metal-dielectric composite coatings c o n s i s t o f v e r y fine m e t a l p a r t i c l e s in a

dielectric host. T h e ensuing optical properties can be intermediate b e t w e e n those
o f t h e m e t a l a n d o f t h e dielectric. T h e effective m e d i u m t h e o r i e s i n t r o d u c e d in
the chapter on "Optical Properties of I n h o m o g e n e o u s T w o - C o m p o n e n t Materials"
a r e o f g r e a t v a l u e for m o d e l l i n g t h e o p t i c a l p e r f o r m a n c e . T h e m e t a l - d i e l e c t r i c
c o n c e p t offers a h i g h d e g r e e o f flexibility, a n d the o p t i m i z a t i o n o f t h e s o l a r selec-
tivity c a n b e m a d e w i t h r e g a r d to the c h o i c e o f c o n s t i t u e n t s , c o a t i n g t h i c k n e s s ,
particle concentration, and the size, shape, and orientation o f the particles. T h e
s o l a r a b s o r p t a n c e c a n b e b o o s t e d b y u s e o f s u i t a b l e s u b s t r a t e m a t e r i a l s a n d anti-
reflection t r e a t m e n t s . T h e c o m p o s i t e c o a t i n g s c a n b e p r o d u c e d b y a v a r i e t y o f
t e c h n i q u e s s u c h as e l e c t r o p l a t i n g , a n o d i z a t i o n , i n o r g a n i c c o l o u r a t i o n o f a n o d i z e d
aluminium, chemical vapour deposition and codeposition of metal and insulator
b y e v a p o r a t i o n a n d s p u t t e r i n g . W e r e t u r n to s e v e r a l o f t h e s e p o s s i b i l i t i e s b e l o w .
Textured surfaces can produce a high solar absorptance b y multiple reflections

a g a i n s t m e t a l d e n d r i t e s t h a t are ~ 2 μ ι η a p a r t , w h i l e t h e l o n g - w a v e l e n g t h e m i t -
t a n c e is r a t h e r u n a f f e c t e d b y this texture. W e l l - k n1 o9w n e x a m p l e s a r e d e n d r i t i c
t u n g s t e n p r e p a r e d b y c h e m i c a l v a p o u r d e p o s i t i o n a20 nd textured copper, nickel,
a n d stainless steel surfaces m a d e b y s p u t t e r e t c h i n g . T e x t u r e d A l - S i (Ref. 2 1 ) will
be d i s c u s s e d later.
T h e final c o n c e p t c o n s i d e r e d h e r e i n v o l v e s a selectively solar-transmitting

coating on a blackbody-like absorber. T h e absorber can be chosen from a m o n g
m a t e r i a l s w i t h p r o v e n l o n g - t e r m d u r a b i l i t y ( s u c h as b l a c k e n a m e l ) , a n d t h e
c o a t i n g c a n b e a h e a v i l y d o p e d o x i d e s e m i c o n d u c t o r (for e x a m p l e SnC>2:F; cf. t h e
f o l l o w i n g c h a p t e r ) . C o a t i n g s o f this t y p e a r e d i s c u s s e d in Ref. 2 2 .
B. R e s u l t s for S o m e P r a c t i c a l l y U s e f u l S u r f a c e s
T h e m o s t w i d e l y u s e d s e l e c t i v e l y s o l a r - a b s o r b i n g surface s e e m s to b e "black
c h r o m i u m " , w h i c h is a c o m p l e x c o m p o s i t e o f m e t a l l i c c h r o m i u m a n d d i e l e c t r i c
C r 0 3 - T h e m e t a l c o n c e n t r a t i o n is l o w at the interface t o w a r d s t h e air a n d in-
2
c r e a s e s w i t h d e p t h i n t o t h e c o a t i n g . T h e s e l e c t i v e s o l a r a b s o r p t i o n a p p e a r s to b e a
c o m b i n a t i o n o f the effect o f t h e m e t a l - d i e l e c t r i c c o m p o s i t e23a n d o f t h e p r o n o u n c e d
s u r f a c e r o u g h n e s s that h a s b e e n o b s e r v e d in t h e s e f i l m s . B l a c k c h r o m i u m h a s 24
a
h i g h v o i d fraction a n d c o n s i s t s o f r o u n d e d p a r t i c l e s w i t h sizes o f a b o u t 1 0 0 n m .
T h e c h r o m i u m c r y s t a l l i t e s a r e s m a l l e r , t2h5o u g h , o n t h e o r d e r o f 10 n m , a n d a r e
p r o b a b l y e m b e d d e d in t h e o x i d e p h a s e . T h e inset in F i g . 4 g i v e s a s c h e m a t i c
p i c t u r e o f t h e m i c r o s t r u c t u r e . T h e o r i g i n a l w o r k o2 n6 b l a c k c h r o m i u m for s o l a r
e n e r g y a p p l i c a t i o n s w a s c a r r i e d o u t b y M c D o n a l d , w h o m o d i f i e d the p r o c e d u r e
for m a k i n g d e c o r a t i v e e l e c t r o p l a t e d l a y e r s . S e v e r a l s u b s e q u e n t s t u d i e s h a v e b e e n
m a d e on the relationship between plating parameters and structural and optical
p r o p e r t i e s ; s e26
e , for e x a m p l e , Ref. 2 7 . S p e c t r a l r e f l e c t a n c e d a t a f r o m M c D o n a l d ' s
initial s t u d y are r e2 p8r o d u c e d in the m a i n part o f F i g . 4 . T h e figure a l s o s h o w s
s p e c t r a l r e f l e c t a n c e for t w o c o m m e r c i a l e l e c t r o p l a t e d b l a c k c h r o m i u m c o a t i n g s ,
specifically for p r o d u c t s b y E n e r g i e S o l a i r e ( E S ) S.A. in S w i t z e r l a n d ( c o a t i n g b a c k e d
by stainless steel) a n d b y M t i S o l a r Inc. in the U . S . ( c o a t i n g b a c k e d b y n i c k e l -
c o v e r e d c o p p e r ) . F o r all o f the c o a t i n g s , the r e f l e c t a n c e is l o w in t h e s o l a r r a n g e
a n d h i g h in t h e t h e r m a l r a n g e , i.e., the s p e c t r a l s e l e c t i v i t y is l a r g e a n d a p p r o x i -
m a t e l y m a t c2h8e s t h e i d e a l c u r v e i n d i c a t e d b y the d o t t e d l i n e s in F i g . 4 . T h e E S 28
coating h a s A 29
s l o- 0.94 a n d E t hm ( 1e0 0 ° rC ) - 0.20, w h e r e a s the M t i c o a t i n g h a s
A l * 0-97 a n d E ( 1 0 0 ° C ) » 0.09. F i g u r e 4 also s h o w s s o m e r e s u l t s for
s o t hm e r
smooth sputter-deposited C r - C r U 3 composite coatings.
2
Other commercially produced selectively solar-absorbing coatings comprise
m e t a l l i c N i p a r t i c3l0e s e m b e d d e d in a n o d i c A I 2 O 3 . T h e initial w o r k w a s b y
Andersson et.al. T h e s e c o a t i n g s a r e m a d e b y a t w o - s t e p p r o c e s s w i t h an initial
a n o d i z a t i o n o f an a l u m i n i u m s h e e t in, for e x a m p l e , d i l u t e p h o s p h o r i c a c i d . T h i s
transforms the surface layer of the metal into porous A I 2 O 3 . Subsequently metal
is p r e c i p i t a t e d i n s i d e t h e p o r e s b y e l e c t r o c h e m i c a l m e a n s , for e x a m p l e b y A C
e l e c t r o l y s i s in a b a t h c o n t a i n i n g n i c k e l sulfate. M e t a l p a r t i c l e s i z e s a r e p r o b a b l y o f
the o r d e r o f a f e w tens o f n a n o m e t r e s . B y m o d i f i c a t i o n o f the s e c o n d s t e p o n e c a n
precipitate particles of other metals. A detailed study of the relation b e t w e e n
1—ι—I ι ι ι ι ι 1—ι 1—ι—ι ι ι ι ι ι 1—ι 1 1—ι I I

100 — R —
_ "Black Chrome"
80 - j /[/ /
j //f—/—McD
• / / / - / — M t ES
i
1w e n " Ϊ// /^~
60 - f II I -
8 E x p . (plated) N i l
2 7 Exp.(sputtered)/ Ν J ~
S 40 - Ideal III/ ^ __^y^^^^^^t ~
20
" v
IJ/\ ~*^^BP • 2
-ES — l ^ ^ N ^ J / ;
o JUtL- ^Ty>< j _
I 1 11II I I I I I I I III I I I I I I I II I
Wavelength (μιη)
0.2 0.5 1 2 5 10 20 50
Fig. 4 . Spectral reflectance m e a s u r e d for "black c h r o m i u m " coatings
on reflecting substrates. Solid curves refer t o electroplated
c o a t i n g s p r e p a r e d b y M c D o n a l d ( M c D ; R e f . 2 6 ) , M t i S o l a r Inc.
(Ref. 2 8 ) , a n d E n e r g i e S o l a i r e S.A. ( E S ; R e f . 2 8 ) . T h e d o t t e d
c u r v e refers t o a s p u t t e r - d e p o s i t e d C r - C r 0 3 c o m p o s i t e c o a t i n g
2
(Ref. 2 9 ) . D o t t e d l i n e s r e p r e s e n t a n i d e a l r e f l e c t a n c e profile.
I n s e t i n d i c a t e s t h e m i c r o s t r u c t u r e for t h e e l e c t r o p l a t e d c o a t i n g s :
a g r a d e d c o m p o s i t e ( l a y e r 2 ) w i t h a r o u g h t o p s u r f a c e ( l a y e r 1).
deposition conditions and spectral selectivity is reported in Ref. 3 1 . In essence, the

coating comprises a nickel-pigmented A I 2 O 3 layer located under a porous A I 2 O 3
l a y e r . T h e p o r o s i t y i s l a r g e s t a t the o u t e r surface. T h e b o t t o m o f t h e c o a t i n g
c o n s i s t s o f a thin c o m p a c t A I 2 O 3 s h e a t h s e r v i n g a s diffusion b a r r i e r . T h i s
m i c r o s t r u c t u r e i s i n d i c a t e d i n t h e i n s e t o f F i g . 5. T h e m a i n p a r t o f t h e f i g u r e
28w o o f t h e m a r e
s h o w s s p e c t r a l r e f l e c t a n c e for t h r e e t y p e s o f N 1 - A I 2 O 3 c o a t i n g s . T
c o m m e r c i a l l y p r o d u c e d b y S u n s2t r3 i2
8p ( S U ) V i k i n g A B i n S w e d e n a n d b y S h o w a
(SH) A l u m i n i u m C o . in J a p a n . 3 '0 T h e t h i r d c o a t i n g 2-8d e n o t e d G r a n g e s ( G R ) -
E
was studied b y Andersson e t . a l . T h e S2 U8 coating h a s A i « 0.88 and
s o
t h e r m ( 1 0 0 ° C ) « 0 . 0380, t h e S H c o a t i n g h a s A
s l »o 0.93 a n d E t hm( 1 e0 0 ° Cr ) - 0 . 1 3 , a n d
the G R coating h a s A - 0.92 and E (65°C) - 0.10.
sl o 33t hm c r
Recently Lanxner and Elgat r e p o r t e d work o n sputter-deposited molybdenum-
b a s e d c o m p o s i t e c o a t i n g s for u s e o n l a r g e - s c a l e t u b u l a r s o l a r c o l l e c t o r s d e s i g n e d t o
o p e r a t e a t τ > 3 0 0 ° C . T h e m i c r o s t r u c t u r e , i n d i c a t e d i n t h e i n s e t o f F i g . 6, e m b o d i e s
two graded Mo-dielectric composite layers backed b y an infrared-reflecting
m o l y b d e n u m l a y e r . A n a n t i r e f l e c t i n g S1O2 l a y e r a t t h e t o p a n d a diffusion b a r r i e r
of A I 2 O 3 at the b o t t o m complete the design. Figure 6 s h o w s that the reflectance
has a high degree of spectral selectivity, with the steepest reflectance c h a n g e
a r o u n d λ « 2 μ ι η . I t s h o u l d b e r e m a r k e d that t h e m a i n r e f l e c t a n c e s t e p s h o u l d
1 1 1 I I M I 1 1 1 1 1 I I I I I 1 1 1 1—I I I I
100 — ---- - ' - —

_ Ni pigmented . s Ç ï ^ / ' _
anodic A l 0 ; / / /
23
80 - > / //
-__ \ ill
£ "
fin EXP- (SH) \! I
ο E x p . (GR) !. / '
ο ΤτιΎτ^.. j —
1 1 1 I I M l 1 I I I I I I I I I I I I l I ι ι
0.2 0.5 1 2 5 10 20 50
Wavelength (μm)
Fig. 5. S p e c t r a l r e f l e c t a n c e m e a s u r e d for n i c k e l - p i g m e n t e d a n o d i c
A I 2 O 3 coatings produced by electrochemical treatment o f an
a l u m i n i u m sheet. C u r v e s refer to c o a t i n g s p r e p a r e d b y
G r a n g e s ( G R ; Ref. 3 0 ) , S h o w a A l u m i n i u m C o . ( S H ; R e f s . 2 8 , 3 2 )
and Sunstrip Viking A B (SU; Ref. 28). Dotted lines represent
a n i d e a l r e f l e c t a n c e profile. I n s e t i n d i c a t e s t h e m i c r o s t r u c t u r e
of the c o a t i n g s : A n a l u m i n i u m o x i d e diffusion b a r r i e r (layer 4 ) ,
a N 1 - A I 2 O 3 c o m p o s i t e (layer 3 ) , a n d a p o r o u s a l u m i n i u m o x i d e
(layer 2 ) w i t h i n c r e a s i n g p o r o s i t y t o w a r d s t h e t o p s u r f a c e
(layer 1).
o c c u r at a s h o r t e r w a v e l e n g t h for a c o a t i n g d e v i s e d to o p e r a t e at a h i g h t e m p e r a -
t u r e t h a n for o n e to b e u s e d at ~ 1 0 03°3C , w h i c h is e a s i l y i n f e r r e d f r o m F i g . 2 . T h e
c o a t i n g in Fig. 6 is c h a r a c t e r i z e d b y A
s I =o 0.97 ± 0.01, E t hm( 5e0 ° C r) - 0 . 1 0 , a n d
Etherm ( 3 5 0 ° C ) = 0.17 ± 0 . 0 1 .
A m o n g t h e r e m a i n i n g c o a t i n g s t h a t h a v e r e a c h e d c o m m e r c i a l i z a t i o n , o r for
w h i c h p r o c e s s e s a d e q u a t e for p r a c t i c a l m a n u f a c t u r i n g a r e k n o w n , w e n o t e c3h e 4 mi-
cally treated rough nickel surfaces (kno 3w35 6n u n d e r the t r a d e n a m e M A X O R B ) ,
"black n i c k e l " m a d e b y e l e c t r o p l a t i n g , ' g r a d e d s t a i n l e s s3 - s3
t7
8e e l c a r b o n c o a t i n g s
d e v e l o p e d39for h i g h p e r f o r m a n c e t u b u l a r s o l a r c o l l e c t o r s , ' 4c0o p p e r o x i d e
c o a t i n g s , and metal-filled coloured stainless-steel s u r f a c e s . In this list w e
s h o u l d a l4s1o n o t e C r - C r 0 3 c o m p o s i t e c o a t i n g s m a d e b y "roll-coating" e v a -
2
p o r a t i o42
n a n d A I - A I 2 O 3 m a d e b y "integral" c o l o u r a t i o n o f a n o d i c a l u m i n i u m
oxide. 4 43
4
W o r k o n s e l e c t i v e l y s o l a r - a b s o r b i n g p a i n t s h o l d s p r o m i s e for e x t r e m e l y
cheap s u r f a c e s . '
ι—ι I ι ι mj ι—ι 1—ι—ι ι ι ι—ι 1—ι 1—ι—ι I Γ

100 — r - —
_ Sputtered '
" Mo-based /
80 - /
_ Composite /
£ 60 - Ε χ \ I
8 - — ρ · \
c — ; / -
2 _ Ideal ;/ 1 / \ -
Si JE · · » » · Φ·
3
j\ —^ÉSËIÉîl^
I I—I ι ι ι I\ I I I I l I I I I \ I I I I I I
0.2 0.5 1 2 5 10 20 50
Wavelength (μm)
Fig. 6. S p e c t r a l r e f l e c t a n c e m e a s u r e d for a m o l y b d e n u m - b a s e d sputter-

d e p o s i t e d c o a t i n g (Ref. 3 3 ) . Different r e c o r d i n g m e t h o d s w e r e
u s e d for λ < 2.5 μ ι η a n d λ > 2.5 μιη, w h i c h e x p l a i n s t h e b r e a k in
t h e c u r v e . D o t t e d lines r e p r e s e n t a n ideal r e f l e c t a n c e profile.
I n s e t s h o w s t h e c o a t i n g m i c r o s t r u c t u r e w i t h five s u p e r i m p o s e d
layers. T h e y c o m p r i s e , from t h e top: S1O2, g r a d e d M0-S1O2,
g r a d e d M 0 - A I 2 O 3 , m o l y b d e n u m , a n d AI2O3. T h e s u b s t r a t e is o f
s t a i n l e s s steel ( S S ) .
III. MODELS FOR MICROSTRUCTURE AND OPTICAL PROPERTIES
In t h e p r e v i o u s s e c t i o n w e f o u n d that m o s t c o m m e r c i a l l y p r o d u c e d s e l e c t i v e l y
solar-absorbing coatings consist o f a mixture of metallic particles in a dielectric
m a t r i x a n d a r e b a c k e d b y a m e t a l l i c s u b s t r a t e . C o m m e r c i a l c o a t i n g s a r e still l a r g e l y
p r o d u c e d b y e l e c t r o c h e m i c a l m e t h o d s (cf. F i g s . 4 a n d 5 ) , b u t p h y s i c a l v a p o u r
deposition techniques, such as sputtering, are b e c o m i n g o f increasing importance
(cf. F i g . 6 ) . I n b a s i c s t u d i e s , h o w e v e r , p h y s i c a l v a p o u r d e p o s i t i o n h a s b e e n w i d e l y
used to extract detailed information o n the relation between microstructural para-
m e t e r s o f t h e c o a t i n g s a n d their o p t i c a l p r o p e r t i e s a n d s p e c t r a l s e l e c t i v i t y . In this
section w e consider microstructural models based o n characterization studies o f
t h e p e r t i n e n t c o a t i n g s . W i t h t h e s e m o d e l s as a b a c k g r o u n d , w e d i s c u s s t h e o r i e s
for t h e o p t i c a l p r o p e r t i e s o f s e l e c t i v e l y s o l a r - a b s o r b i n g s u r f a c e s w i t h a m e t a l -
dielectric composite configuration.
A. Microstructure
It is s u i t a b l e to m a k e a d i s t i n c t i o n b e t w e e n m e t a l - d i e l e c t r i c c o m p o s i t i e s w i t h
homogeneous and graded composition. A homogeneous layer has the same
structure throughout, while a graded layer displays a metal content that varies
w i t h t h e d e p t h in t h e layer. I n p r a c t i c e it is m o s t a d v a n t a g e o u s t o h a v e a m e t a l
c o n t e n t t h a t is h i g h c l o s e t o t h e s u b s t r a t e , a n d c o n t i n u o u s l y d e c r e a s e s as o n e
a p p r o a c h e s t h e front s u r f a c e .
A l a r g e a m o u n t o f r e s e a r c h h a s b e e n c a r r i e d o u t o n m e t a l - d i e l e c t r1 i3
c composite
( a l s o c a l l e d " c e r m e t " ) c o a t i n g s , a s c a n b e s e e n in t h e b i b l i o g r a p h y . A single
c o m p o s i t e l a y e r o n t o p o f a m e t a l s u b s t r a t e often d o e s n o t g i v e sufficient s o l a r 4 46 5
absorptance, and there are only a few cases w h e r e A j > 0.90 has b e e n r e p o r t e d '
s o
for h o m o g e n e o u s c o m p o s i t e l a y e r s b a c k e d b y m e t a l . T h e r e f o r e m o r e c o m p l i c a t e d
d e s i g n s h a v e to b e u s e d . T h e r e a r e b a s i c a l l y t w o w a y s to i m p r o v e t h e o p t i c a l
p r o p e r t i e s o f t h e c o a t i n g s ; t h e y a r e s h o w n s c h e m a t i c a l l y in F i g . 7. F i r s t , o n e m a y
u s e a n t i r e f l e c t i o n c o a t i n g s o n t o p o f t h e c o m p o s i t e l a y e r . T h i s " T y p e I" d e s i g n
c o n s i s t s of, in o r d e r f r o m t h e b o t t o m , a m e t a l s u b s t r a t e , a m e t a l - d i e l e c t r i c c o m p o -
site l a y e r , a n a n t i r e f l e c t i o n l a y e r , u s u a l l y c o m p r i s e d o f a d i e l e c t r i c , a n d a r o u g h
s u r f a c e l a y e r that m a y o r m a y n o t b e p r e s e n t . T h e o u t e r m o s t l a y e r c a n b e r e g a r d e d
as a c o m p o s i t e o f d i e l e c t r i c a n d air. T h i s T y p e I c o n f i g u r a t i o n is often u s e d in
selective solar absorbers produced b y evaporation and sputtering. T h e absorbing
l a y e r u s u a l l y c o n s i s t s o f a t r a n s i t i o n m e t a l d i s p e r s e d in a n o x i d e , a n d it is
convenient to p r o d u c e the antireflection layer from the s a m e oxide. R e p o r t e d
s t u d i e s h a v e c o n c e r n e d t h e m a t e r i a l s N i - S i 0 (Ref. 4 7 ) , N i - M g O (Ref. 4 7 ) , C r - C r 0
2 23
(Ref. 2 9 ) , C o - A l 0 (Ref. 4 8 ) , P t - A l 0 (Ref. 4 9 ) a n d N i - A l 0 (Ref. 5 0 ) . I n g e n e r a l ,
23 23 23 30
o n e c a n o b t a i n A i « 0.95 a n d E h
s o t e m(r1 0 0 ° C ) r a n g i n g f r o m 0.05 to 0 . 1 0 . A m o n g
t h e c o m m e r c i a l l y u s e d c o a t i n g s , it h a s b e e n s h o w n b y A n d e r s s o n e t . a l . t h a t t h e
s t r u c t u r e o f m e t a l p i g m e n t e d a n o d i c a l u m i n i u m o x i d e s o l a r a b s o r b e r s is w e l l
d e s c r i b e d b y t h e T y p e I c o n f i g u r a t i o n in F i g . 7. T h e m o d e l d e s c r i b e s t h e o p t i c a l
p r o p e r t i e s o f t h e c o a t i n g s as w e l l as t h e d e g r a d a t i o n o f t h e s o l a r a b s o r p t a n c e at
h i g h t e m p e r a t u r e s as w e w i l l r e t u r n to b e l o w .
Type I T y p e 7L
ΛΛ/ΙΛΛΛΛ NA / W V W | Dielectric-air "composite"

Dielectric
Metal-dielectric c o m p o s i t e
Metal
Fig. 7. M i c r o s t r u c t u r a l m o d e l s for s e l e c t i v e l y s o l a r - a b s o r b i n g c o a t i n g s .
In t h e s e c o n d c o n f i g u r a t i o n ( T y p e II in F i g . 7 ) , t h e h o m o g e n e o u s m e t a l - d i e l e c t r i c
c o m p o s i t e l a y e r h a s b e e n r e p l a c e d b y a g r a d e d o n e . O t h e r w i s e t h e d e s i g n is s i m i l a r
t o t h a t o f T y p e I. A s b e f o r e , t h e u p p e r d i e l e c t r i c - a i r l a y e r m a y o r m a y n o t b e
p r e s e n t . In p r i n c i p l e , t h e T y p e II s t r u c t u r e c a n g i v e a h i g h e r A i t h a n t h e T y p e I
s o
s t r u c t u r e , b u t in m o s t c a s e s t h e i m p r o v e m e n t is n o t v e r y l a r g e . M o d e l c a l c u l a -
t i o n s a n d a d i s c u s s i o n o f o p t i m u m g r a d i n g profiles a r e r e p o r t e d in R e f . 5 1 . T h e
u s e o f g r a d e d m e t a l - d i e l e c t r i c c o a t i n g s for s e l e c t i v e s o l a r a b s o r b e r s w a s r e v i e w e d
52
by Craighead. C o a t i n g s p r o d u c e d b y e v a p o r a t i o n a n d s p u t t e r i n g in m o s t c a s e s
e m p l o y o n l y a g r a d e d l a y e r o n 53 a s u b s t r a t e , b u t in a f e w c a s e s a n antireflection l a y e r
is a l s o i n c l u d e d in t h e d e s i g n . Metal-dielectric composite layers have been
p r o d u c e d f r o m a5w54 5i d e r a n g e o f t r a n s i t i o n a n d n o b l e m e t a l s u s u a l l y e m b e d d e d in
various o x i d e s . ' A m o n g the more widely studied combinations, P t - A l 0
23
(Refs. 5 3 , 5 6 ) , N i - A l 0 (Ref. 5 6 ) a n d N i - M g F (Ref. 5 7 ) s h o u l d b e m e n t i o n e d .
23 2
C h e m i c a l l y a n d e l e c t r o c h e m i c a l l y d e p o s i t e d c o a t i n g s , s u c h as t h e c o m m o n c o m -
mercial ones discussed above, display a very complex structure with graded or
h o m o g e n e o u s composite layers, voids, oxide films, surface roughness, etc. This
m a k e s t h e m o d e l l i n g o f their o p t i c a l p r o p e r t i e s m o r e difficult t h a n for t h e s p u t -
t e r e d a n d e v a p o r a t e d c o a t i n g s , w h i c h a r e d e p o s i t e d in a m o r e c o n t r o l l e d w a y .
H o w e v e r , t h e T y p e II c o n f i g u r a t i o n in Fig. 7 a p p e a r s to b e a s u i t a b l e q u a l i t a t i v e
m o d e l for s e l e c t i v e s o l a r a b s o r b e r s w i t h a c o m p l e x m i c r o s t r u c t u r e in m a n y c a s e s .
In p a r t i c u l a r , T y p e II m o d e l s h a v e r e c e n t l y b e e n u s e d to m o d e l t h e o p t i c a l p r o p e r -
ties as w e l l as t h e d e g r a d a t i o n o f the 5s8o l a r a b s o r p t a n c e in a series o f i n v e s t i6 g0a t i o n s
b y S c h e r e r et.al. c o v e r i n g b l a c k z i n c , N i - A l 0 (Ref. 5 9 ) a n d c o p p e r o x i d e
23
c o a t i n g s . B l a c k c h r o m e is r e a l i z e d to h a v e a v e r y c o m p l e x s t r u c t u r e (cf. F i g2. 6 44) 61
2a n d
24
g r a d i n g m o d e l s h a v e b e e n tried in o r d e r to d e s c r i b e its o p t i c a l p r o p e r t i e s . ' ' A
v e r y e l a b o r a t e m o d e l b y S w e e t e t . a l . c o u l d q u a l i t a t i v e l y d e s c r i b e f e a t u r e s o f the
d e g r a d a t i o n b e h a v i o u r for this k i n d o f c o a t i n g . T h i s latter m o d e l e m p l o y e d a
t h r e e - c o m p o n e n t m i x t u r e o f c h r o m i u m , C r 0 a n d air, w h e r e b o t h t h e m e t a l a n d
2 3
v o i d fractions w e r e t a k e n to b e g r a d e d . T h e v a l i d i t y o f this m o d e l is in q u e s t i o n ,
t h o u g h , as w e w i l l c o m e b a c k to b e l o w .
A further r e f i n e m e n t o f t h e m i c r o s t r u c t u r a l m o d e l s c a n b e m a d e b y c o m b i n i n g
t h e T y p e I a n d T y p e II c o n f i g u r a t i o n s so that the m u l t i l a y e r c o a t i n g c o n s i s t s of, in
order from the bottom, a metal substrate, a h o m o g e n e o u s composite layer, a
g r a d e d c o m p o s i t e l a y e r , a n antireflection c o a t i n g , a n d , p o s s i b l y , s u r f a c e r o u g h n e s s
m o d e l l e d b y a n i n s u l a t o r - a i r g r a d i n g . U n f o r t u n a t e l y this k i n d o f m o d e l h a s n o t
b e e n fully t e s t e d a g a i n s t e x p e r i m e n t a l d a t a , a l t h o u g h the s t r u c t u r e a p p e a r s
p h y s i c a l l y r e a l i s t i c . W e w i l l later p r e s e n t an e x a m p l e o f a c a l c u l a t i o n o f o p t i c a l
p r o p e r t i e s b a s e d o n this m o d e l , w h i c h w e call " T y p e III".
B. A p p l i c a b i l i t y o f E f f e c t i v e M e d i u m T h e o r y for t h e O p t i c a l P r o p e r t i e s
T h e m i c r o s t r u c t u r a l m o d e l s in F i g . 7 f o r m a s u i t a b l e s t a r t i n g p o i n t for o p t i c a l
m o d e l l i n g b y u s e o f Effective M e d i u m T h e o r y ( E M T ) . S e v e r a l f o r m u l a t i o n s o f
this t y p e o f t h e o r y w e r e p r e s e n t e d in the c h a p t e r o n O p t i c a l P r o p e r t i e s o f I n h o m o -
geneous T w o - C o m p o n e n t Materials above. T h e E M T s give the c o m p l e x dielectric
p e r m e a b i l i t y o f t h e c o m p o s i t e m a t e r i a l in t e r m s o f the p e r m e a b i l i t i e s a n d v o l u m e
f r a c t i o n s o f t h e c o n s t i t u e n t s , p r o v i d e d that the m i c r o s t r u c t u r e is s p e c i f i e d in
sufficient detail. I n g e n e r a l , it is p o s s i b l e to r e c o n c i l e e x p e r i m e n t a l d a t a a n d E M T s
for s e l e c t i v e l y s o l a r - a b s o r b i n g c o a t i n g s p r e p a r e d b y e v a p o r a t i o n a n d s p u t t e r i n g .
C a l c u l a t i o n s b a s e d o n E M T s a n d t h e c o n f i g u r a t i o n s in F i g . 7 l e a d to q u a l i t a t i v e
a g r e e m e n t b e t w e e n t h e o r y a n d e x p e r i m e n t a l s o for s o m e c h e m i c a l l y a n d e l e c t r o -
c h e m i c a l l y d e p o s i t e d c o a t i n g s , b u t the fits a r e n o t a l w a y s q u a n t i t a t i v e a n d m a y
differ in detail. T h i s is n o t s u r p r i s i n g in v i e w o f the c o m p l e x i t y o f t h e s e latter
c o a t i n g s , for w h i c h t h e m o d e l s in F i g . 7 s h o u l d b e r e g a r d e d a s a p p r o x i m a t i o n s
only.
It is a p p r o p r i a t e t o m a k e s o m e c o m m e n t s o n t h e u s e o f a g r a d e d c o m p o s i t i o n
profile t o d e s c r i b e s u r f a c e r o u g h n e s s effects b y E M T . I n t h e s e c a s e s t h e profile o f
t h e d i e l e c t r i c p e r m e a b i l i t y is d e r i v e d f r o m t h e c o m p o s i t i o n p r o f i l e b y E M T , as
p r o p o s e d in R e f . 6 3 . T h i s p r o c e d u r e is q u e s t i o n a b l e , t h o u g h , u n l e s s t h e a v e r a g e
p e r i o d o f t h e s u r f a c e r o u g h n e s s is m u c h less t h a n t h e w a v e l e n g t h o f light.64T h e
c a s e o f g r a t i n g s w i t h a n a r b i t r a r y profile h a s b e e n i n v e s t i g a t e d r i g o r o u s l y . L i m i t s
o f v a l i6 d i t64
5
y for t h e g r a d i n g m o d e l b a s e d o n E M T h a v e b e e n d e r i v e d for t h e s e g r a -
t i n g s , ' a n d it w a s s h o w n t h a t the w a v e l e n g t h - t o - p e r i o d r a t i o h a s t o b e l a r g e r
t h a n a n u m b e r in t h e r a n g e o f 5 to 4 0 in o r d e r that t h e q u a s i s t a t i c limit, that
underlies the E M T , should b e attained. T h e 6 l5
imit of validity o f the E M T depends
a l s o o n t h e h e i g h t o f t h e s u r f a c e r o u g h n e s s . T h i s l i m i t is e v i d e n t l y q u i t e
r e s t r i c t i v e , a n d t h e s u r f a c e r o u g h n e s s e s s e e n for e x a m p l e in e l e c t r o c h e m i c a l l y
d e p o s i t e d s e l e c t i v e l y s o l a r a b s o r b i n g c o a t i n g s is often o f a l a r g e r m a g n i t u d e . In
these cases one should b e cautious with the use of grading models. A concep-
t u a l l y b e t t e r a p p r o a c h is p r o v i d e d b y diffraction t h e o r y , w h i c h h a s b e e n u23 s e d to
m o d e l the optical properties of black c h r o m i u m coatings b y Smith e t . a l .
Diffraction t h e o r y m o d e l s t h e r o u g h s u r f a c e as a b i g r a t i n g . It w a s s h o w n that as-
d e p o s i t e d b l a c k c h r o m i u m e x h i b i t s a p r o n o u n c e d23s u r f a c e r o u g h n e s s w i t h a n
a v e r a g e p e r i o d w e l l o u t s i d e t h e q u a s i s t a t i c l i m i t . T h e diffraction t h e o r y y i e l d s
o p t i c a l p r o p e r t i e s in q u a l i t a t i v e a g r e e m e n t w i t h e x p e r i m e n t s a n d s h o u l d b e
p r e f e r r e d o v e r g r a d i n g m o d e l s for this c o a t i n g . U n f o r t u n a t e l y , r e s t r i c t i o n s o n t h e
h e i g h t - t o - p e r i o d r a t i o that c a n b e t r e a t e d b y c u r r e n t a l g o r i t h m s l i m i t t h e
a p p l i c a b i l i t y o f diffraction t h e o r y for g e n e r a l r o u g h s u r f a c e s .
C C o m p u t a t i o n a l Procedures for M u l t i l a y e r e d C o a t i n g s
W e n o w b r i e f l y d e s c r i b e t h e m e t h o d s u s e d for c a l c u l a t i o n s o f t h e o p t i c a l p r o p e r -
ties o f c o a t i n g s c o n s i s t i n g o f m u l t i l a y e r e d thin films, s u c h as t h o s e o f F i g . 7.
G r a d e d l a y e r s c a n a l s o b e t r e a t e d as m u l t i l a y e r s , i.e., t h e g r a d i n g p r o f i l e c a n b e
a p p r o x i m a t e d b y a l a r g e n66 u m b e r o f superimposed h o m o g e n e o u s layers. A s a rule
o f t h u m b , w e h a v e f o u n d that a g o o d a p p r o x i m a t i o n is o b t a i n e d b y r e p l a c i n g the
g r a d i n g w i t h 2 5 to 5 0 i n d i v i d u a l l a y e r s . T h e o p t i c a l p r o p e r t i e s o f a m u l t i l a y e r thin
film c a n b e c a l c u l a t e d b y s t a n d a r d m e t h o d s (see, for e x a m p l e , R e f . 6 7 ) . T h e b a s i c
s t e p s a r e as f o l l o w s :
(i) First the wavelength-dependent dielectric permeability ε(λ) o f the various

l a y e r s n e e d s t o b e k n o w n . F o r c o m p o s i t e l a y e r s , E M T c a n b e u s e d for this p u r p o s e ,
p r o v i d e d t h a t t h e d i e l e c t r i c p e r m e a b i l i t i e s o f t h e c o m p o n e n t s a n d t h e c o m p6 o8s i -
tion a r e k n o w69 n. T h e most widely used E M T s are those of Maxwell G a r n e t t and
B r u g g e m a n . F o r e x p l i c i t e x p r e s s i o n s w e refer to t h e e a r l i e r c h a p t e r . T h e p e r m e -
abilities o f t h e c o n s t i t u e n t s , o f t h e a n t i r e f l e c t i n g c o a t i n g , a n d t h e m e t a l s u b s t r a t e
m a y b e o b t a i n e d f r o m i n d7 e p7e0
1n d e n t m e a s u r e m e n t s o r f r o m e x t e n s i v e t a b u l a t i o n s
that a r e r e a d i l y a v a i l a b l e . '
(ii) T h i s i n f o r m a t i o n , t o g e t h e r w i t h t h e t h i c k n e s s (d) o f t h e i n d i v i d u a l l a y e r s ,
c a n n o w b e u s e d to o b t a i n t h e o p t i c a l r e s p o n s e o f t h e m u l t i l a y e r s t6 a7c k . T h e m o s t
c o n v e n i e n t w a y is p r o b a b l y t h e m e t h o d o f c h a r a c t e r i s t i c m a t r i c e s . T h e c h a r a c -
teristic m a t r i x , m , o f a s i n g l e l a y e r is w r i t t e n as
(4)
\m
m
21 22 /
67
where
m m cs 2π
o η
ll = 22 = [ ( λ ) d cos θ / λ ] (5)
a n d θ d e n o t e s t h e a n g l e o f i n c i d e n c e o f t h e light. T h e c o m p l e x r e f r a c t i v e i n d e x
η ( λ ) is t h e s q u a r e r o 6
o7
t o f t h e d i e l e c t r i c p e r m e a b i l i t y . T h e o t h e r c o m p o n e n t s o f the
matrix are given b y
m
12 = -i sin [2π η(λ) d cos θ / λ ] / Ρ (6)
and
m
21 = -i Ρ sin [2π η(λ) d cos θ / λ ] . (7)
H e r e Ρ = λ) ε / μ cos θ for s-polarised light a n d Ρ = λ) μ / ε c o s θ for p - p o l a r i s e d light,

w h e r e μ is t h e m a g n e t i c p e r m e a b i l i t y ( w h i c h often c a n b e set to u n i t y ) . W i t h
k n o w l e d g e o f t h e c h a r a c t e r i s t i c m a t r i c e s o f t h e v a r i o u s l a y e r s i n t h e s t a c k , it67is
n o w fairly s i m p l e to o b t a i n t h e r e s u l t i n g o p t i c a l r e s p o n s e . It c a n b e s h o w n that
t h e c h a r a c t e r i s t i c m a t r i x o f the m u l t i l a y e r s t a c k , M , is s i m p l y t h e p r o d u c t o f t h e
matrices o f the constituent layers.
(iii) W e n o w c o n s i d e r a s t a c k w i t h l a y e r s n u m b e r e d f r o m 1 at t h e s u r f a c e to N ,
denoting the substrate. Since w e are presently considering metallic substrates,
w h i c h a r e o p a q u e , o n l y t h e reflection f r o m t h e s y s t e m is n o6 n7- z e r o . T h e reflection
coefficient r o f t h e m u l t i l a y e r film is r e a d i l y o b t a i n e d f r o m
R ( Μ
1 Μ
1ΐ Ρ Ν2+) Ρ ΐ - ( Μ 2 Μ ΐ2 Ρ Ν
+)2
" (Μ +Μ ΡΝ)ΡΙ + (M +M P ) '
Π 1 2 2 12 N 2
H e r e P j a n d Pjvj d e n o t e t h e v a l u e s o f the q u a n i t y Ρ d e f i n e d a b o2v e for l a y e r s 1 a n d
N , r e s p e c t i v e l y . F i n a l l y , the reflectivity ( R ) is g i v e n b y R = I r 1 .
IV. CASE STUDY ONE: OPTICAL PROPERTIES O F NICKEL

PIGMENTED ALUMINIUM OXIDE
This section gives an e x a m p l e o f the application o f the structural multilayer

m o d e l s a n d t h e c o m p u t a t i o n a l t e c h n i q u e s for the o p t i c a l p r o p e r t i e s d i s c u s s e d
72
a b o v e . W e p r e s e n t results f r o m r e c e n t c a l c u l a t i o n s for v a r i o u s n i c k e l p i g m e n -
ted a l u m i n i u m o x i d e c o a t i n g s o n a l u m i n i u m s u b s t r a t e s . A l a t e r s e c t i o n will
p r e s e n t m o d e l s for their e l e v a t e d t e m p e r a t u r e d e g r a d a t i o n . T h e m a n u f a c t u r i n g
o f t h e c o a t i n g s w a s d i s c u s s e d briefly in c o n n e c t i o n w i t h F i g . 5.
A. Model
A m u l t i l a y e r m o d e l for t h e o p t i c a l p r o p e r t i e s , b a s e d o n t h e m o s t p r o m i n30 ent

structural features o f t h72 e c o a t i n g , w a s first a d v a n c e d b y A n d e r s s o n e t . a l . a n d h a s
since been elaborated. T h e structural m o d e l , d e p i c t e d in the inset o f F i g . 5,
c o n s i s t s o f four l a y e r s . T h e y a r e n u m b e r e d from the air i n t e r f a c e to t h e s u b s t r a t e
interface. N e x t to t h e a l u m i n i u m s u b s t r a t e , a thin b a r r i e r l a y e r o f d e n s e a l u m i -
n i u m o x i d e is p r e s e n t . W e will30n e g l e c t this l a y e r s i n c e it h a s o n l y a m i n o r influ-
ence on the optical p r o p e r t i e s . L a y e r 3 c o n s i s t s o f s m a l l n i3
c0k e l p a r t i c l e s u n i f o r m -
ly d i s t r i b u t e d in the p o r o u s o x i d e . P r e v i o u s l y , it w a s s h o w n that g o o d a g r e e -
m e n t w i t h e x p e r i m e n t s c a n b e o b t a i n e d w h e n the p a r t i c l e s a r e t a k e n to b e
69
s p h e r i c a l a n d the effective dielectric p e r m e a b i l i t y o f t h e c o m p o s i t e is g i v e n b y the
Bruggeman E M T . L a y e r 2 consists o f p o r o u s o x i d e w i t h o u t m e t a l p a r t i c l e s . It is
a s s u m e d that the p o r o s i t y g r a d u a l l y i n c r e a s e s t o w a r d s t h e t o p o f t h e s t a c k , a n d in
l a y e r 1 w e t a k e a l i n e a r refractive i n d e x g r a d i n g o f a l u m i n i u m o x i d e w i t h air.
T h i s c o a t i n g s t r u c t u r e c o r r e s p o n d s to T y p e I in Fig. 7.
T h e dielectric p e r m e a b i l i t y o f t h e c o m p o s i t e l a y e r w a s o b t a i n e d f r o m t h e p e r m e -
abilities o f t h e c o n s t i t u e n t s b y u s e o f E M T . Specifically, t h e effective 69 d i e l e c t r i c
permeability, ε = + ί ε , was given b y the B r u g g e m a n f o r m u l a
2
fA (EA- ε ) / ( ε + 2 ε ) + ( 1 - ί ) ( ε - ε ) / ( ε + 2 ε ) = 0 , (9)
Α Α Β Β
w h e r e f is the v o l u m e fraction, o r filling factor, o f c o m p o n e n t A , a n d ε , Β
A Α
denote the dielectric permeabilities of the constituents. O n e can use literature
7 77
8
d a t a for the w a v e l e n g t h - d e p e n d e n t d i e l e c t r i c p e r m e a b i l i t i e s o f n i c k e l (Refs. 7 3 - 7 5 ) ,
A I 2 O 3 (Ref. 7 6 ) , as w e l l as for the a l u m i n i u m s u b s t r a t e . '
T h e dielectric p e r m e a b i l i t y o f t h e p o r o u s o x i d e in l a y e r 2 p o s e s a p r o b l7e m 89
0. T h e
p o r o s i t y o f a n o d i z e d A l c a n b e a p p r e c i a b l e , typically u p to 3 0 p e r c e n t . ' 76h e r e -
T
fore o n e m u s t u s e a l o w e r ε t h a n that o f h o m o g e n e o u s a l u m i n i u m o x i d e . For
s i m p l i c i t y o n e m a y fix ε = 2 o v e r t h e w h o l e v i s i b l e a n d n e a r infrared w a v e l e n g t h
r a n g e . T h e a b s o r p t i o n o f t h e o x i d e in this r a n g e is n e g l i g i b l e . In the g r a d e d l a y e r 4
it w a s a s s u m e d that ε d e c r e a s e s linearly from 2 to u n i t y at the air interface.
B. Comparison of Theory and Experiment
F i g u r e 8 c o m p a r e s c a l c u l a t e d r e f l e c t a n c e s p e c t r a to e x p e r i m e n t s for four n i c k e l
p i g m e n t e d a l u m i n i u m o x i d e c o a t i n g s . O p t i c a l d a t a for t h r e e o f t h e s e w e r e g i v e n
in F i g . 5. T h e first test r e g a r d s the G r a n g e s ( G R ) c o a t i n3 g0, w h i c h a p p e a r s to b e the
b e s t c h a r a c t e r i z e d o n e . A c c o r d i n g to A n d e r s s o n e t . a l . o n e c a n u s e d = 0.3 μπ\
3
a n d d j + d = 0.4 μιη w h e r e dj d e n o t e s the t h i c k n e s s o f l a y e r i. W e c o n s i d e r a
2
0.4 c—1 1 1 1 1 1 1 1 I ι I π
1 lo.ispm THEORY (a)

- 0 . 2 5 μιη EXP.
* . % * .. · 0.3 μπι f = 0.23
/
^ / ^ \
>/ )
GRANGES
0.4 ζ—ι—ι—·—ι—ι—ι—ι—ι—ι—'—ι—t
I [0.15 gm
0.22 μιη SHOWA

1
* . * > · . *. 0 . 2 5 μιη f = 0.23
Λo Al ^ - χ
0.2- / / \ V
J κ%
ο
4 "ί^Τ^'ί—ι—ι—ι—ι—ι 1—ι 1—γ
λ Α 10.15 Mm s χ '
Uj°- " 0.55 Mm / \ SUNSTRIP "
CC * « * . * » 0 . 2 8 Mm f « 0 . 2 0 / .
f\j/
1 1 1 1 1 1 1 1 ! 1 1 h
l 10.28 urn
. » . * . 0.1 Mm f = 0-0.25 SCHERER ET AL.

0.2- Λ'.'.' 0.3 Mm f= 0.25
' AI '
0 "T^^f-î^î^ ^1 ι ι \ ι ι
0.2 1.0
0.6 1.4 18 2.2 2.6
W A V E L E N G T H (pm)
Fig. 8. R e f l e c t a n c e as a f u n c t i o n o f w a v e l e n g t h for n i c k e l p i g m e n t e d
a l u m i n i u m o x i d e c o a t i n g s p r o d u c e d b y (a) G r a n g e s , ( b ) S h o w a ,
(c) S u n s trip a n d ( d ) S c h e r e r et.al. D a s h e d c u r v e s s h o w
experimental data, and continuous curves s h o w results o f
calculations using the structural models a n d parameter
values s h o w n in the insets. ( F r o m Ref. 7 2 ) .
2
coating with a nickel density 0.62 g / m , w h i c h in c o m b i n a t i o n with t h e value o f
d y i e l d s a filling factor for n i c k e l e q u a l t o f = 0 . 2 3 . I n t h e a n a l y s i s w e h a v e v a r i e d
3
t h e v a l u e s o f d^ a n d d , k e e p i n g t h e i r s u m c o n s t a n t , i n o r d e r t o o b t a i n g o o d
2
agreement with the experimental spectrum. A calculation with the model
p r e s e n t e d a b o v e is c o m p a r e d t o e x p e r i m e n t a l d a t a in F i g . 8 a . W e h a v e u s e d
d j = 0.15 μ ι η a n d d = 0.25 μ ι η . It is s e e n that t h e o v e r a l l a g r e e m e n t is v e r y g o o d .
2
S m a l l d i s c r e p a n c i e s a r e p r e s e n t at λ < 0.6 μ ι η , w h e r e t h e e x p e r i m e n t a l r e f l e c t a n c e
is l o w e r . T h i s is p r o b a b l y d u e to a c e r t a i n r o u g h n e s s o3 f0t h e i n t e r f a c e s b e t w e e n t h e
v a r i o u s l a y e r s in t h e c o a t i n g , a s p r e v i o u s l y d i s c u s s e d .
F i g u r e 8 b is b a s e d o n t h e S h o w a ( S H ) c o a t i n g . T h e c l o s e s i m i l a r i t y b e t w e e n t h e
o p t i c a l p r o p e r t i e s o f t h e G r a n g e s a n d S h o w a c o a t i n g s s u g g e s t s that t h e p a r a m e t e r s
in t h e o p t i c a l m o d e l s h o u l d b e r a t h e r s i m i l a r . T h e final c o m p a r i s o n w i t h t h e
28
e x p e r i m e n t a l d a t a , w h i c h is p r e s e n t e d in F i g . 8 b , u s e d t h e t h i c k n e s s v a l u e s
d i = 0.15 μ ι η , d = 0.22 μ ι η a n d d = 0.25 μιη. T h e a g r e e m e n t is a g a i n v e r y g o o d
2 3
e x c e p t at t h e s h o r t w a v e l e n g t h e n d o f t h e s p e c81
t r u m . T h e total t h i c k n e s s is
consistent with electron microscopic studies.
Before considering s o m e other coatings w e m u s t m a k e a short digression on the

infrared properties o f nickel p i g m e n t e d a l u m i n i u m oxide. Figure 9 presents a
c o m p a r i s o n o f t h e o r y a n d e x p e r i m e n t in t h e i n f r a r e d w a v e l e n g t h r a n g e for t h e
G r a n g e s a n d S h o w a c o a t i n g s . T h e m o d e l c a l c u l a t i o n s a c c o u n t v e r y w e l l for t h e
features in t h e s p e c t r a . A t still l o n g e r w a v e l e n g t h s ( a b o v e 10 μ ι η ) , t h e o p t i c a l
p r o p e r t i e s a r e d o m i n a t e d b y the lattice v i b r a t i o n s o f a l u m i n i u m o x i d e . T h e s e
effects i n c r e a s e t h e t h e r m a l e m i t t a n c e o f the c o a t i n g s , e s p e c i a l l y o f t h e h e a v i l y
d e g r a d e d o n e s . M o d e l l i n g o f o p t i c a l s p e c t r a in this r e g i o n is n o t o r i o u s l y difficult
since the phonon properties of the porous and probably impure anodic oxide
c a n n o t b e e x p e c t e d to c o i n c i d e w i t h the p h o n o n s o f thin films p r e p a r e d u n d e r
well-controlled conditions.
A n i m p o r t a n t p a r a m e t e r for t h e n i c k e l p i g m e n t e d a l u m i n i u m o x i d e c o a t i n g s is
t h e c r o s s o v e r w a v e l e n g t h λ*, w3 h0i c h is d e f i n e d as t h e w a v e l e n g t h w h e r e t h e
r e f l e c t a n c e is 0.5. E m p i r i c a l l y , this w a v e l e n g t h d e p e n d s l i n e a r l y o n t h e n i c k e l
LOI 1 1 1 ^ I ^HT~
if
ι α
s 4 0
il
î - I' SH GR "
l υ EXP
/. yfl THEORY
oJ± I I I I I
0 2 4 6 8 10
WAVELENGTH ( pm)
Fig. 9. S p e c t r a l r e f l e c t a n c e for n i c k e l p i g m e n t e d a l u m i n i u m o x i d e
coatings produced by S h o w a (SH) and Granges (GR).
E x p e r i m e n t a l r e s u l t s a r e c o m p a r e d to c a l c u l a t i o n s b a s e d o n the
m o d e l s d e p i c t e d in F i g s . 8 a a n d b . E a c h i n d i c a t e d c u r v e is
e x p l a i n e d in t h e inset. ( F r o m R e f . 7 2 ) .
c o n t e n t o f t h e film. T h e c o m p u t a t i o n s s h o w e d t h a t λ* is p r i m a r i l y d e p e n d e n t o n
t h e n i c k e l filling factor a n d , to a l e s s e r d e g r e e , o n t h e t h i c k n e s s o f t h e c o m p o s i t e
layer.
W e n o w c o n s i d e r t h e S u n s t r i p c o a t i n g , for w h i c h v e r y little s t r u c t u r a l i n f o r m a -
tion is p r e s e n t l y a v a i l a b l e . F o r t h e d a t a s h o w n in F i g . 5 , t h e c r o s s o v e r w a v e l e n g t h
is λ* « 3 to 3.5 μ ι η , w h i c h s u g g e s t s t h a t t h e n i c k e l filling f a c t o r is l o w e r t h a n for
t h e S h o w a c o a t i n g . A c c o r d i n g to Ref. 3 02, t h e s h o w n v a l u e o f λ* c o r r e s p o n d s to a
n i c k e l d e n s i t y o f a p p r o x i m a t e l y 0.5 g / m . S e v e r a l i n t e r f e r e n c e fringes a r e p r e s e n t
in t h e e x p e r i m e n t a l r e f l e c t a n c e s p e c t r u m . A fit o f t h e c a l c u l a t i o n s t o t h e s e fringes
s h o w s t h a t t h e o x i d e t h i c k n e s s d ] + d s h o u l d b e in t h e r a n g e 0.6 to 0.7 μ ι η . F i g u r e
2
8 c c o m p a r e s a c o m p u t a t i o n28w i t h f = 0 . 2 0 , d j = 0.15 μιη, d = 0 . 5 5 μπα a n d d = 0.28
2 3
μ ι η to e x p e r i m e n t a l d a t a . These parameter values are not unique, and equally
g o o d fits c o u l d b e o b t a i n e d w i t h s o m e o t h e r c o m b i n a t i o n s . T h e a g r e e m e n t
b e t w e e n t h e o r y a n d e x p e r i m e n t w a s f o u n d to b e r e a s o n a b l e at s h o r t w a v e l e n g t h s .
D i s c r e p a n c i e s a p p e a r e d a b o v e 1.5 μ ι η , w h e r e t h e c a l c u l a t i o n s h o w e d m o r e
p r o n o u n c e d i n t e r f e r e n c e o s c i l l a t i o n s t h a n t h o s e p r e s e n t in t h e m e a s u r e d
r e f l e c t a n c e s p e c t r u m . O n e m a y s p e c u l a t e that this p o i n t s to a m i n o r i n a d e q u a c y in
t h e B r u g g e m a n E M T w h e n a p p l i e d to t h e s e c o a t i n g s .
F i n a l l5y9, s o m e c o m m e n t s a r e g i v e n o n t h e h e a v i l y p i g m e n t e d c o a t i n g s o f S c h e r e r
et.al. In this c a s e o n e h a s to d e p a r t from t h e T y p e I m o d e l s u s e d a b o v e a n d
i n s t e a d a p p l y t h e m o r e c o m p l e x T y p e III m o d e l to t h e s t r u c t u r e o f t h e c o a t i n g .
I n d e e d , it is n e c e s s a r y to i n s e r t a l i n e a r l y g r a d e d n i c k e l - a l u m i n i u m o x i d e l a y e r
b e t w e e n l a y e r s 2 a n d 3 i n o r d e r to o b t a i n a c c e p t a b l e a59 greement with experiments.
A c o m p a r i s o n o f c a l c u l a t i o n s a n d e x p e r i m e n t a l d a t a is g i v e n in F i g . 8 d . T h e
c a l c u l a t i o n e m p l o y e d a g r a d e d l a y e r w i t h d ^ = 0.1 μπα b e t w e e n d = 0.3 μπα a n d
3
d = 0.28 μπα. T h e filling factor in l a y e r 3 w a s p u t to 0 . 2 5 , w h i c h is r e a s o n a b l e s i n c e
2
this h e a v i l y c o l o u r e d c o a t i n g p r o b a b l y h a s a h i g h e r n i c k e l c o n t e n t t h a n the o t h e r s .
A g r a d e d o x i d e - a i r l a y e r w a s n o t n e c e s s a r y in o r d e r to o b t a i n t h e e x c e l l e n t a g r e e -
m e n t w i t h t h e e x p e r i m e n t s s h o w n in F i g . 8 d . A n a l m o s t e q u a l l y g o o d fit w a s
o b t a i n e d b y u s i n g d | = 0.15 μπα, as in the o t h e r c a s e s , a n d at t h e s a m e t i m e d e c r e a -
s i n g d to 0.2 μπα. It is e v i d e n t that h e a v i l y p i g m e n t e d c o a t i n g s c a n b e d e s c r i b e d b y
2
a s i m p l e e x t e n s i o n o f t h e s t r u c t u r a l m o d e l s h o w n in t h e i n s e t o f F i g . 5.
IV. C A S E S T U D Y T W O : T E X T U R E D Al-Si C O M P O S I T E C O A T I N G S
T h i s s e c t i o n g i v e s a n e x a m p l e o f a c a l c u l a t i o n b a s e d o n a g r a d i n g m o d e l for 2 a1
s e l e c t i v e l y s o l a r a b s o r b i n g c o a t i n g w i t h a r o u g h surface. W e p r e s e n t r e s u l t s for
c h e m i c a l l y e t c h e d m e t a l l i c A l - S i c o m p o s i t e films d e p o s i t e d o n g l a s s s u b s t r a t e s .
Al-Si coatings, consisting of a mixture of small aluminium and silicon particles,

w e r e produced b y simultaneous evaporation of the constituents from two
e l e c t r o n - b e a m s o u r c e s . T h e o p t i c a l p r o p e r t i e8s 82
3a n d d i e l e c t r i c p e r m e a b i l i t y o f a s -
d e p o s i t e d films w e r e d i s c u s s e d e l s e w h e r e . ' T h e films c o n t a i n e d - 2 0 v o l . % Si
a n d h a d t h i c k n e s s e s o f 1.2 μιη. After d e p o s i t i o n t h e films 3 w e r e e t c h e d i n a n 21
u l t r a s o n i c a l l y stirred b a t h w i t h 2.5 m o l e s N a O H p e r d m o f d e i o n i z e d w a t e r . As
the etching proceeded, the appearance of the samples changed from shiny metallic
to a y e l l o w c o l o u r , a n d t h e n b e c a m e p r o g r e s s i v e l y d a r k e r . Etch times of approxi-

m a t e l y o n e m i n u t e w e r e n e c e s s a r y i n o r d e r to p r o d u c e a b l a c k a p p e a r a n c e .
S c a n n i n g e l e c t r o n m i c r o s c o p21
y s h o w e d that the etched films h a d very irregularly
textured surface structures. T h e lateral s i z e o f t h e p r o t r u s i o n s s e e m e d to b e in
the 20-50 n m range. F r o m examination of the e d g e of cleaved samples, the
t e x t u r i n g d e p t h ,21
h, a p p e a r e d t o b e r o u g h l y 1 0 0 - 4 0 0 n m w i t h t h e d e p t h i n c r e a s i n g
with etch t i m e . W e b e l i e v e t h a t t h e s u r f a c e r o u g h n e s s is d u e t o p r e f e r e n t i a l
e t c h i n g o f t h e a l u m i n i u m p h a s e . A s c h e m a t i c r e p r e s e n t a t i o n o f t h e s t r u c t u r e is
s h o w n21i n t h e i n s e t o f F i g . 1 0 . T h e s o l i d c u r v e s h o w s t h e e x p e r i m e n t a l r e f l e c -
t a n c e for a n A l - S i c o m p o s i t e e t c h e d in N a O H for 5 5 s. T h e d a t a c o r r e s p o n d to
Α « 0.95 a n d E « 0.2.
μ1 t hm e r
- (%) j ^
Reflectance of ; / '
— 80 chemically etched / >^ _
A l - S i composite. / f
_ // Experiment _
j/ Theory
_ QQ j / Ideal curve _
4 0
0 — - ^ ^ ^ ^ "
I
0.2
I I0.5
I I I I 1I 1 i 2 l l 5
I 1 I I 10
II1 I
20
I I I
50
I I I
Wavelength (urn)
Fig. 1 0 . S p e c t r a l r e f l e c t a n c e for a c h e m i c a l l y e t c h e d A l - S i s u r f a c e .
The dotted lines indicate the ideal reflectance, the solid curve
represents experimental results obtained on an Al-Si c o m p o -
site e t c h e d i n N a O H for 5 5 s, a n d t h e d a s h e d c u r v e s h o w s t h e
result of a computation based on a graded refractive index
m o d e l e m p l o y i n g t e x t u r e s 3 0 0 n m d e e p . (After R e f . 2 1 ) .
T h e s u r f a c e t e x t u r e o f t h e e t c h e d A l - S i films w a s m o d e l e d as a g r a d i n g o f t h e b u l k
A l - S i m a t e r i a l w i t h air. T h e t e x t u r e w a s r e p r e s e n t e d as h a l f - s p h e r o i d s s u b d i v i d e d
i n t o m a n68y layers. T h e refractive index profile w a s obtained from the M a x w e l l
G a r n e t t E M T a s a p p l i e d to e a c h l a y e r . T h e filling factor p r o f i l e w a s g i v e n b y
2
f(z) = l - [ ( z - h ) / h ] , (10)
w h e r e t h e z - c o o r d i n a t e is z e r o at t h e o u t e r s u r f a c e o f t h e g r a d e d l a y e r a n d
increases towards the substrate. W e e m p h a s i z e that grading m o d e l s should b e
u s e d w i t h c a u t i o n for this s u r f a c e , s i n c e o n e c a n n o t b e s u r e t h a t t h e q u a s i s t a t i c
l i m i t is a t t a i n e d at all w a v e l e n g t h s . H o w e v e r , t h e l a t e r a l s i z e o f t h e r o u g h n e s s is
sufficiently s m a l l t h a t t h e g r a d i n g m o d e l b a s e d o n E M T s h o u l d b e v a l i d at l e a s t in
t h e t h e r m a l infrared w a v e l e n g t h r a n g e . T h e d a s h e d c u r v e in F i g . 10 s h o w s t h e
result of a calculation with the model outlined above, using a grading depth of 300
n m . T h e a g r e e m e n t w i t h t h e e x p e r i m e n t a l c u r v e is a c c e p t a b l e , d e s p i t e t h e
v a r i o u s s i m p l i f i c a t i o n s m a d e in t h e t h e o r e t i c a l m o d e l .
W e b e l i e v e t h a t this s i m p l e e t c h t r e a t m e n t c a n b e a p p l i e d to A l - S i s u r f a c e s p r o d u -
ced b y a m o r e production-oriented method than electron-beam evaporation.
A l u m i n i u m - s i l i c o n a l l o y s a r e w i d e l y u s e d in i n d u s t r y . S u c h a l l o y s , o f s u i t a b l e
microstructure, conceivably could b e rendered spectrally selective b y etching.
VI. DEGRADATION AND DURABILITY
T h e d u r a b i l i t y a n d d e g r a d a t i o n a r e o f e x t r e m e i m p o r t a n c e for t h e t e c h n i c a l
a p p l i c a t i o n o f s e l e c t i v e l y s o l a r - a b s o r b i n g c o a t i n g s . T h e i n t e r e s t in d e g r a d a t i o n
s t u d i e s , a n d t h e d e t e r m i n a t i o n o f s e r v i c e life o f s o l a r a b84 sorbers from accelerated
a g e i n g tests, h a s i n c r e a s e d r a p i d l y d u r i n g r e c e n t y85 ears. Important studies on
b l a c k c h r o m i u m h a v e b e e n carried ou8 t b867y P e t t i t , a n d s e v e r a l c o m m e r c i a l c o a t -
ings have been studied b y Kohl e t . a l . ' Studies of degradation and durability of
s o l a r c o l l e c t o r c o a t i n g s h a v e b e e n g i v e n a m a j o r i m p e t u s2 b88 y the establishment of
the International Energy A g e n c y (IEA) Task X p r o g r a m . ' This six-year
c o l l a b o r a t i v e effort, i n v o l v i n g e l e v e n c o u n t r i e s , w a s b e g u n in 1 9 8 5 .
A. Accelerated Ageing Tests
W e first b r i e f l y r e v i e w t h e m o s t c o m m o n a c c e l e r a t e d a g e i n g tests that h a v e b e e n

a p p l i e d to s t u d y the i n f l u e n c e o f v a r i o u s d e g r a d a t i o n f a c t o r s o n s e l e c t i v e l y solar-
absorbing coatings.
2 88 847
(i) A g e i n g at e l e v a t e d t e m p e r a t u r e s in air h a s b e e n a c o m m o n t e s t . ' " It
g i v e s i n f o r m a t i o n o n t h e p e r f o r m a n c e a n d d u r a b i l i t y o f a c o a t i n g as a function o f
applied temperature.
(ii) T h e influence of atmospheric constituents on coatings can b e studied by

e x p o s i n g t h e m to i n c r e a s e d c o n c e n t r a t i o n s o f t h e s e s u b s t a n c e s o r b y i n c r e a s i n g the
temperature. Probably the m o s t important of these degradation factors are
h u m i d i t y a n d S 0 . A c c8 e7l e r a t e d h u m i d i t y tests a r e often p e r f o r m28 e d at 9 0 ° C a n d
2
95 % relative h u m i d i t y , but lower loads have also been u s e d .
(iii) D u r i n g n i g h t t h e t e m p e r a t u r e o f s o l a r c o l l e c t o r s m a y d r o p b e l o w the d e w -
p o i n t a n d c o n s e q u e n t l y c o n d e n s a t i o n c a n o c c u r in t h e air g a p b e t w e e n a b s o r b e r
a n d g l a z i n g . It is i m p o r t a n t that the d u r87 a b i l i t y o f solar a b s o r b e r c o a t i n g s u n d e r
these conditions be thoroughly t e s t e d .
(iv) T h e i n f l u e n c e o f s o l a r r a d i a t i o n c a n b e t e s t e d b y s o l a r s i m u l a t i o n l a m p s 84in
the l a b o r a t o r y . T h e effect o f U V - r a d i a t i o n a p p e a r s to b e e s p e c i a l l y i m p o r t a n t .
(v) O f c o u r s e , t h e v a r i o u s a c c e l e r a t e d tests m u s t b e v a l i d a t e d b y c o m p a r i s o n
with results of outdoor exposures, which m a y b e carried out under stagnation or
operating conditions.
A t p r e s e n t w e focus o n a c c e l e r a t e d a g e i n g tests in air at e l e v a t e d t e m p e r a t u r e s .

T h e r e a s o n for this is s i m p l y that t h e d e g r a d a t i o n p r o c e s s e s in this c a s e a p p e a r to
b e quite well understood and detailed models can b e formulated. T w o commer-
cial s e l e c t i v e l y s o l a r - a b s o r b i n g c o a t i n g s , w i l l b e c o n s i d e r e d b e l o w , n a m e l y n i c k e l
p i g m e n t e d a l u m i n i u m o x i d e a n d b l a c k c h r o m i u m . T h i s is d o n e b e c a u s e t h e s e
c o a t i n g s w e r e s e l e c t e d for d e2t a8i8l e d s t u d i e s in t h e I E A T a s k X p r o g r a m , a n d a
w e a l t h o f d a t a is a v a i l a b l e . ' It s e e m s that a d e c r e a s e o f A i u p o n h i g h
s o
t e m p e r a t u r e t r e a t m e n t s is t h e m a i n r e a s o n for t h e d e g r a d a t i o n o f t h e p e r f o r m a n c e
of these solar absorber coatings. E h
t e mrm a y e i t h e r d e c r e a s e o r i n c r e a s e u p o n
e x p o s u r e to e l e v a t e d t e m p e r a t u r e s , b u t t h e c h a n g e s a r e28u s u s a l l y s m a l l e r a n d affect
t h e p e r f o r m a n c e less t h a n t h e a b s o r p t a n c e v a r i a t i o n s . H o w e v e r , it s h o u l d b e
n o t e d t h a t l a r g e i n c r e a s e s o f t h e r m a l e m i t t a n c e h a v e b e e n o b s e r v e2d 88 in n i c k e l
pigmented aluminium oxide absorbers upon condensation t e s t s . '
B. Modelling of Optical Properties during Ageing
In o r d e r to d e v e l o p s o m e u n d e r s t a n d i n g o f the u n d e r l y i n g c a u s e s o f t72 he degra-

dation, w e model the changes of the optical properties during a g e i n g by use of
t h e t h e o r e t i c a l f r a m e w o r k in the e a r l i e r s e c t i o n s . W e first c o n s i d e r t h e a g e d
n i c k e l - a l u m i n i u m o x i d e c o a t i n g s a n d i n v e s t i g a t e the s t r u c t u r a l c h a n g e s w h i c h
l e a d to t h e o b s e r v e d c h a n g e s in t h e o p t i c a l s p e c t r a . After h e a t t r e a t m e n t s in air at
elevated temperatures, the optical properties of the S h o w a and Sunstrip coatings
c h a n g e in t h e s a m e w a y . T h e m a i n effect is a g r a d u a l i n c r e a s e in t h e r e f l e c t a n c e at
λ > 128 μ ι η as t h e h e a t t r e a t m e n t p r o g r e s s e s , as c l e a r l y s e e n in F i g . 11 w h i c h d e p i c t s
data for28t h e S h o w a c o a t i n g . Q u a l i t a t i v e l y s i m i l a r 2results
8887 8 w e r e o b t a i n e d for
Sunstrip. T h i s effect l e a d s to a g r a d u a l l o w e r i n g ' ' o f A i . A l s o a slight
s o
shift to s h o r t e r w a v e l e n g t h s o f t h e p e a k at28a b o u t 1 μιη c a n b e s e e n in F i g . 1 1 . In the
infrared o n e c a n n o t i c e t h a t λ* d e c r e a s e s , w h i c h s u g g e s t s that o x i d a t i o n o f t h e
n i c k e l p a r t i c l e s is t h e m a i n d e g r a d a t i o n m e c h a n i s m .
T h e o x i d a t i o n o f the n i c k e l in t h e c o a t i n g c a n b e d e s c r i b e d t h r o u g h t w o l i m i t i n g
m o d e l s . O n e p o s s i b i l i t y is that t h e o x i d a t i o n o f n i c k e l in l a y e r 3 t a k e s p l a c e uni-
f o r m l y t h r o u g h o u t t h e l a y e r . In this c a s e t h e filling factor d e c r e a s e s as d e g r a d a t i o n
p r o c e e d s , b u t d r e m a i n s c o n s t a n t . M o d e l c a l c u l a t i o n s for this c a s e a r e s h o w n in
3
Fig. 1 2 a w i t h p a r a m e t e r s p e r t i n e n t to the S h o w a c o a t i n g . T h e c a l c u l a t i o n s r e p r o -
d u c e t h e q u a l i t a t i v e features o f t h e e x p e r i m e n t s , e x c e p t that t h e shift o f t h e p e a k at
~1 μ ι η a p p e a r s to b e l a r g e r in the e x p e r i m e n t a l data. F u r t h e r , t h e e x p e r i m e n t s
s h o w v e r y flat r e f l e c t a n c e c u r v e s at λ > 1.5 μ ι η , w h i l e t h e c a l c u l a t e d r e f l e c t a n c e
increases s o m e w h a t with wavelength. However, these discrepancies are only
m i n o r , a n d o n e c a n b e c o n f i d e n t that t h e d e g r a d a t i o n m e c h a n i s m is a r a t h e r
u n i f o r m o x i d a t i o n o f t h e n i c k e l p a r t i c l e s t h r o u g h o u t the c o m p o s i t e l a y e r .
1-0 1 —ι 1 1 1 1 r
SHOWA
0.8 UNAGED
A F T E R 100h A T 723 Κ
AFTER 6H A T 773 Κ
^ 0.6 I
<
O
ÏÏ 0.4)
u.
LU
ce
0 2
" / / / ^ \ ^
Ο ^sCç^^y ι ι I
0.2 0.6 1.0 1.4 1.8 2.2
W A V E L E N G T H (Mm)
Fig. 1 1 . R e f l e c t a n c e as a f u n c t i o n o f w a v e l e n g t h for n i c k e l p i g m e n t e d
anodic aluminium oxide coatings produced b y Showa.
T h e c o n t i n u o u s c u r v e s h o w s e x p e r i m e n t a l r e s u l t s for a n
unaged coating, while dashed and dash-dotted curves s h o w
results for c o a t i n g s a g e d for 1 0 0 h at 7 2 3 Κ a n d 6 h at 7 7 3 K ,
r e s p e c t i v e l y . ( F r o m Ref. 2 8 ) .
S e c o n d l y , a n o x i d a t i o n front m a y p r o c e e d into t h e c o a t i n g , c a u s i n g d to g r a d u a l l y
3
d e c r e a s e a n d d to i n c r e a s e as d e g r a d a t i o n c o n t i n u e s . T h i s p o s s i b i l i t y is e x p l o r e d
2
in F i g . 1 2 b , w h i c h p r e s e n t s c a l c u l a t i o n s p e r t i n e n t to t h e S h o w a c o a t i n g w i t h
f = 0 . 2 3 a n d v a r i o u s v a l u e s o f d . T h e n i c k e l c o n t e n t is g i v e n b y t h e r e l a t i v e v a l u e
3
Q , w h i c h is d e f i n e d b y
Q = W/Wq, (11)
w h e r e W is t h e a c t u a l n i c k e l c o n t e n t a n d Wq d e n o t e s t h e initial n i c k e l c o n t e n t . I n
Fig. 1 2 b , Q is t h e ratio o f the c o m p o s i t e l a y e r t h i c k n e s s after a n d b e f o r e d e g r a d -
ation. T h e v a l u e s o f Q w e r e c h o s e n s o t h a t t h e y s h o u l d b e t h e s a m e as in t h e
c a l c u l a t i o n s in F i g . 1 2 a , w h e r e Q is g i v e n s i m p l y b y t h e r a t i o o f t h e a c t u a l filling
factor to its initial v a l u e . It is s e e n in F i g . 1 2 b t h a t o n l y s l i g h t c h a n g e s in t h e
r e f l e c t a n c e s p e c t r a o c c u r as Q d e c r e a s e s . A i a c t u a l l y i n c r e a s e s s l i g h t l y 2as88Q87
8is
s o
d e c r e a s e d . T h i s is c l e a r l y in c o n t r a d i c t i o n to the e x p e r i m e n t a l r e s u l t s ' ' and
t h e r e f o r e t h e o x i d a t i o n front m o d e l c a n n o t e x p l a i n t h e e x p e r i m e n t a l s p e c t r a o f
h e a t t r e a t e d s a m p l e s . C a l c u l a t i o n s for t h e S u n s t r i p c o a t i n g y i e l d e d t h e s a m e
q u a l i t a t i v e features as t h o s e for S h o w a . H e n c e o n e m u s t c o n c l u d e t h a t in this c a s e
a l s o o x i d a t i o n o f n i c k e l t a k e s p l a c e u n i f o r m l y in t h e c o m p o s i t e l a y e r .
1.0 Ι — Ι — Ι — Ι 1 1—Ι—Ι—I
SH
SH M
MOODDE
ELL f = 0.23 (a)
f «0.20
0.8 - , f = 0.18
( 0 . 1 5 Mm
0 . 2 2 pm
f =0.15-----
0.6 - 0.25 m
M
0.4- x-..
o o"°^V^—ι—ι—ι—ι—\ H 1 1 H
LU (b)
U.0.8- I lm«UM Q=1
yj 0 . 1 5 Mm Q.0.87
DC 0.22 • ( 1 -0)0.25Mm Q = 0.78 _|
0.6- . ' · ' » · Q 0 . 2 5 Mm Q = 0.65
I Al
0.4-
0.2 0.6 1.0 1.4 1.8 2.2 2.6

W A V E L E N G T H (um)
Fig. 1 2 . C a l c u l a t e d r e f l e c t a n c e as a f u n c t i o n o f w a v e l e n g t h for n i c k e l
pigmented aluminium oxide coatings. T h e calculations were
carried out using parameters pertinent to the S h o w a coating.
I n (a) c a l c u l a t i o n s for four different filling factors a r e s h o w n .
In (b) r e s u l t s for four different t h i c k n e s s e s o f t h e c o m p o s i t e
l a y e r a n d a filling factor o f 0.23 a r e d e p i c t e d . T h e p a r a m e t e r Q
d e n o t e s t h e n o r m a l i z e d n i c k e l c o n t e n t in t h e film. T h e s t r u c -
tural m o d e l s a n d p a r a m e t e r s u s e d in t h e c a l c u l a t i o n s , a s w e l l
as t h e i n d i c a t e d c u r v e s , a r e s h o w n in t h e i n s e t s . ( F r o m
Ref. 7 2 ) .
C. Parameterization of the Degradation
H a v i n g e s t a b l i s h e d t h e d e g r a d a t i o n m e c h a n i s m as o x i d a t i o n o f n i c k e l p a r t i c l e s in
t h e c o m p o s i t e , w e n o w t u r n t o t h e q u e s t i o n a s to w h e t h e r t h e d e g r a d a t i o n c a n b e
d e s c r i b e d b y p a r a m e t e r s in a s i m p l e w a y . T o this e n d e x t e n s i v e c a l c u l a t i o n s o f
A i w e r e p e r f o r m e d w i t h p a r a m e t e r s p e r t i n e n t ot t h e S h o w a a n d S u n s t r i p
s o 89
s a m p l e s . E q u a t i o n (1) w a s u s e d to o b t a i n n u m e r i c a l data. F o r 0 j w
s o e employed
t h e air m a s s 1.5 s p e c t r u m , in a c c o r d a n c e w i t h t h e A S T M s t a n d a r d . A n interes-
Q
ting relationship w a s found between 1 - ( A i / A j ) and the quantity Q defined
s os o
above. Here A denotes the solar absorptance of the coating prior to degradation.
sl o
ο
F i g u r e 13 s h o w s a l o g - l o g p l o t o f 1 - ( A i / A i ) as a function o f 1 - Q. It is s e e n that
s os o
t h e c a l c u l a t e d p o i n t s fall o n a s t r a i g h t l i n e b o t h for t h e S H a n d S U m o d e l s . H e n c e
w e infer t h e r e l a t i o n s h i p
î-^/AsoVa-Q)*, (12)
which can r e w r i t t e n in t e r m s o f t h e c h a n g e in s o l a r a b s o r p t a n c e ,
A A i = A i - A j , as
s o s o s o
ΔΑ /Α ν((^-0/^
5θ1 5ο 03)
for t h e c a s e o f d e g r a d a t i o n o c c u r r i n g b y d e c r e a s e o f t h e filling factor i n t h e c o m -
posite layer. H e n c e w e have found that the normalized solar absorptance change
b e h a v e s as a p o w e r o f t h e n o r m a l i z e d c h a n g e o f n i c k e l c o n t e n t . F r o m F i g . 13 it is
s e e n t h a t β « 2.5 for t h e S H a n d S U m o d e l s .
1 Γ Η I I I J I I ι ι ι ι ι ι y
~ Ni-Al 0
23 I Ζ
• SH MODEL /
• SU MODEL À
7 ~
< I
*~ "/
0.01 — / —
I I I I I I I I I ι ι ι ι I
0.1 0.2 0.5 1
1-Q o
Fig. 1 3 . N o r m a l i z e d s o l a r a b s o r p t a n c e c h a n g e (1 - ( A j / A i ) ) v e r s u s
s o s o
n o r m a l i z e d d e c r e a s e in n i c k e l c o n t e n t ( 1 - Q ) . S q u a r e s a n d
circles d e n o t e c a l c u l a t i o n s c a r r i e d o u t w i t h p a r a m e t e r s p e r t i n -
e n t to t h e S h o w a a n d S u n s t r i p c o a t i n g s , r e s p e c t i v e l y . T h e
s t r a i g h t l i n e r e p r e s e n t s E q . (12) w i t h β = 2 . 5 . ( F r o m R e f . 7 2 ) .
M o d e l c a l c u l a t i o n s for a s - d e p o s i t e d a n d d e g r a d e d s a m p l e s s i m i l a r to t h o s e a b o v e
h a v e n o t y e t b e e n c a r r i e d o u t for b l a c k c h r o m i u m c o a t i n g s . A s n o t e d a b o v e , diff-
r a c t i o n t h e o r y s h o u l d b e a p p l i c a b l e to this p r o b l e m , b u t t h e c o m p l e x i t y o f t h e
c a l c u l a t i o n s h2
a3v e s o far p r e v e n t e d o t h e r t h a n q u a l i t a t i v e c o m p a r i s o n s w i t h
experiments. A l s o t h e d e g r a d a t i o n p r o c e s s a p p e a r s to b e c o m p l i c a t e d , i n v2o l9v
3
0i n g
b o t h o x i d a t i o n o f c h r o m i u m p a r t i c l e s a n d a d e c r e a s e in s u r f a c e r o u g h n e s s . '
Figure 14 depicts literature data on A i of black c h r o m i u m versus relative metal

s o
c o n t e n t , Q (Refs. 2 4 , 9 0 , 9 1 ) . O n l y a f e w d a t a p o i n t s a r e a v a i l a b l e ; t h e y c a n b e fitted
to E q . ( 1 2 ) w i t h a n e x p o n e n t β ~ 7. T h e c u r v e e x t r a p o l a t e s w e l l to c a l c u l9a2t e d A j
s o
(Ref. 2 8 ) for thin Cr C>3 films o n c h r o m i u m , a n d to e x p e r i m e n t a l d a t a .
2
_ ι ι ι ι ι I I I I I
' ''I -
I BLACK CHROME
• EXP. -
SWEET.PETTIT.SOWELL,
CHAMBERLAIN
• THIN Cr 0
2 3F I L M S
EXP. K A R L S S O N ET.AL. / _
CALC. SMITH ET.AL.
0.1
6
/ —
(,oe
0v/ ' v)-i
os
0.01
__L I I I I I I Μ,Γ
0.1 0.2 0.5 1
1- Q
o
Fig. 14. N o r m a l i z e d solar a b s o r p t a n c e c h a n g e (1 - ( A i / A i ) ) v e r s u s
s o s o
n o r m a l i z e d d e c r e a s e in c h r o m i u m c o n t e n t (1 - Q ) for b l a c k
c h r o m i u m c o a t i n g s . D o t s d e n o t e e x p e r i m e n t s o f P e t t i t et.al.
(Ref. 9 1 ) a n d S w e e t et.al. (Ref. 2 4 ) . S q u a r e s d e n o t e r e s u l t s for
thin C r 0 3 films f r o m K a r l s s o n et.al. (Ref. 9 2 ) a n d S m i t h et.al.
2
(Ref. 2 3 ) . T h e straight l i n e r e p r e s e n t s E q . (12) w i t h β = 7.
S o far w e h a v e o n l y c o n s i d e r e d o n e o f the p a r a m e t e r s affecting t h e p e r f o r m a n c e o f

a solar absorbing coating, namely A i . T h e magnitude of E h
s o t e , rc om n s i d e r e d in
Ref. 2 8 , s e e m s to d e c r e a s e s l i g h t l y as d e g r a d a t i o n p r o c e e d s in m o s t c a s e s . T h i s can
b e a s c r i b e d to t h e s a m e m e c h a n i s m as t h e d e c r e a s e in A j . T h e i n c r e a s e o f the o t
s o
r e f l e c t a n c e at λ > 1 μ ι η c o n t i n u e s i n t o t h e infrared r a n g e a n d c a u s e s E h
t e mr
d e c r e a s e g r a d u a l l y . O n t h e o t h e r h a n d , as d e g r a d a t i o n p r o g r e s s e s t h e a m o u n t o f
o x i d e in t h e c o a t i n g i n c r e a s e s . T h i s l e a d s to a n i n c r e a s e d i n f r a r e d a b s o r p t i o n d u e
to t h e l a t t i c e v i b r a t i o n m o d e s o f t h e o x i d e . H e n c e this m e c h a n i s m t e n d s to
increase E i
t i e. It r isme v i d e n t t h a t m o d e l l i n g o f t h e c h a n g e s in e m i t t a n c e d u r i n g
d e g r a d a t i o n is a m u c h m o r e c o m p l e x t a s k t h a n t h e m o d e l l i n g o f t h e c h a n g e s in
solar absorptance considered above.
D. Oxidation Kinetics of Metals
T h e a n a l y s i s a b o v e i d e n t i f i e d t h e o x i d a t i o n o f m e t a l p a r t i c l e s as t h e m a i n r e a s o n
for t h e e l e v a t e d t e m p e r a t u r e d e g r a d a t i o n o f s o m e t e c h n i c a l l y i m p o r t a n t s e l e c -
tively s o l a r a b s o r b i n g c o a t i n g s . I n o r d e r to p r o g r e s s t o w a r d s a f u n d a m e n t a l
u n d e r s t a n d i n g o f t h e d e g r a d a t i o n , it is i m p o r t a n t to h a v e a c l e a r n o t i o n o f t h e
c u r r e n t t h e o r i e s o f t h e o x i d a t i o n k i n e t i c s o f m e t a l s . T h i s s u b j e c t is b r i e f l y
reviewed below.
9 53 - 9
T h e oxidation kinetics o f metals has been extensively studied for m a n y y e a r s .
W h e n a c l e a n m e t a l s u r f a c e is e x p o s e d to o x y g e n , a n initial fast o x i d a t i o n o c c u r s
until a f e w m o n o l a y e r s h a v e b e e n f o r m e d . F o r t h e d e g r a d a t i o n o f p r e s e n t
i n t e r e s t , h o w e v e r , o n e is m a i n l y c o n c e r n e d w i t h t h e s u b s e q u e n t s l o w o x i d a t i o n ,
w h i c h c a n b e d u e to cation o r a n i o n diffusion a s s i s t e d b y a n e l e c t r i c field t h a t is set
u p a c r o s s t h e o x i d e c o a t i n g . T h e r a t e l i m i t i n g s t e p m a y b e diffusion o f i o n s , o r
t r a n s p o r t o f e l e c t r o n s i n o r d e r to e s t a b l i s h t h e e l e c t r i c field a c r o s s t h e o x i d e .
O x i d e9s3 o f t h e f o r m M O , l i k e N i O , c a n b e c h a r a c t e r i z e d as s o c a l l e d n e t w o r k m o d i -
fiers. H e r e one expects ca9 t6i o n t r a n s p o r t to d o m i n a t e t h e o x i d a t i o n p r o c e s s .
X e n o n m a r k e r e x p e r i m e n t s indicate that cation transport controls the oxidation
o f c h r o m i u m as w e l l . W h e n the diffusion o f t h e c a t i o n s is t h e r a t e l i m i t i n g97 s t e p ,
the oxidation kinetics m a y b e described b y the theory of Cabrera and M o t t .
C a b r e r a a n d M o t t a s s u m e d that a d s o r b e d o x y g e n m o l e c u l e s o n the s u r f a c e d i s s o -
ciate and produce electron traps b e l o w the Fermi level of the metal. Electrons
f r o m t h e m e t a l c a n t h e n b e t r a n s p o r t e d t h r o u g h t h e o x i d e l a y e r a n d fill t h e s e
traps. E l e c t r o n t r a n s p o r t m a y b e b y t u n n e l l i n g , o r b y t h e r m i o n i c e m i s s i o n for
l a r g e r o x i d e t h i c k n e s s e s a n d h i g h e r t e m p e r a t u r e s . T h e e l e c t r o n t r a n s p o r t l e a d s to
t h e f o r m a t i o n o f o x y g e n i o n s at t h e s u r f a c e 9a n9 3d 9h5
7e n c e a n e l e c t r i c field is e s t a -
b l i s h e d in t h e o x i d e l a y e r . It w a s a s s u m e d " ' that t h e p o t e n t i a l d r o p , V , is
i n d e p e n d e n t o f o x i d e t h i c k n e s s so that t h e field, F , is i n v e r s e l y p r o p o r t i o n a l to the
t h i c k n e s s . A v e r y s t r o n g field c a n o c c u r for thin o x i d e films. T h i s e l e c t r i c field
p r o m o t e s t h e diffusion o f c a t i o n s t h r o u g h t h e o x i d e . W h e n t h e diffusion o f i o n s
is t9h e93 5r a t e l i m i t i n g s t e p , t h e ion c u r r e n t , Jj, c a n b e w r i t t e n in a s i m p l i f i e d w a y
as '
Ji = A N v e x p ( - E i / k i ) sinh ( e a F / 2 k x ) , (14)
0
95
w h e r e A is a p p r o x i m a t e l y c o n s t a n t , N is the n u m b e r o f m e t a l i o n s p e r u n i t area
0
o n t h e m e t a l / o x i d e i n t e r f a c e , ν d e n o t e s a j u m p f r e q u e n c y , Ej is t h e a c t i v a t i o n
e n e r g y for i o n m o v e m e n t , e is t h e ion c h a r g e , α is t h e lattice c o n s t a n t a n d k is
B o l t z m a n n ' s c o n s t a n t . E q u a t9i5o n (14) m a y b e r e a r r a n g e d to y i e l d t h e t i m e d e p e n -
dent oxide thickness L(t) b y
dL(t)/dt = ( L / t ) s i n h (L /L(t)), (15)

c c c
w h e r e L = e « V / 2 k t a n d t = ( L / ΑΝ νν{) e x p ( E j / k x ) , w h e r e Vj is t h e v o l u m e o f
c c c 0
o x i d e f o r m e d b y a m e t a l ion. H e n c e E q . (15) d e s c r i b e s t h e r a t e o f m e t a l o x i d a t i o n
b y c a t i o n diffusion. A g r e e m e n t o f E q . (15) w i t h e x p e r i m e n t s d o e s n o t e s t a b l i s h
u n e q u i v o c a l l y t h e p h y s i c a l m e c h a n i s m , h o w e v e r . T h e r a t e e q u a t i o n for t h e c a s e
w h e n t h e r m i o n i c e m i s s i o n o f e l e c t r o n s is t h e r a t e l i m i t i n g s t e p95l e a d s t o c l o s e l y
s i m i l a r o x i d a t i o n k i n e t i c s if t h e o x i d e film is s u f f i c i e n t l y t h i n . Indeed various
a s s u m9 pt9
i8
5
o n s r e g a r d i n g t h e p h y s i c a l m e c h a n i s m s l e a d t o a p l e t h o r9 a8 o f r a t e
l a w s , ' s o m e o f which can b e closely approximated b y Eq. ( 1 5 ) . F o r t h i c k films
( L » L ) t h e C a b r e r a - M o t t l a w g r a d u a l l y c r o s s e s o v e r t o a diffusion l i m i t e d b e h a -
C
viour characterized b y a parabolic rate law.
The oxidation kinetics 9 of 1 9

n5
i c0
kel has been a subject of active study b y m a n y groups
for t h e last fifty y e a r s . " T1h5e0 most detailed w o r k appears to b e the recent
measurements of Sales e t . a l . in t h e v i c i n i t y o f t h e C u r i e t e m p e r a t u r e . T h e i r
experimental oxide thicknesses are depicted on a log-log plot as a function o f time
in F i g . 1 5 . It is p o s s i b l e to let their d a t a , o b t a i n e d at different t e m p e r a t u r e s , fall o n
a s i n g l e " m a s t e r " c u r v e b y t r a n s l a t i o n a l o n g t h e t i m e axis. T h i s is a c o n s e q u e n c e
o f t h e a c t i v a t e d b e h a v i o u r o f t in E q . ( 1 5 ) . T h e l o c a t i o n o f t h e ten m i n u t e m a r k
c
1 1 1—r Τ
I ι ι ι—τη ι 1—~p
OXIDATION OF NICKEL
MOTT-CABRERA THEORY
20θ|-
0) - Jt
</> w*
Ζ J*
Ξ100- JUr
9 80-
60- ^Υ^ Δ
L O C A T I O N O F 10 MIN.MARK
631 648
Α Ο • A
40 h T(K) 603 611
621 639
658
JL 1_ JL
1 10 10' 10"
T I M E A T 6 0 3 Κ (MIN)
Fig. 1 5 . O x i d e t h i c k n e s s a s a f u n c t i o n o f o x i d a t i o n t i m e for s i n t e r e d
n i c k e l . E x p e r i m e n t a l p o i n t s f r o m R e f . 1 0 5 , t a k e n at different
temperatures, have been superimposed on a single curve by
translation along the time axis. T h e inset s h o w s the location of
the 1 0 m i n u t e m a r k for different t e m p e r a t u r e s . S y m b o l s
p e r t a i n i n g t o all t h e t e m p e r a t u r e s a r e g i v e n in t h e inset.
T h e c u r v e d e p i c t s a p r e d i c t i o n o f t h e o x i d a t i o n k i n e t i c s b y the
Cabrera-Mott theory. (From Ref. 72).
o n t h e t i m e a x i s is s h o w n for e a c h o f t h e t e m p e r a t u r e s in F i g . 1 5 . It is s e e n that
t h e e x p e r i m e n t a l p o i n t s in t h e figure a r e in e x c e l l e n t a g r e e m e n t w i t h t h e
p r e d i c t i o n o f t h e C a b r e r a - M o t t t h e o r y in E q . ( 1 5 ) . H e n c e o n e c a n c o n c l u d e that the
o x i d a t i o n o f n i c k e l c a n b e d e s c r i b e d w i t h this t h e o r y , at l e a s t for o x i d e t h i c k n e s s e s
b e l o w 3 01 n m 03. 1T h-e 1q u a0l i t a t i v e f e a t u r e s in F i g . 15 a g r e e w i t h e a r l i e r o x i d a t i o n
studies for t e m p e r a t u r e s in the 6 5 0 - 8 0 0 Κ r a n g e . It s h o u l d b e n o t e d t h a t the
o x i d a t i o n k i n e t i c s in F i g . 15 c a n b e a p p r o x i m a t e d b y t h e p o w e r l a w L - over
r e g i o n s o f o n e d e c a d e o r m o r e in t i m e . In the figure, φ is a p p r o x i m a t e l y 0.2 at
s h o r t t i m e s a n d i n c r e a s e s t o 0.4 for l o n g e r t i m e s . A t t e m p e r a t u r e s b e l o w 6 0 0 K ,
t h e o x i d a t i o n k i n e t i c s o f n i c k e l c a n also b e a p p r o x i m a t e d b y a p o w e r l a w . I n this
r e g i o n , w h i c h c o r r e s p o n d s to l o w e r o x i d e t h i c k n e s s e s t h a n t h o s e p e r t i n e n t for F i g .
1 5 , t h e e x p o9n e1n9t 0 1φ4is0 l o w e r . F o r e x a m p l e , v a l u e s o f φ b e t w e e n 0 . 0 6 a n d 0 . 1 3 h a v e
been f o u n d ' ' at 4 7 0 - 4 7 5 K . T h e s e l o w e x p o n e n t v a l u e s a r e a l s o in l i n e w i t h
the Cabrera-Mott theory.
T h e a c t i v a t i o n e n e r g y o f t h e o x i d a t i o n p r o c e s s c a n b e o b t a i n e d f r o m t h e shifts o f
150
t h e c u r v e s r e f e r r i n g to different t e m p e r a t u r e s in F i g . 1 5 . A n e q u i v a l e n t p r o c e d u r e
was used b y Sales e t . a l . to e v a l u a t e a c t i v a t i o n e n e r g i e s . T h e y f o u n d a r e m a r -
k a b l e c h a n g e in t h e a c t i v a t i o n e n e r g y at t h e C u r i e t e m p e r a t u r e o f n i c k e l (631 K ) .
B e l o w t h e C u r i e t e m p e r a t u r e t h e a c t i v a t i o n e n e r g y w a s f o u n d to b e 2 . 6 5 e V , b u t
t h e a c t i v a t i o n e n e r g y w a s o n l y 1.60 e V at h i g h e r t e m p e r a t u r e s . A n o m a l o u s 1 70
o x i d a t i o n b e h a v i o u r at t h e C u r i e t e m p e r a t u r e w a s s e e n a l s o in o t h e r w o r k ,
w h e r e t h e o x i d a t i o n r a t e s h o w e d a m a r k e d d i s c o n t i n u i t y at this t e m p e r a t u r e , b u t
t h e a c t i v a t i o n e n e r g i e s differed o n l y slightly.
R e s u l t s o n t h e o x i d a t i o n o f c h r o m i u m at r e d u c e d o x y g e n p r e s s u r e a n d t e m p e r a -
t u r e s i n t h e r a n g e 5 7 3 to 6 7 3 Κ h a v e a l s o b e e n fitted to t h e C a b r e r a - M o t t t h e o r y ,
w h e n t h e o x i d e t h i c k n e s s w a s b e l o w 6 n m (Ref. 1 0 6 ) . T h e d a t a c a n b e w e l l
approximated b y a p o w e r law with exponent 0.12. T h e activation energy was
f o u n d to b e 1.8 e V . A t h i g h e r o x i d e t h i c k n e s s e s , the o x i d a t i o n c r o s s e s o v e r to a
different r e g i m e w i t h e x p o n e n t 0.5. H e n c e it s e e m s t h a t t h e o x i d a t i o n o f c h r o m i -
u m is m o r e c o m p l e x t h a1n70 for n i c k e l , h a v i n g different m e c h a n i s m s c o m p e t i n g .
Shanker and H o l l o w a y s t u d i e d t h e o x i d a t i o n o f r o u g h c h r o m i u m s u r f a c e s in
air for t e m p e r a t u r e s b e t w e e n 5 4 0 a n d 7 6 0 K . T h e y r e p o r t e d a l o g a r i t h m i c r a t e l a w
for o x i d e t h i c k n e s s e s u p to 1 0 0 n m , b u t the r e s u l t s c o u l d a l s o b e fitted to p o w e r
l a w s w i t h k i n e t i c e x p o n e n t s in t h e r a n g e 0 . 0 7 to 0 . 1 3 . T h e o x i d a t i o n r a t e w a s
f o u n d to b e d e p e n d e n t o n s a m p l e p r e p a r a t i o n , a n d it w a s s u g1 g7e s0t e d t h a t a n
i n c r e a s e d s u r f a c e r o u g h n e s s can d e c r e a s e the o x i d a t i o n r a t e .
V e r y little is k n o w n a b o u t t h e o x i d a t i o n b e h a v i o u r o f s m a l l m e t a l p a r t i c l e s .1 0 198 0
H o w e v e r , it h a s b e e n s h o w n that t h e y c a n b e p a s s i v a t e d b y s l o w o x i d a t i o n ' 1 01
a n d a r e t h e n r e m a r k a b l y r e s i s t a n t to further o x i d a t i o n . R e c e n t l y it w a s f o u n d
t h a t t h e s u r f a c e o x i d e o n a m e t a l p a r t i c l e is t h i n n e r t h e s m a l l e r t h e p a r t i c l e s i z e .
T h i s effect w a s i n t e r p r e t e d w i t h i n t h e C a b r e r a - M o t t t h e o r y as b e i n g d u e to the
charging energy o f the particles, which would prevent electron transport across
t h e o x i d e a n d h e n c e s l o w d o w n t h e o x i d a t i o n . F u r t h e r m o r e t h e r o u g h n e s s effect
a l l u d e d to a b o v e i n d i c a t e s that s m a l l p a r t i c l e s m a y d i s p l a y o x i d a t i o n r a t e s q u i t e
different f r o m t h o s e o f t h e b u l k .
In o r d e r to a p p l y t h e a b o v e c o n s i d e r a t i o n s to t h e d e s c r i p t i o n o f t h e o x i d a t i o n o f
m e t a l p a r t i c l e s in s o l a r c o l l e c t o r c o a t i n g s , o n e first n e e d s s o m e s i m p l e p a r a m e t e r s
that d e s c r i b e the o x i d a t i o n k i n e t i c s . A s n o t e d a b o v e , a s i m p l e p o w e r l a w is a g o o d
a p p r o x i m a t i o n to t h e C a b r e r a - M o t t t h e o r y for o n e to t w o d e c a d e s o f t i m e . H e n c e
w e propose the relation
(l-Q)~(t/qft (16)
w h e r e φ is t h e effective o x i d a t i o n e x p o n e n t r e f e r r e d to a b o v e , a n d q is a s s u m e d to
b e t h e r m a l l y a c t i v a t e d a c c o r d i n g to t h e r e l a t i o n
q = q exp ( E / k t ) , (17)
G a
w h e r e E d e n o t e s t h e a c t i v a t i o n e n e r g y . It s h o u l d b e n o t e d t h a t a s i m i l a r r e l a t i o n
a
h a s b e8 e5n p r e v i o u s l y u s e d to8 a7
n6a l y8z e d u r a b i l i t y tests o n s o l a r a b s o r b e r c o a t i n g s b y
P e t t i t and by Kohl e t . a l .
E. D e g r a d a t i o n K i n e t i c s o f Solar A b s o r b e r C o a t i n g s
In S e c . V I C it w a s f o u n d t h a t t h e n o r m a l i z e d s o l a r a b s o r p t a n c e c h a n g e c o u l d b e
d e s c r i b e d as a p o w e r l a w o f t h e n o r m a l i z e d d e c r e a s e in m e t a l c o n t e n t . A n a l o -
g o u s l y , f r o m S e c . V I D o n e c a n infer that t h e o x i d a t i o n k i n e t i c s o f a m e t a l often
c a n b e a p p r o x i m a t e d b y a p o w e r l a w o v e r at l e a s t o n e to t w o d e c a d e s o f t i m e .
Based o n these considerations, w e propose a simple parametric equation that can
b e u s e d to c h a r a c t e r i z e a n d c o m p a r e d e g r a d a t i o n c u r v e s o f s o l a r c o l l e c t o r c o a t i n g s .
C o m b i n i n g E q s . (12) a n d (16) o n e o b t a i n s
1 - (A
s / oA Jlj ) = Β (t/q)Y, (18)
w h e r e Β is a c o n s t a n t a n d t h e k i n e t i c e x p o n e n t is g i v e n b y γ = βφ. In r e c e n t y e a r s ,
m a n y studies of the degradation kinetics of selectively solar absorbing coatings
h a v e b e e n c a r r i e d out. H e r e w e a n a l y z e d a t a o b t a i n e d for n i c k e l p i g m e2
n8t e d
a l u m i n i u m o x i d e a n d b l a c k c h r o m i u m w i t h i n the I E A T a s k X p r o j e c t . In t h e s e
s t u d i e s , r e f e r r e d to a b o v e , A i w a s m e a s u r e d after a n n e a l i n g in air for v a r i o u s
s o
t i m e s at different t e m p e r a t u r e s .
In F i g . 1 6 w e i n v e s t i g a t e to w h a t e x t e n t Eq. (18) c a n d e s c r i b e t h e d e g r a d a t i o n o f A i
s o
for s e l e c t i v e l y s o l a r a b s o r b i n g c o a t i n g s u p o n e x p o s u r e to e l e v a t e d t e m p e r a t u r e s .
In t h e p l o t s the e x p e r i m e n t a l d a t a w e r e n o r m a l i z e d to a s i n g l e c u r v e b y shifting
t h e r e s u l t s o b t a i n e c ^ a t v a r i o u s t e m p e r a t u r e s p a r a l l e l to t h e t i m e axis. F i g u r e 1 6 a
d e p i c t s 1 - ( A i / A i ) as a function o f t i m e , o n a l o g - l o g p l o t , for t h e S u n s t r i p
s o s o
c o a t i n g . T h e e x p e r i m e n t a l p o i n t s fall w i t h a g o o d a p p r o x i m a t i o n o n a s i n g l e l i n e ,
w h i c h c a n b e d e s c r i b e d b y E q . (18) w i t h γ = 0.17. It is r e m a r k a b l e that t h e p o w e r l a w
b e h a v i o u r s e e m s to p e r s i s t for m o r e t h a n f o u r d e c a d e s o n t h e t i m e a x i s in this
c a s e . F i g u r e 1 6 b d i s p l a y s a s i m i l a r p l o t for t h e d e g r a d a t i o n o f a b l a c k c h r o m i u m
coating produced b y Energie Solaire. H e r e γ shows a considerably higher value,
I ι I I I I
0.4
T(K) 603 623 673 723 773
8 • • • > • • Δ
573 653 703 823
L O C A T I O N O F 10h MARK
V 0.1
_
0.04
-
(a)
SUNSTRIP
-
V=0.17
I I 2 I 3 I 4 ι s ι 6
-
10 10 10 10 10 10
TIME A T 603K (h)
Fig. 1 6 a .
! I I ι I I
0.4
T(K) 573 603 623 723 773 823 873 "
• 6• 5ο 3 • • V • Δ <
673 753
LOCATION OF 10h MARK
I 0.1 —
°<
ô
<
0.04 (b)
• ENERGIE SOLAIRE
0.01 Y =0.38 ~~
/ ο
I
J I I I
10 10' 10 10* 10* 10
TIME AT 573 Κ (h)
Fig. 1 6 b . N o r m a l i z e d c h a n g e in s o l a r a b s o r p t a n c e as a f u n c t i o n o f a g e i n g
t i m e for ( a ) n i c k e l p i g m e n t e d a l u m i n i u m o x i d e ( S u n s t r i p ) a n d
(b) b l a c k c h r o m i u m ( E n e r g i e S o l a i r e ) c o a t i n g s . E x p e r i m e n t a l
d a t a ( R e f . 2 8 ) o b t a i n e d a t different t e m p e r a t u r e s w e r e n o r m a -
l i z e d t o a s i n g l e c u r v e b y shifting a l o n g t h e t i m e a x i s , as
i n d i c a t e d i n t h e i n s e t s . L i n e s w e r e d r a w n for c o n v e n i e n c e .
(From Refs. 2 8 and 72).
w h i c h is in l i n e w i t h t h e l a r g e r v a l u e s o f β (see F i g . 1 4 ) for b l a c k c h r o m i u m . T h e
a c t i v a t i o n e n e r g i e s for t h e d e g r a d a t i o n p r o c e s s c a n b e d e t e r m i n e d f r o m t h e shifts
o f t h e c u r v e s p e r t a i n i n g to different t e m p e r a t u r e s in F i g . 16 ( s e e E q s . 1 7 a n d 1 8 ) . In
Fig. 17 w e d e p i c t t h e l o g a r i t h m o f t h e l o c a t i o n o f t h e 10 h m a r k , as g i v e n at t h e top
o f F i g . 1 6 a , as a function o f i n v e r s e t e m p e r a t u r e for t h e S u n s t r i p c o a t i n g . T h e
f i g u r e a l s o c o n t a i n s d a t a for t h e S h o w a c o a t i n g . T h e a c t i v a t i o n e n e r g y w a s
o b t a i n e d f r o m fits o f t h e d a t a p o i n t s to s t r a i g h t l i n e s a s i n d i c a t e d in t h e figure.
T h e s c a t t e r in t h e e x p e r i m e n t a l p o i n t s p r e v e n t s a n a c c u r a t e d e t e r m i n a t i o n o f the
a c t i v a t i o n e n e r g y , b u t d a t a a b o v e t h e C u r i e t e m p e r a t u r e fall c l o s e to a s t r a i g h t line,
a n d w e o b t a i n a n a c1 t i5
v0a t i o n e n e r g y o f 2 . 4 e V . T h i s v a l u e is m u c h l a r g e r t h a n the
result of Sales e t . a l . for the o x i d a t i o n o f b u l k n i c k e l . H o w e v e r , q u i t e different
a c t i v a t i o n e n e r g i e s h a v e b e e n f o u n d in different e x p e r i m e n t s . F o r e x a m p l e , 120
v a l u e s c o m p a r a b l e w i t h o u r r e s u l t for t h e S u n s t r i p c o a t i n g h a v e b e e n f o u n d
b o t h b e l o w a n d a b o v e t h e C u r i e t e m p e r a t u r e in a n o t h e r s t u d y . A s i m i l a r a n a l y s i s ,
s h o w n in F i g . 1 8 , for t h e b l a c k c h r o m i u m c o a t i n g y i e l d s a n a c t i v a t i o n e1n6e0 r g y o f 1.5
e V , w h i c h is n o t far f r o m t h e v a l u e for o x i d a t i o n o f b u l k c h r o m i u m .
e— ι 1 1 1 1 X
- A <> Ni-Al 0 _
10 us2 3
\ I ·
£ °1 4
Φ
\ E =2.4eV
Ε a
\ ·
2
A \
10
χ •
\ «·
1 I I I I I
1.2 1.4 1.6 3 1.8 2.0
1/T(10 /K)
Fig. 17. F i l l e d circles s h o w t h e l o c a t i o n s o f t h e 10 h m a r k s o n the t i m e

axis o f F i g . 1 6 a as a function o f i n v e r s e t e m p e r a t u r e for
Sunstrip (SU) coatings. Filled triangles indicate analogous
d a t a for S h o w a ( S H ) c o a t i n g s . A s t r a i g h t l i n e fit to t h e d a t a
gave the shown activation energy. T h e Curie temperature of
n i c k e l is d e n o t e d x . ( F r o m R e f . 7 2 ) .
c
6 —j—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—
10 - \ ·
\ Black C h r o m e
\ ES
5
10 - \
5 4 · \ E = 1.5 e V
a
I 10 - \
Ρ ·\
3 •\
10 - \
2
10 - \
• \
1
10 I I t > ι ι I ι Χ ι ι I ι
1.0 3
1.5 2.0
ι/τ(ΐο /κ)
Fig. 1 8 . L o c a t i o n s o f t h e 1 0 h m a r k s o n t h e t i m e a x i s as a f u n c t i o n o f
i n v e r s e t e m p e r a t u r e for b l a c k c h r o m i u m c o a t i n g s m a d e b y
E n e r g i e S o l a i r e (ES). T h e r e s u l t s a r e b a s e d o n a n a n a l y s i s
s i m i l a r to t h e o n e in F i g . 17. A s t r a i g h t l i n e fit to t h e d a t a
gives the shown activation energy.
It is p o s s i b l e to m a k e a p r e l i m i n a r y c o m p a r i s o n o f t h e d e g r a d a t i o n k i n e t i c s o f t h e
solar absorber coatings with the oxidation behaviour of the bulk metals. F r o m the
e x p o n e n t γ, d e s c r i b i n g t h e d e g r a d a t i o n k i n e t i c s , a n d t h e e x p o n e n t β, i n t r o d u c e d in
Sec. V I C , o n e e a s i l y o b t a i n s t h e k i n e t i c e x p o n e n t φ for t h e o x i d a t i o n o f m e t a l in
t h e s e l e c t i v e l y s o l a r - a b s o r b i n g c o a t i n g s . T h e d a t a p r e s e n t e d a b o v e for n i c k e l
p i g m e n t e d a l u m i n i u m o x i d e a n d b l a c k c h r o m i u m c o a t i n g s l e a d to s m a l l v a l u e s
of φ, in t h e r a n g e o f 0.05 to 0.07. T h i s is l o w e r t h a n m o s t o f t h e r e s u l t s for b u l k
nickel and chromium. These low values of φ could b e compatible with the
C a b r e r a - M o t t t h e o r y if t h e o x i d e c o a t i n g is v e r y thin. F o r t h e c a s e o f n i c k e l o x i d e ,
t h i c k n e s s e s less t h a n 3 n m a r e i m p l i e d .
ο
I n a d d i t i o n , it f o l l o w s f r o m F i g . 13 that a c h a n g e o f 0.1 i n Δ Α ι / Α ι c o r r e s p o n d s
5 0δ ο
t o a n o x i d e t h i c k n e s s o f a b o u t o n e tenth o f t h e m e t a l p a r t i c l e d i a m e t e r for the c a s e
of nickel pigmented aluminium oxide. H e n c e thicknesses of n o m o r e than a few
n a n o m e t r e s a r e p r o b a b l y p r e s e n t in q u i t e h e a v i l y d e g r a d e d c o a t i n g s .
There exists one major discrepancy between the oxidation of bulk metals and
w h a t c a n b e inferred f r o m F i g . 1 6 . A n 1 o x i0 1d e6 t50h i c k n e s s o f 5 n m is u s u a l l y esta-
b l i s h e d in less t h a n o n e h o u r at 6 0 0 K . ' O n t h e o t h e r 4h a n d , t h e d e g r a d a t i o n
o f N 1 - A I 2 O 3 a n d b l a c k c h r o m i u m c o n t i n u e s e v e n after 1 0 h o u r s at this t e m p e r a -
ture. P a r t i c l e s w i t h s i z e s o f a f e w tens o f n a n o m e t r e s s h o u l d o x i d i z e c o m p l e t e l y in
a m u c h s h o r t e r t i m e than this, if t h e b u l k k i n e t i c s w e r e o b e y e d .
T h e r e a s o n for t h e s l o w o x i d a t i o n o f t h e m e t a l p a r t i c l e s in s e l e c t i v e l y s o l a r -
a b s o r b i n g c o a t i n g s is n o t k n o w n a n d calls for f u n d a m e n t a l s t u d i e s . T h e o x i d a t i o n
m e c h a n i s m s in s m a l l m e t a l p a r t i c l e s is l a r g e l y a n o p e n q u e s t i o n , a n d it is n o t clear
w h e t h e r t h e C a b r e r a - M o t t t h e o r y is a p p l i c a b l e at all, o r if this t h e o r y c a n b e m o d i -
fied to i n c l u d e p a r t i c l e s i z e effects.
F. Lifetime Evaluations
F i n a l l y , w e m a k e s o m e c o m m e n t s o n l i f e t i m e e v a l u a t i o n s for s o l a r c o l l e c t o r
c o a t i n g s b a s e d o n a c c e l e r a t e d a g e i n g tests. T h e p u r p o s e o f s u c h tests is to o b t a i n
t h e s a m e d e g r a d a t i o n o f t h e s a m p l e as after a l i f e t i m e u n d e r o p e r a t i n g c o n d i t i o n s ,
b u t in a m u c h s h o r t e r p e r i o d . In h i g h t e m p e r a t u r e d e g r a d a t i o n tests, this is
a c c o m p l i s h e d b y e x p o s i n g t h e s a m p l e to h i g h e r t e m p e r a t u r e s t h a n t h o s e u s u a l l y
encountered d 8u 8
r47
i n g n o r m a l o p e r a t i o n o f a solar c o l l e c t o r . T h e s o c a l l e d a c c e l e -
r a t i o n f a c t o r " d e s c r i b e s t h e difference in t h e d e g r a d a t i o n b e h a v i o u r b e t w e e n
t h e test t e m p e r a t u r e x
t tea nsd a r e f e r e n c e t e m p e r a t u r e τ Γ( w h i c h r e p r e s e n t s , for
e x a m p l e , n o r m a l o p e r a t i n g c o n d i t i o n s ) . It w a s s h o w n in S e c . V I Ε that t h e
degradation of the solar absorptance of nickel pigmented a l u m i n i u m oxide and
b l a c k c h r o m i u m c o a t i n g8s is 847 t h e r m a l l y a c t i v a t e d . In this c a s e t h e a c c e l e r a t i o n
factor, a , is g i v e n b y '
t e s t h
a = e xa (
1 1 T (19)
test Pt"k" ~ " >J-
τ test
In o r d e r to a p p l y this e q u a t i o n to p r a c t i c a l c o a t i n g s , t h e f o l l o w i n g s t e p s s h o u l d b e
taken, (i) A criterion m u s t b e e s t a b l i s h e d , w h i c h states t h e d e c r e a s e in s o l a r
a b s o r p t a n c e that is c o n s i d e r e d a c c e p t a b l e for t h e p e r f o r m a n c e o f t h e s o l a r a b s o r b e r ,
(ii) A c c e l e r a t e d tests at different t e m p e r a t u r e s s h o u l d b e p e r f o r m e d until this level
o f d e g r a d a t i o n is r e a c h e d , (iii) T h e a c t i v a t i o n e n e r g y E s h o u l d b e c a l c u l a t e d , (iv)
a
E q u a t i o n (19) s h o u l d b e u s e d to c a l c u l a t e t h e a c c e l e r a t i o n factor a n d h e n c e the
lifetime o f the selectively solar-absorbing coating under operating conditions.
A b o v e , w e c o n f i n e d the d i s c u s s i o n to t h e c a s e o f d e g r a d a t i o n o f A i , b u t a c c e l8e -84

7
s o
ration factors c a n b e u s e d to d e s c r8i4b e t h e effect o f v a r i o u s d e g r a d a t i o n m o d e s '
a s w e l l as c o m b i n a t i o n s o f t h e m . In t h e s e c a s e s t h e functional 8 84
7 forms of a
t te msa y
differ d e p e n d i n g o n t h e p h y s i c s o f the d e g r a d a t i o n m o d e s . '
W e a l s o r e m a r k that E q . ( 1 8 ) , if v a l i d a t e d for a p a r t i c u l a r s e l e c t i v e l y solar a b s o r -

b i n g c o a t i n g , p e r m i t s the p r e d i c t i o n o f t h e future d e g r a d a t i o n o f a s a m p l e f r o m
the d e g r a d a t i o n that h a s o c c u r r e d in a certain time. H o w e v e r , it is n o t k n o w n
w h e t h e r f u n c t i o n s o f this f o r m a p p l y to d e g r a d a t i o n f a c t o r s o t h e r t h a n e x p o s u r e to
high temperatures.
VII. CONCLUSIONAND REMARKS
T h i s c h a p t e r i n t r o d u c e d s p e c t r a l l y s e l e c t i v e a b s o r b e r s u r f a c e s for efficient p h o t o -
t h e r m a l c o n v e r s i o n o f s o l a r e n e r g y . T h e k e y f e a t u r e is a h i g h s o l a r a b s o r p t a n c e
c o m b i n e d w i t h a l o w t h e r m a l e m3 i t t3-a n 1
c e . T h e e x p o s i t i o n is n o t c o m p l e t e b u t
s e r v e s to u p d a t e e a r l i e r r e v i e w s , p a r t i c u l a r l y as r e g a r d s p r a c t i c a l l y useful
c o a t i n g s , a n d to p r o v i d e a d e t a i l e d d i s c u s s i o n o n r e c e n t a d v a n c e s in u n d e r -
s t a n d i n g d e g r a d a t i o n a n d durability.
S e v e r a l different d e s i g n p r i n c i p l e s for a c h i e v i n g s p e c t r a l l y s e l e c t i v e a b s o r p t i o n
w e r e p r e s e n t e d . In m a n y c a s e s , a m e t a l - d i e l e c t r i c c o m p o s i t e l a y e r is r e s p o n s i b l e
for t h e h i g h s o l a r a b s o r p t a n c e , w h e r e a s the r e f l e c t a n c e o f a n u n d e r l y i n g m e t a l
s u b s t r a t e g i v e s t h e l o w t h e r m a l e m i t t a n c e . T h e s o l a r a b s o r p t a n c e is often a u g -
m e n t e d b y t h e u s e o f antireflecting l a y e r s , p o r o s i t y , s u r f a c e r o u g h n e s s , e t c . A t least
t h e m a j o r i t y o f t h e p r a c t i c a l l y useful s e l e c t i v e l y s o l a r - a b s o r b i n g s u r f a c e s o f t o d a y
h a v e a m e t a l - d i e l e c t r i c l a y e r as their m o s t c r u c i a l c o m p o n e n t . M a n y o f t h e c o a -
tings - including black c h r o m i u m and nickel pigmented anodic aluminium oxide
- a r e p r e p a r e d b y e l e c t r o c h e m i c a l t e c h n o l o g y , b u t t h e r e a p p e a r s t o b e a t e n d e n c y to
p u t m o r e e m p h a s i s o n c o a t i n g s m a d e b y p h y s i c a l v a p o u r d e p o s i t i o n , s u c h as
m a g n e t r o n s p u t t e r i n g . In o u r o p i n i o n , t h e s p u t t e r - d e p o s i t e d c o a t i n g s m a d e b y
L U Z I n d u s t r i e s Israel - r e p o r t e d o n in F i g . 6 a b o v e - r e p r e s e n t s a l i n e o f p r o b a b l e
future development. T h e electrochemically produced coatings can b e m a d e with
relatively inexpensive equipment, but require processing of large quantities of
hazardous chemicals. Physical vapour deposition utilizes m o r e capital-intensive
e q u i p m e n t , b u t d o e s n o t n o r m a l y l e a d to h a z a r d o u s e x h a u s t s .
T h e different m i c r o s t r u c t u r e s o f r e l e v a n c e for s e l e c t i v e l y s o l a r a b s o r b i n g s u r f a c e s
w e r e i n t r o d u c e d , a n d t h e p e r t i n e n t Effective M e d i u m T h e o r i e s - n e e d e d for
c o m p u t i n g o p t i c a l p r o p e r t i e s - w e r e c o v e r e d superficially. A m o r e d e t a i l e d e x p o s i -
tion o f t h e s e t h e o r i e s is g i v e n in t h e c h a p t e r o n O p t i c a l P r o p e r t i e s o f T w o - C o m p o -
n e n t M a t e r i a l s e a r l i e r in this b o o k . M u l t i l a y e r c o n f i g u r a t i o n s , s u r f a c e r o u g h n e s s ,
and graded metal-dielectric compositions w e r e discussed. T w o case studies are
i n c l u d e d w i t h t h e p u r p o s e o f illustrating to w h a t e x t e n t t h e o p t i c a l p r o p e r t i e s c a n
b e u n d e r s t o o d f r o m b a s i c t h e o r y ; specifically w e d i s c u s s n i c k e l p i g m e n t e d a n o d i c
a l u m i n i u m oxide and textured Al-Si composite coatings.
A n i m p o r t a n t p a r t o f this c h a p t e r d e a l t w i t h d e g r a d a t i o n a n d d u r a b i l i t y o f s o m e
p r a c t i c a l l y useful s e l e c t i v e l y s o l a r - a b s o r b i n g surfaces. T h e first p a r t o f t h e
d i s c u s s i o n o n this s u b j e c t r e g a r d s m o d e l l i n g o f the o p t i c a l p r o p e r t i e s o f different
t y p e s o f N 1 - A I 2 O 3 a n d b l a c k c h r o m i u m surfaces s u b j e c t e d to a c c e l e r a t e d
d e g r a d a t i o n b y h e a t t r e a t m e n t in air. F r o m c o m p u t a t i o n s b a s e d o n Effective
M e d i u m T h e o r y it w a s s h o w n that the d e g r a d a t i o n o f N 1 - A I 2 O 3 p r o g r e s s e d via
o x i d a t i o n o f t h e n i c k e l , so that the d e n s i t y o f m e t a l l i c n i c k e l d e c r e a s e d u n i f o r m l y
a c r o s s t h e m e t a l p i g m e n t e d l a y e r . A n a l t e r n a t i v e m o d e l , w i t h an o x i d a t i o n front
that m o v e s gradually toward the substrate during degradation, could not explain
t h e data. In t h e n e x t s t e p o f t h e a n a l y s i s , t h e d e g r a d a t i o n w a s p a r a m e t e r i z e d , a n d
it w a s s h o w n that t h e n o r m a l i z e d s o l a r a b s o r p t a n c e b e h a v e s as a p o w e r l a w o f the
n o r m a l i z e d n i c k e l m e t a l c o n t e n t . W e l l - d e f i n e d v a l u e s o f t h e e x p o n e n t in t h e
p o w e r l a w c o u l d b e e x t r a c t e d . T h e t h i r d step in t h e a p p r o a c h to a d e t a i l e d
u n d e r s t a n d i n g o f t h e d e g r a d a t i o n i n v o l v e d a m o d e l for t h e o x i d a t i o n k i n e9t7i c s o f
flat m e t a l l i c surfaces. H e r e it is p o s s i b l e to a p p l y t h e C a b r e r a - M o t t t h e o r y , w h i c h
is k n o w n to b e a d e q u a t e for n i c k e l a n d c h r o m i u m , for e x a m p l e . S p e c i f i c a l l y , t h e
o x i d a t i o n k i n e t i c s c a n b e r e p r e s e n t e d b y a p o w e r l a w w i t h a fixed e x p o n e n t o v e r
o n e to t w o d e c a d e s in t i m e . S m a l l m e t a l l i c p a r t i c l e s h a v e o x i d a t i o n k i n e t i c s that
a r e different f r o m the k i n e t i c s o f flat s u r f a c e s , t h o u g h , a n d t r a n s f o r m i n t o o x i d e at
a m u c h s l o w e r rate. T h i s p h e n o m e n o n c l e a r l y is c o n d u c i v e to l o n g - t e r m d u r a -
bility. A s a final s t e p , t h e p o w e r l a w for t h e n o r m a l i z e d c h a n g e in s o l a r a b s o r p -
t a n c e w a s c o m b i n e d w i t h t h e p o w e r l a w i n h e r e n t in t h e C a b r e r a - M o t t t h e o r y in
o r d e r to f o r m u l a t e a p a r a m e t r i c e q u a t i o n for t h e a b s o r p t i o n d e g r a d a t i o n o f
selectively solar-absorbing coatings comprising a metal-dielectric composite. The
p a r a m e t e r s o f this e q u a t i o n c a n n o t y e t b e o b t a i n e d f r o m b a s i c p h y s i c s , w h i c h to a
l a r g e d e g r e e is a m a n i f e s t a t i o n o f o u r l a c k o f u n d e r s t a n d i n g o f t h e o x i d a t i o n
k i n e t i c s o f fine m e t a l p a r t i c l e s . It is h o p e d that c o n t i n u e d w o r k o n s o l a r c o l l e c t o r
d u r a b i l i t y , a n d o n t h e d u r a b i l i t y o f o t h e r m e t a l - d i e l e c t r i c c o m p o s i t e s d e s i g n e d to
o p e r a t e at e l e v a t e d t e m p e r a t u r e , will s t i m u l a t e t h e n e e d e d e x p e r i m e n t a l a n d
t h e o r e t i c a l w o r k to u n d e r s t a n d t h e i n t r i g u i n g l y s l o w o x i d a t i o n o f m e t a l p a r t i c l e s .
T h e d e g r a d a t i o n k i n e t i c s o f the t h e r m a l e m i t t a n c e is o f i n t e r e s t for s o l a r c o l l e c t o r
s u r f a c e s , b u t this effect h a s n o t yet b e e n i n v e s t i g a t e d in detail s i n c e it is m u c h
m o r e difficult to treat t h a n t h e a b s o r p t a n c e d e g r a d a t i o n .
REFERENCES

Applications (SPIE Opt. Engr. Press, Bellingham, 1989).
2. P. M o o n , J . F r a n k l i n Inst. 2 3 0 , 5 8 3 ( 1 9 4 0 ) .
3. A . B . M e i n e l a n d M . P . M e i n e l , Applied Solar Energy: An Introduction
( A d d i s o n - W e s l e y , R e a d i n g , 1 9 7 6 ) , C h a p . 9.
4. B . O . S é r a p h i n a n d A . B . M e i n e l , in Optical Properties of Solids - New
Developments, edited by B.O. Séraphin (North-Holland, Amsterdam,
1 9 7 6 ) , C h a p . 17.
5. R.E. H a h n and B.O. Séraphin, Phys. Thin Films 10, 1 (1978).
6. B . O . S é r a p h i n , in Solar Energy Conversion: Solid State Physics Aspects, Vol.
31 o f Topics in Applied Physics, e d i t e d b y B . O . S é r a p h i n ( S p r i n g e r , B e r l i n ,
1 9 7 9 ) , p. 5; in Solar Energy Conversion: An Introductory Course, edited by
A.E. Dixon and J.D. Leslie (Pergamon, N e w York, 1979), p. 287.
7. C M . L a m p e r t , S o l a r E n e r g y M a t e r . 1, 3 1 9 ( 1 9 7 9 ) ; 2 , 1 ( 1 9 7 9 ) .
8. P . K . C . Pillai a n d R . C . A g a r w a l , P h y s . Stat. Sol. A 6 0 , 11 ( 1 9 8 0 ) .
9. O . P . A g n i h o t r i a n d B . K . G u p t a , Solar Selective Surfaces ( W i l e y , N e w Y o r k ,
1981).
10. M . M . K o l t u n , Selektivnye Opticheskie Poverknosti Preobrazovatelei
Solnechnoi Energii ( N a u k a P r e s s , M o s c o w , 1 9 7 9 ) . E n g l i s h t r a n s l a t i o n :
Selective Optical Surfaces for Solar Energy Converters (Allerton Press, N e w
Y o r k , 1981).
11. S.A. H e r z e n b e r g a n d R . S i l b e r g l i t t , P r o c . S o c . P h o t o - O p t . I n s t r u m . E n g r . 3 2 4 ,
92 (1982).
12. W . F . B o g a e r t s a n d C M . L a m p e r t , J. M a t e r . S c i . 1 8 , 2 8 4 7 ( 1 9 8 3 ) .
13. G . A . N i k l a s s o n a n d C . G . G r a n q v i s t , J. M a t e r . S c i . 1 8 , 3 4 7 5 ( 1 9 8 3 ) .
14. E. Randich and D.D. Allred, Thin Solid Films 8 3 , 393 (1981); E. Randich and
R . B . Pettit, S o l a r E n e r g y M a t e r . 5 , 4 2 5 ( 1 9 8 1 ) .
15. B . O . S é r a p h i n , T h i n S o l i d F i l m s 3 9 , 8 7 (1976); 5 7 , 2 9 3 ( 1 9 7 9 ) .
16. M . Janai, D.D. Allred, D.C. Booth and B.O. Séraphin, Solar Energy Mater. \ ,
11 ( 1 9 7 9 ) ; D . C . B o o t h , D . D . A l l r e d a n d B . O . S é r a p h i n , S o l a r E n e r g y M a t e r . 2 ,
107 ( 1 9 7 9 ) .
17. R.N. Schmidt and K.C. Park, Appl. Opt. 4, 917 (1965).
18. J.A. Thornton and J.L. L a m b , Thin Solid Films 9 6 , 175 (1982).
19. G . D . Pettit, J . J . C u o m o , T . H . D i S t e f a n o a n d J . M . W o o d a l l , I B M J . R e s .
D e v . 2 2 , 3 7 2 (1978).
20. G . L . H a r d i n g a n d M . R . L a k e , S o l a r E n e r g y M a t e r . 5, 4 4 5 ( 1 9 8 1 ) .
21. G . A . N i k l a s s o n a n d H . G . C r a i g h e a d , J. A p p l . P h y s . 5 4 , 5 4 8 8 ( 1 9 8 3 ) .
22. F . S i m o n i s , M . v a n d e r Leij a n d C . J . H o o g e n d o o r n , S o l a r E n e r g y M a t e r . 1
221 ( 1 9 7 9 ) .
23. G.B. Smith, R.C. McPhedran and G.H. Derrick, Appl. Phys. A 3 6 , 1 9 3
(1985).
24. J . N . S w e e t , R . B . Pettit a n d M . B . C h a m b e r l a i n , S o l a r E n e r g y M a t e r . 1 0 ,
251 ( 1 9 8 4 ) .
25. C M . L a m p e r t a n d J . W a s h b u r n , S o l a r E n e r g y M a t e r . 1 81 ( 1 9 7 9 ) .
26. G.E. M c D o n a l d , Solar Energy 1 7 , 1 1 9 (1975).
27. K.J. Cathro, Metal Finishing 76, (10), 57 (1978).
28. B . C a r l s s o n , e d i t o r , Accelerated Life Testing of Solar Energy Materials:
Case Study of some Selective Solar Absorber Coatings for DHW-systems,
I E A S H C T e c h n i c a l R e p o r t (to b e p u b l i s h e d ) .
29. J.C.C. F a n a n d S.A. S p u r a , A p p l . P h y s . Lett. 3 0 , 5 1 1 (1977).
30. Â . A n d e r s s o n , O . H u n d e r i a n d C . G . G r a n q v i s t , J . A p p l . P h y s . 51 7 5 4 (1980).
31. M . U c h i n o , S. A s o , S. H o z u m i , H . T o k u m a s u a n d Y . Y o s h i o k a , M a t s u s h i t a
Electr. I n d . N a t l . T e c h n . R e p . 2 5 , 9 9 4 ( 1 9 7 9 ) .
32. S. T s u d a a n d Y . A s a n o , B e l g . - N e d . T i j d s c h r . O p p e r v l a k t e t e c h n . M e t . 2 2 , 3
(1978).
33. M. Lanxner and Z. Elgat, Proc. Soc. Photo-Opt. Instrum. Engr. 1272, 240
(1990).
34. J.J. M a s o n and T.A. Brendel, Proc. Soc. Photo-Opt. Instrum. Engr. 324,
139 ( 1 9 8 2 ) .
35. H.Y.B. Mar, R.E. Peterson and P.B. Zimmer, Thin Solid Films 3 9 , 95 (1976).
36. P.K. Gogna, K.L. Chopra and S . C Mullick, Energy Res. 4, 3 1 7 (1980).
37. S. C r a i g a n d G . L . H a r d i n g , T h i n S o l i d F i l m s 1 0 1 , 9 7 ( 1 9 8 3 ) .
38. Z . - C Yin, private communication.
39. A . R o o s , T. C h i b u y e a n d B . K a r l s s o n , S o l a r E n e r g y M a t e r . 7, 4 5 3 ( 1 9 8 3 ) ;
A . R o o s a n d B . K a r l s s o n , S o l a r E n e r g y M a t e r . 7, 4 6 7 ( 1 9 8 3 ) .
40. J.J. Mason, Proc. Soc. Photo-Opt. Instrum. Engr. 4 2 8 , 1 5 9 (1983).
41. U L V A C Corp., Tokyo, Japan.
42. W . C Cochran and J.M. Powers, Aluminium (Dusseldorf) 5 4 , 147 (1978).
43. S.W. Moore, Proc. Soc. Photo-Opt. Instrum. Engr. 3 2 4 , 1 4 8 (1982).
44. B . O r e l , I. R a d o c z y a n d Z . C r n j a k O r e l , S o l a r a n d W i n d T e c h n o l . 3 , 4 5 ( 1 9 8 6 ) ;
Z. C r n j a k O r e l , B . O r e l a n d A . K r a i n e r , P r o c . S o c . P h o t o - O p t . I n s t r u m . E n g r .
1272, 274 (1990).
45. U.Kh. Gaziev, Sh.A. Faiziev, V.V. Li and V.S. Trukhov, Geliotekh. 16, 30
(1980) [ A p p l . S o l a r E n e r g y 1 6 , 3 0 ( 1 9 8 0 ) ] .
46. F . G a r n i c h a n d E . S a i l e r , S o l a r E n e r g y M a t e r . 2 0 , 81 ( 1 9 9 0 ) .
47. M. O k u y a m a , K. Furusawa and Y. H a m a k a w a , Solar Energy 2 2 , 4 7 9 (1979).
48. G.A. Niklasson and C.G. Granqvist, J. Appl. Phys. 5 5 , 3382 (1984).
49. T . K . V i e n , C. S e l l a , J . Lafait a n d S. B e r t h i e r , T h i n S o l i d F i l m s 1 2 6 , 1 7 ( 1 9 8 5 ) .
50. T . S . S a t h i a r a j , R. T h a n g a r a j a n d O . P . A g n i h o t r i , S o l a r E n e r g y M a t e r . 1 8 , 3 4 3
(1989).
51. I.T. R i t c h i e a n d B . W i n d o w , A p p l . O p t . 1 6 , 1 4 3 8 ( 1 9 7 7 ) ; B . W i n d o w , S o l a r
Energy Mater. 2 , 3 9 5 (1980).
52. H.G. Craighead, Proc. Soc. Photo-Opt. Instrum. Engr. 4 0 1 , 3 5 6 (1983).
53. J.A. Thorton and J.L. L a m b , Thin Solid Films 8 3 , 3 7 7 (1981); Solar Energy
M a t e r . 9 , 4 1 5 (1984).
54. R . C . B a s t i e n , R . R . A u s t i n a n d T.P. P o t t e n g e r , P r o c . S o c . P h o t o - O p t . I n s t r u m .
E n g r . 1 4 0 , 1 4 0 (1978).
55. D . R . M c K e n z i e , A p p l . P h y s . Lett. 3 4 , 2 5 ( 1 9 7 9 ) ; T h i n S o l i d F i l m s 6 2 , 3 1 7
(1979).
56. H.G. Craighead and R.A. Buhrman, J. Vac. Sci. Technol. 1 5 , 2 6 9 (1978).
57. M . M a s t , K. G i n d e l e a n d M . K o h l , T h i n S o l i d F i l m s 1 2 6 , 3 7 ( 1 9 8 5 ) .
58. A . S c h e r e r a n d O.T. Inal, A p p l . O p t . 2 4 , 3 3 4 8 ( 1 9 8 5 ) .
59. A . S c h e r e r , O . T . Inal a n d R . B . Pettit, J . M a t e r . S c i . 2 3 , 1 9 3 4 ( 1 9 8 8 ) .
60. A . S c h e r e r , O . T . I n a l a n d R . B . Pettit, J . M a t e r . S c i . 2 3 , 1 9 2 3 ( 1 9 8 8 ) .
61. I.T. R i t c h i e , S.K. S h a r m a , J . V a l i g n a t a n d J . S p i t z , S o l a r E n e r g y M a t e r . 2 , 1 6 7
(1979/1980).
62. G . Zajac, G . B . S m i t h a n d A . I g n a t i e v , J . A p p l . P h y s . 5 1 , 5 5 4 4 ( 1 9 8 0 ) .
63. R . B . S t e p h e n s a n d G . D . C o d y , T h i n S o l i d F i l m s 4 5 , 19 ( 1 9 7 7 ) .
64. J . M . Bell, G . H . D e r r i c k a n d R . C . M c P h e d r a n , O p t . A c t a 2 9 , 1 4 7 5 ( 1 9 8 2 ) .
65. R.C. McPhedran, L.C. Botten, M.S. Craig, M. Nevière and D. Maystre, Opt.
Acta 2 9 , 289 (1982).
66. G.A. Niklasson, unpublished results.
67. M . B o r n a n d E . W o l f , Principles of Optics, 6th edition (Pergamon, Oxford,
1980).
68. J . C . M . G a r n e t t , P h i l o s . T r a n s . R . S o c . ( L o n d o n ) 2 0 3 , 3 8 5 ( 1 9 0 4 ) ; 2 0 5 , 2 3 7 (1906).
69. D.A.G. Bruggeman, Ann. Phys. (Leipzig) 24, 636 (1935).
70. J . M . W e a v e r , C. K r a f k a , D . W . L y n c h , a n d E . E . K o c h , Physics Data: Optical
Properties of Metals ( F a c h i n f o r m a t i o n s z e n t r u m E n e r g i e , P h y s i k ,
M a t h e m a t i k G m b H , K a r l s r u h e , 1 9 8 1 ) , V o l s . 18-1 a n d 1 8 - 2 .
71. E . D . P a l i k , e d i t o r , Handbook of Optical Constants of Solids ( A c a d e m i c ,
N e w York, 1985).
72. G.A. Niklasson, Proc. Soc. Photo-Opt. Instrum. Engr. 1272, 250 (1990).
73. P.B. Johnson and R.W. Christy, Phys. Rev. Β 9, 5056 (1974).
74. A . P . L e n h a m a n d D . M . T r e h e r n e , in Optical Properties and Electronic
Structure of Metals and Alloys, e d i t e d b y F . A b e l e s , ( N o r t h - H o l l a n d ,
A m s t e r d a m , 1 9 6 6 ) , p. 1 9 6 .
75. A . S . S i d d i q u i a n d D . M . T r e h e r n e , Infrared P h y s . 1 7 , 3 3 ( 1 9 7 7 ) .
76. T.S. Eriksson, A. Hjortsberg, G.A. Niklasson and C.G. Granqvist, Appl. Opt.
20,2742(1981).
77. A . G . M a t h e w s o n a n d H.P. M y e r s , P h y s . S c r i p ta 4 , 2 9 1 ( 1 9 7 1 ) .
78. H.J. H a g e m a n n , W . G u d a t a n d C . K u n z , D E S Y S R - 7 4 / 7 , M a y 1 9 7 4 .
79. T. Pavlovic and A. Ignatiev, Thin Solid Films 1 3 8 , 97 (1986).
80. A. Scherer and O.T. Inal, Thin Solid Films 1 0 1 , 311 (1983).
81. P . R . D o l l e y a n d M . G . H u t c h i n s , in Solar Optical Materials: Proc. Conf.
Oxford, U.K., 12-13 April 1988, e d i t e d b y M . G . H u t c h i n s , ( P e r g a m o n , O x f o r d ,
1988), p. 9 1 .
82. G.A. Niklasson and H.G. Craighead, Appl. Opt. 2 2 , 1 2 3 7 (1983).
83. G.A. Niklasson, D.E. Aspnes and H.G. Craighead, Phys. Rev. Β 3 3 , 5 3 6 3
(1986).
84. Β . C a r l s s o n , e d i t o r , Solar Materials Research and Development: Survey of
Service Life Prediction Methods for Materials in Solar Heating and Cooling
( S w e d i s h C o u n c i l for B u i l d i n g R e s e a r c h , S t o c k h o l m , 1 9 8 9 ) .
85. R . B . Pettit, S o l a r E n e r g y M a t e r . 8, 3 4 9 ( 1 9 8 3 ) .
86. M . Kôhl, K. Gindele and M. Mast, Solar Energy Mater. 16, 155 (1987).
87. M . K ô h l , Κ . G i n d e l e , U . F r e i a n d T. H à u s e l m a n n , S o l a r E n e r g y M a t e r .
19, 2 5 7 ( 1 9 8 9 ) .
88. M . G . H u t c h i n s , P . R . D o l l e y , K . G i n d e l e , M . K ô h l , U . F r e i , B . O . C a r l s s o n , S.
Tanemura, K.G.T. Hollands, A.J. Faber, P.A. van Nijnatten and E.
Mezquida, Proc. Soc. Photo-Opt. Instrum. Engr. 1016, 2 7 9 (1988).
89. A S T M S t a n d a r d Ε 8 9 1 - 8 2 , Annual Book of ASTM Standards, Vol. 12.02
(1986).
90. P . H . H o l l o w a y , K . S h a n k e r , R . B . Pettit a n d R . R . S o w e l l , T h i n S o l i d F i l m s 7 2 ,
121 ( 1 9 8 0 ) .
91. R . B . P e t t i t , J . N . S w e e t a n d R . R . S o w e l l , in American Society for Testing and
Materials, S p e c . T e c h n . P u b l . N o . 7 9 2 , p. 2 6 3 ( 1 9 8 3 ) .
92. B . K a r l s s o n , T. K a r l s s o n a n d C . - G . R i b b i n g , P r o c . S o c . P h o t o - O p t . I n s t r u m .
E n g r . 3 2 4 , 1 5 6 (1982).
93. F.P. F e h l n e r a n d N . F . M o t t , O x i d a t i o n o f M e t a l s 2 , 5 9 ( 1 9 7 0 ) .
94. K . R . L a w l e s s , R e p . P r o g r . P h y s . 3 7 , 2 3 1 (1974).
95. A T . F r o m h o l d , J r . , Theory of Metal Oxidation, (North-Holland,
Amsterdam, 1976), Vols. 1 and 2.
96. G. Salomonsen, N . N o r m a n , O. Lonsjo and T.G. Finstad, J. Phys. Condens.
Matter, i , 7843 (1989).
97. N . Cabrera and N.F. Mott, Rep. Progr. Phys. 1 2 , 1 6 3 (1948-49).
98. D.J. Y o u n g and M J . Dignam, J. Phys. C h e m . Solids 3 4 , 1235 (1973).
99. W . E . Campbell and U . B . T h o m a s , Trans. Electrochem. Soc. 9 1 , 623 (1947).
100. W . S c h e u b l e , Z. P h y s . 1 3 5 , 1 2 5 (1953).
101. H.-J. E n g e l l , K . H a u f f e a n d B . I l s c h n e r , Z . E l e k t r o c h e m . 5 8 , 4 7 8 ( 1 9 5 4 ) .
102. H . U h l i g , J . P i c k e t t a n d J . M a c n a i r n , A c t a M e t . 7, 111 ( 1 9 5 9 ) .
103. K . H a u f f e , L . P e t h e , R. S c h m i d t a n d S. R o y M o r r i s o n , J . E l e c t r o c h e m . S o c .
1 1 5 , 4 5 6 (1968).
104. M.J. G r a h a m and M. Cohen, J. Electrochem. Soc. 119, 879 (1972).
105. B . C . S a l e s a n d M . B . M a p l e , P h y s . R e v . Lett. 3 9 , 1 6 3 6 ( 1 9 7 7 ) ; B . C . S a l e s , M . B .
M a p l e a n d F . L . V e r n o n III, P h y s . R e v . Β 1 8 , 4 8 6 ( 1 9 7 8 ) .
106. D.J. Y o u n g and M . Cohen, J. Electrochem. Soc. 1 2 4 , 769 (1977).
107. K . S h a n k e r a n d P.H. H o l l o w a y , T h i n S o l i d F i l m s 1 0 5 , 2 9 3 ( 1 9 8 3 ) .
108. K. H a n e d a and A.H. Morrish, Nature 2 8 2 , 1 8 6 (1979).
109. A . J o h g o , E . O z a w a , H . I s h i d a a n d K. S h o d a , J . M a t e r . S c i . Lett. 6, 4 2 9 ( 1 9 8 7 ) .
110. S. S a k o , K . O h s h i m a a n d T. Fujita, J . P h y s . S o c . J a p a n 5 9 , 6 6 2 ( 1 9 9 0 ) .
Chapter 5
ENERGY-EFFICIENT WINDOWS:
PRESENT AND FORTHCOMING TECHNOLOGY
C.G. Granqvist
Physics Department
ABSTRACT
C u r r e n t r e s e a r c h a n d d e v e l o p m e n t offers i m p o r t a n t o p p o r t u n i t i e s for i m p r o v e d
e n e r g y efficiency o f a r c h i t e c t u r a l w i n d o w s . T h i s c h a p t e r c o v e r s t h e d e s i g n criteria
for different c l i m a t e s a n d r e v i e w s m e a n s to fulfill t h e s e criteria b y p r o p e r m a t e -
rials s e l e c t i o n . W e d i s c u s s g l a s s p r o p e r t i e s , t h e i m p o r t a n c e o f m u l t i p l e g l a z i n g ,
the m a n y uses of surface coated glass, and possibilities connected with materials
i n t e r p o s e d b e t w e e n g l a s s p a n e s . A m o n g the c o a t i n g s , w e treat t h o s e b a s e d o n
n o b l e m e t a l s a n d o n d o p e d o x i d e s e m i c o n d u c t o r s , b o t h o f w h i c h h a v e static
s p e c t r a l l y s e l e c t i v e p r o p e r t i e s , as w e l l as e l e c t r o c h r o m i c s - b a s e d a n d t h e r m o -
chromic coatings which enable a dynamic control of the throughput o f radiant
energy. T h e fascinating possibilities with electrochromic "smart w i n d o w s " are
p o i n t e d out. A n g u l a r - s e l e c t i v e c o a t i n g s are d i s c u s s e d b r i e f l y . N o v e l a n t i r e f l e c t i o n
c o a t i n g s m a k e it p o s s i b l e to b o o s t the t r a n s m i t t a n c e b o t h o f c o a t e d a n d u n c o a t e d
glass. Regarding materials interposed between the panes, the discussion includes
g a s e s a n d g a s m i x t u r e s , c o a t e d p l a s t i c foils, silica a e r o g e l s , p h o t o c h r o m i c p l a s t i c s ,
thermochromic cloud gels, and electrically switched liquid-crystal-based materials.
I. INTRODUCTION
S p a c e c o n d i t i o n i n g o f r e s i d e n t i a l a n d c o m m e r c i a l b u i l d i n g s a c c o u n t s for s u b s t a n -
tial p a r t s o f t h e a n n u a l e n e r g y c o n s u m p t i o n in m a n y c o u n t r i e s . F o r t h e c a s e o f
S w e d e n , this a m o u n t s to a b o u t 4 0 %. O n the o r d e r o f o n e s i x t h is r e q u i r e d to
offset h e a t l o s s e s t h r o u g h w i n d o w s , i.e., r o u g h l y 7 % o f t h e a n n u a l e n e r g y c o n -
s u m p t i o n is t i e d to f e n e s t r a t i o n p e r f o r m a n c e . It is b e l i e v e d that s i m i l a r n u m b e r s
a r e v a l i d for m a n y o t h e r c o u n t r i e s . H e n c e it is o b v i o u s t h a t w i n d o w p r o p e r t i e s
h a v e a s i g n i f i c a n t effect n o t o n l y o n v i s u a l a n d t h e r m a l c o m f o r t b u t a l s o o n
e n e r g y c o n s u m p t i o n at a g l o b a l l e v e l . T h e p u r p o s e o f this p a p e r is to r e v i e w
c u r r e n t r e s e a r c h a n d d e v e l o p m e n t o n m a t e r i a l s for e n e r g y efficient w i n d o w s a n d
to p o i n t o u t o p t i o n s in p r e s e n t a n d f o r t h c o m i n g t e c h n o l o g y . W e w i l l s h o w h o w
106
Energy-efficient Windows: Present and Forthcoming Technology 107
superior thermal insulation can be combined with good visual transmittance,

h o w o v e r h e a t i n g c a n b e a v o i d e d b y reflecting off t h e i n f r a r e d p a r t o f t h e s o l a r
s p e c t r u m , a n d h o w t o d a y ' s r e s e a r c h o n m a t e r i a l s for o p t i c a l m o d u l a t i o n m a y l e a d
t o t o m o r r o w ' s s m a r t w i n d o w s w h i c h w i l l b e a b l e to r e g u l a t e t h e t h r o u g h p u t o f
r a d i a n t e n e r g y in a c c o r d a n c e w i t h d y n a m i c n e e d s . E a r l i e r r e v i e w s o1n 5m a t e r i a l s
for e n e r g y6 - e7f f i c i e n t w i n d o w s h a v e b e e n g i v e n r e c e n t l y b y G r a n q v i s t " a n d
Lampert. '
W e consider only w i n d o w s c o m p o s e d o f two or m o r e panes of a transparent

m a t e r i a l ( n o r m a l l y g l a s s ) w i t h an i n t e r p o s e d s u b s t a n c e ( n o r m a l l y a g a s ) . T h e
f u n c t i o n o f t h e w i n d o w , in g e n e r a l t e r m s , is to t r a n s m i t a c o n t r o l l e d a m o u n t o f
l u m i n o u s r a d i a t i o n (for v i s i o n ) a n d solar r a d i a t i o n (for s p a c e h e a t i n g ) at a specific
- u s u a l l y m i n i m i z e d - h e a t transfer. T h e h e a t transfer c o m p r i s e s a d d i t i v e
c o n t r i b u t i o n s f r o m t h e r m a l r a d i a t i o n , c o n d u c t i o n in s o l i d s a n d g a s e s , a n d g a s
c o n v e c t i o n . T h e u b i q u i t o u s r a d i a t i o n is o f p a r t i c u l a r s i g n i f i c a n c e for at l e a s t four
r e a s o n s : (i) t h e m o s t f u n d a m e n t a l object o f a w i n d o w is to t r a n s m i t l i g h t , (ii)
r a d i a t i v e transfer often a c c o u n t s for a l a r g e fraction o f t h e h e a t l o s s , (iii) r a d i a t i v e
p r o p e r t i e s c a n b e c o n v e n i e n t l y m o d i f i e d b y thin c o a t i n g s a n d s u r f a c e t r e a t m e n t s
o n t h e g l a s s , a n d (iv) d y n a m i c c o n t r o l o f t h e r a d i a t i v e p r o p e r t i e s c a n b e a c h i e v e d
in s m a r t w i n d o w s . S e c t i o n II b e l o w l a y s t h e g r o u n d for a scientific d i s c u s s i o n o f
e n e r g y efficiency b y e x a m i n i n g t h e r a d i a t i o n in o u r s u r r o u n d i n g s . It w i l l b e
s h o w n t h a t l u m i n o u s , s o l a r a n d t h e r m a l r a d i a t i o n a r e c o n f i n e d to s p e c i f i c a n d
w e l l d e f i n e d w a v e l e n g t h i n t e r v a l s . A k e y c o n c e p t for e n e r g y efficiency is s p e c t r a l
s e l e c t i v i t y , i m p l y i n g that t h e r a d i a t i v e p r o p e r t i e s s h o u l d b e q u a l i t a t i v e l y different
for different w a v e l e n g t h r a n g e s so that, for e x a m p l e , it is p o s s i b l e to c o m b i n e
t r a n s m i t t a n c e o f l u m i n o u s r a d i a t i o n w i t h r e f l e c t a n c e (i.e., s u p p r e s s e d e m i s s i o n ) o f
thermal radiation. Section II also defines integrated quantities w h i c h g o v e r n the
r a d i a t i v e p e r f o r m a n c e , a n d d e f i n e s t h e g o a l s o n e s h o u l d a i m for b y p r o p e r
m a t e r i a l s s e l e c t i o n . S e c t i o n III c o n t a i n s s o m e n o t e s o n t h e o p t i c a l p r o p e r t i e s o f
s t a n d a r d w i n d o w g l a s s e s . T h i s i n f o r m a t i o n p r o v i d e s a b a s e l i n e for s u b s e q u e n t
d i s c u s s i o n s o f w a y s to i m p r o v e t h e e n e r g y efficiency. W e a l s o i n c l u d e s o m e d a t a
for p h o t o c h r o m i c g l a s s . S e c t i o n I V treats a v a r i e t y o f m e a n s for u s i n g thin s u r f a c e
c o a t i n g s to i m p r o v e t h e r a d i a t i v e p r o p e r t i e s o f g l a s s . After a p r i m e r o n l a r g e - s c a l e
c o a t i n g t e c h n o l o g i e s , w e g i v e a superficial d i s c u s s i o n o f v a r i o u s m a t e r i a l s o p t i o n s .
Then w e follow with m o r e elaborate accounts of spectrally selective noble-metal
based coatings, spectrally selective doped oxide semiconductor coatings, electro-
chromic coatings with electrically controlled transmittance, thermochromic
coatings with temperature dependent transmittance, angular-selective coatings,
a n d c e r t a i n n o v e l a n t i r e f l e c t i o n t r e a t m e n t s . S o far w e h a v e o n l y l o o k e d at w a y s to
modify the radiative properties. However, conduction and convection are
p o s s i b l e to c o n t r o l t h r o u g h t h e m a t e r i a l i n t e r p o s e d b e t w e e n t h e p a n e s . T h e s e
a s p e c t s a r e c o v e r e d in S e c . V . T h e m o s t r a d i c a l c o n t r o l is a c h i e v e d b y i n t r o d u c i n g
v a c u u m , in w h i c h c a s e b o t h c o n d u c t i v e a n d c o n v e c t i v e h e a t t r a n s f e r v a n i s h . L e s s
efficient, b u t m u c h e a s i e r to a c c o m p l i s h in p r a c t i c e , is to w o r k w i t h g a s e s w h i c h
y i e l d a l o w e r h e a t c o n d u c t i o n a n d a s m a l l e r c o n v e c t i o n t h a n air. C o n v e c t i o n c a n
b e p r e v e n t e d if t h e s p a c e b e t w e e n the p a n e s is b r o k e n u p i n t o l a y e r s or cells w i t h
d i m e n s i o n s n o l a r g e r t h a n a few m m . I f t h e cell sizes a r e m u c h l e s s t h a n t h e
w a v e l e n g t h s o f v i s i b l e l i g h t - w h i c h is t h e c a s e o f h i g h l y p o r o u s silica a e r o g e l - the
i n t e r p o s e d s o l i d m a t e r i a l c a n b e a l m o s t i n v i s i b l e . S e c t i o n V a l s o treats s o m e
m e a n s to a c c o m p l i s h v a r i a b l e t r a n s m i t t a n c e b y u s e o f p h o t o c h r o m i c p l a s t i c s ,
thermochromic cloud-gels, and liquid-crystal-based materials with electrically

c o n t r o l l e d o p a c i t y . S e c t i o n V I , finally, g i v e s a s u m m a r y o f t h e m a i n r e s u l t s a n d
a t t e m p t s s o m e p r e d i c t i o n s a b o u t t h e future o f e n e r g y efficient a r c h i t e c h t u r a l
windows.
It s h o u l d b e o b v i o u s f r o m t h e a b o v e s u r v e y o f t h e c o n t e n t s o f this c h a p t e r , that
t h e r e a r e a g r e a t m a n y w a y s t o i m p r o v e t h e e n e r g y efficiency o f w i n d o w s . T h i s
p a p e r d o e s n o t p u r p o r t to c o v e r all o f t h e m in detail. I n s t e a d w e f o c u s o n r e s e a r c h
a n d d e v e l o p m e n t w h i c h , i n t h e a u t h o r ' s v i e w , h o l d s p a r t i c u l a r p r o m i s e for t h e
future. T h u s t h e p r e s e n t a t i o n o f t h e p r o p e r t i e s o f s t a n d a r d w i n d o w g l a s s is brief,
w h e r e a s t h e t r e a t m e n t o f s u r f a c e c o a t i n g s - e s p e c i a l l y t h e e l e c t r o c h r o m i c o n e s - is
m o r e e l a b o r a t e . E c o n o m i c e s t i m a t e s r e l a t e d to n e w f e n e s t r a t i o n t e c h n o l o g y a r e
g i v e n o n l y at a f e w p l a c e s . T h e o n g o i n g r e s e a r c h o n w i n d o w s , a n d o n t h e
m a t e r i a l s r e q u i r e d for their e n e r g y efficiency, is v e r y v i g o r o u s a n d c a r r i e d o u t
w o r l d w i d e , a n d it s e e m s p r e m a t u r e to try to set d o w n c o s t s o f p r o d u c t s , s u c h as the
e a r l i e r m e n t i o n e d s m a r t w i n d o w , w h i c h a r e in e a r l y s t a g e s o f d e v e l o p m e n t a n d
for w h i c h n o g e n e r a l l y a g r e e d u p o n t e c h n o l o g y h a s b e e n e s t a b l i s h e d .
IL ENERGY EFFICIENCY IN DIFFERENT CLIMATES
A. Ambient radiation
T h e k e y to e n e r g y efficiency o f w i n d o w s lies in a c l e a r u n d e r s t a n d i n g o f t h e
r a d i a t i v e p r o p e r t i e s o f o u r n a t u r a l s u r r o u n d i n g s . T h e s e a r e i l l u s t r a t e d in F i g . 1
w i t h a c o m m o n l o g a r i t h m i c w a v e l e n g t h s c a l e o n t h e a b s c i s s a . T h e m o s t funda-
m e n t a l p r o p e r t y is that m a t t e r e m i t s r a d i a t i o n . Its c h a r a c t e r is c o n v e n i e n t l y
discussed b y starting from the ideal blackbody, w h o s e emitted spectrum - k n o w n
as t h e P l a n c k s p e c t r u m - is u n i q u e l y d e f i n e d if t h e a b s o l u t e t e m p e r a t u r e is k n o w n .
P l a n c k ' s l a w is a c o n s e q u e n c e o f t h e q u a n t u m n a t u r e o f e l e c t r o m a g n e t i c r a d i a -
tion. T h e r i g h t - h a n d p a r t o f F i g . 1 d e p i c t s P l a n c k s p e c t r a for t w o t e m p e r a t u r e s o f
p r a c t i c a l s i g n i f i c a n c e for w i n d o w s . T h e v e r t i c a l s c a l e d e n o t e s p o w3 e r per unit area
and wavelength increment (hence the queer-looking unit M W m ~ ) . T h e spectra
a r e b e l l - s h a p e d a n d c o n f i n e d to t h e 2 < λ < 5 0 μιη r a n g e , w h e r e λ s i g n i f i e s the
w a v e l e n g t h . T h e p e a k in t h e s p e c t r u m for 5 0 ° C lies at a s h o r t e r w a v e l e n g t h than
t h e p e a k in t h e s p e c t r u m for 0 ° C , w h i c h is a m a n i f e s t a t i o n o f W i e n ' s d i s p l a c e m e n t
l a w . A t r o o m t e m p e r a t u r e t h e p e a k o c c u r s at a b o u t 1 0 μιη. T h e r m a l r a d i a t i o n
f r o m a m a t e r i a l is o b t a i n e d b y m u l t i p l y i n g t h e P l a n c k s p e c t r u m b y a n u m e r i c a l
factor - t h e e m i t t a n c e - w h i c h is less than u n i t y . In g e n e r a l , t h e e m i t t a n c e is
wavelength dependent.
T h e s o l i d c u r v e in the left-hand p a r t o f F i g . 1 r e p r o d u c e s a s o l a r s p e c t r u m for

r a d i a t i o n that h a s p a s s e d p e r p e n d8i9 cularly through the earth's atmosphere under
t y p i c a l c l e a r w e a t h e r c o n d i t i o n s . ' T h e c u r v e h a s a b e l l s h a p e c o r r e s p o n d i n g to
t h e s u n ' s s u r f a c e t e m p e r a2t u r e ( ~ 6 0 0 0 ° C ) . T h e i n t e g r a t e d a r e a u n d e r t h e c u r v e is
a p p r o x i m a t e l y 1 0 0 0 W n r ; this is the l a r g e s t p o s s i b l e p o w e r d e n s i t y o n a s u r f a c e
o r i e n t e d p e r p e n d i c u l a r to t h e s u n in t h e p r e s e n c e o f a t m o s p h e r i c c l a m p i n g . S o l a r
r a d i a t i o n is s e e n t o b e c o n f i n e d t o t h e 0.3 < λ < 3 μ ι η r a n g e . T h e m i n i m a in the
solar spectrum are caused b y atmospheric absorption, m a i n l y b y water vapour,
1 1 11 1
ι— I 1 TT
3
(GW/m ) Relative luminous
efficiency of the e y e Blackbody
h-0.5
HP ν ^ — z^Sfc o-
J L - J . I I. . . .I L _ J • . I
0.2 0.5
1 2 5 10 20 50
W a v e l e n g t h (μιη)
Fig. 1. S p e c t r a for b l a c k b o d y r a d i a t i o n at t w o t e m p e r a t u r e s ,
s o l a r r a d i a t i o n that h a s p a s s e d t h r o u g h t h e e a r t h ' s
atmosphere, and relative sensitivity of the h u m a n eye.
c a r b o n d i o x i d e , a n d o z o n e . A n i n t e r e s t i n g f e a t u r e , w h i c h is n o t i l l u s t r a t e d in F i g .
1, is t h a t t h e t r a n s m i t t a n c e t h r o u g h t h e a t m o s p h e r e c a n b e l a r g e in t h e 8 < λ < 13
μ ι η r a n g e , p r o v i d e d t h a t t h e h u m i d i t y is m o d e r a t e l y l o w . T h u s s o m e t h e r m a l
r a d i a t i o n c a n g o a l m o s t u n p e r t u r b e d f r o m an o b j e c t a t g r o u n d l e v e l i n t o s p a c e , 2
w h i c h g i v e s a s o u r c e o10 f p a s s i v e c o o l i n g w i t h a p o w e r d e n s i t y o f a b o u t 1 0 0 W m ~ at
a m b i e n t t e m p e r a t u r e as w e r e t u r n to in t h e final c h a p t e r o f this b o o k . T h e fact
t h a t t h e s u n s u b t e n d s a s m a l l e l e m e n t o f s o l i d a n g l e , w h o s e p o s i t i o n in t h e
h e a v e n s is p r e c i s e l y k n o w n for e a c h g e o g r a p h i c a l l o c a t i o n a n d for e a c h t i m e ,
o p e n s possibilities to exploit surfaces with strongly angular-dependent properties.
T h e d a s h e d c u r v e in t h e left-hand p a r t o f F i g . 1 s h o w s t h e r e l a t i v e s p e c t r a l
s e n s i t i v i t y o f t h e h u m a n e y e i n its l i g h t - a d a p t e d ( p h o t o p i c ) s t a t e . T h e b e l l - s11 haped
c u r v e e x t e n d s a c r o s s t h e 0.4 < λ < 0.7 μ ι η i n t e r v a l w i t h its p e a k at 0.555 μ ι η . In
its d a r k n e s s - a d a p t e d ( s c o t o p i c s t a t e ) , t h e e y e ' s s e n s i t i v i t y is d i s p l a c e d a b o u t 0 . 0 5 μιη
t o w a r d s s h o r t e r w a v e l e n g t h s . P h o t o s y n t h e s i s o p e r a t e s w i t h w a v e l e n g t h s in t h e
s a m e r a n g e as t h o s e 1 for13
2t h e h u m a n e y e , w h i c h is o f o b v i o u s r e l e v a n c e for g r e e n -
house applications. '
B. W h a t is E n e r g y Efficiency?
A n e n e r g y efficient w i n d o w is a d e v i c e c a p a b l e o f p r o v i d i n g g o o d l i g h t i n g d u r i n g
the d a y a n d g o o d t h e r m a l c o m f o r t b o t h d u r i n g d a y a n d n i g h t at m i m i m u m
d e m a n d o f p a i d e n e r g y . T h e r m a l c o m f o r t i m p l i e s t h a t o v e r h e a t i n g as w e l l as
e x c e s s i v e c o o l i n g s h o u l d b e a v o i d e d , that d r a u g h t s h o u l d b e s m a l l , e t c . T h u s
e n e r g y e f f i c i e n c y i n v o l v e s c o n t r o l o f r a d i a t i v e i n f l o w , a n d o f h e a t l o s s e s d u e to
radiation, conduction and convection. T h e radiative c o m p o n e n t to energy
e f f i c i e n c y is c o n v e n i e n t l y d i s c u s s e d w i t h r e f e r e n c e to t h e a b o v e m e n t i o n e d
a m b i e n t r a d i a t i o n . It is s u i t a b l e to m a k e a s e p a r a t i o n i n t o t h e r e q u i r e m e n t s
imposed b y a warm, a cold, and a temperate climate.
In a warm c l i m a t e it is f r e q u e n t l y t h e c a s e t h a t t h e s o l a r e n e r g y w h i c h e n t e r s
t h r o u g h t h e w i n d o w s a n d is a b s o r b e d in t h e r o o m c a u s e s o v e r h e a t i n g . S p a c e
c o n d i t i o n i n g t h e n r e q u i r e s air c o o l i n g e q u i p m e n t . It is c l e a r l y e n e r g y effective to
h a v e "solar c o n t r o l " w i n d o w s w h i c h b l o c k the infrared p a r t o f t h e s p e c t r u m (0.7 <
λ < 3 μιη) w i t h o u t e x c e s s i v e l o w e r i n g o f t h e l u m i n o u s t r a n s m i t t a n c e ( 0 . 4 < λ < 0.7
μιη). F r o m t h e s p e c t r a l d i s t r i b u t i o n o f s o l a r e n e r g y it is i n f e r r e d that, in p r i n c i p l e ,
it is p o s s i b l e to exclude about half of the solar energy at no decrease in luminous
transmittance. Another approach regards angularly dependent transmittance and
is b a s e d o n t h e fact t h a t t h e l u m i n o u s t r a n s m i t t a n c e t h r o u g h w i n d o w s u s u a l l y h a s
to b e l a r g e o n l y for n e a r - h o r i z o n t a l lines-of-sight, w h e r e a s t h e s u n is far a b o v e the
h o r i z o n d u r i n g m o s t o f t h e t i m e w h e n o v e r h e a t i n g is a s e v e r e p r o b l e m . T h u s
having w i n d o w s with properly tailored angular dependence o f the transmittance
is c o n d u c i v e to e n e r g y efficiency. A n g u l a r s e l e c t i v i t y is o f i m p o r t a n c e for i n c l i n e d
w i n d o w s as e l a b o r a t e d o n b e l o w . A c o m b i n a t i o n o f s p e c t r a l s e l e c t i v i t y a n d
s t r o n g l y a n g u l a r d e p e n d e n t t r a n s m i t t a n c e c l e a r l y is t h e s u p e r i o r o p t i o n .
In a cold c l i m a t e a w i n d o w f r e q u e n t l y c a u s e s a n u n d e s i r e d l o s s o f e n e r g y , a n d
h e n c e s p a c e c o n d i t i o n i n g i n v o l v e s h e a t i n g . It is o b v i o u s t h a t e n e r g y - e f f i c i e n c y
hinges on a decrease of the heat losses. Convection can b e diminished b y use of
m u l t i p l y - g l a z e d w i n d o w s i n c o r p o r a t i n g o n e o r m o r e s l a b s o f e s s e n t i a l l y still g a s .
T h e h e a t transfer c a n b e further l o w e r e d b y d i m i n i s h i n g t h e t h e r m a l r a d i a t i o n . In
o r d e r to d e v e l o p a feeling for t h e o r d e r - o f - m a g n i t u d e i m p r o v e m e n t o n e c14 an
a c c o m p l i s h , w e r e p r o d u c e in F i g . 2 s o m e results o f a s t 1 u5d y b y R u b i n et 14 a l .
A n a l o g o u s d a t a h a v e b e e n r e p o r t e d b y K a r l s s o n et a l . R u b i n et a l . i n v e s t i g a t e d
w i n d o w s w i t h o n e , t w o , o r t h r e e p a n e s s e p a r a t e d b y air g a p ( s ) o f 1 2 . 7 m m . T h e
s u r f a c e s a r e d e s i g n a t e d b y c o n s e c u t i v e n u m b e r s , w i t h t h e o u t s i d e s u r f a c e l a b e l e d 1.
O n e o f t h e s u r f a c e s is a s s i g n e d a n e m i t t a n c e in t h e 0-85 % r a n g e , w h e r e t h e u p p e r
l i m i t refers to n o r m a l g l a s s , a n d t h e t h e r m a l c o n d u c t a n c e - i.e., t h e k - v a l u e - is
c o m p u t e_ d . 1T h e d a t a refer to a n o u t s i d e t e m p e r a t u r e o f - 1 8 ° C a n d a w i n d s p e e d o f
2 4 k m h . T h e u p p e r t w o c u r v e s s h o w that if t h e e m i t t a n c e o f o n e o f t h e surfaces
in a s i n g l e - p a n e w i n d o w is2 l o_w 1 e r e d , t h e r e is a m a r g i n a l d r o p in t h e k - v a l u e f r o m
its m a g n i t u d e o f - 6 W m ~ K for2n o r1m a l g l a s s . In t h e d o u b l e - g l a z e d2u n i1t , t h e
k - v a l u e c a n d r o p f r o m - 2 . 8 W m ~ K " for n o r m a l g l a s s to ~ 1.4 W m * K " w h e n
t h e e m i t t a n c e o f e i t h e r o f t h e s u r f a c e s f a c i n g t h e air g a p is b r o u g h t to z e2r o . F o r
triple g l a z i n g , the c o r r e s p o n d i n g i m p r o v e m e n t is f r o m 1.8 to 1.2 W m ~ K " l . it [
s
i m p o r t a n t to n o t e that all o f t h e s e i m p r o v e m e n t s d e a l w i t h r a d i a t i o n at λ > 3 μιη,
i.e., o u t s i d e t h e s o l a r r a n g e . O n e finds t h a t it is p o s s i b l e , in p r i n c i p l e , to improve
the thermal insulation of a double-glazed window by about a factor two at no
decrease in solar transmittance.
In a temperate c l i m a t e t h e r e is s o m e t i m e s a n e e d for p r e v e n t i n g e x c e s s i v e s o l a r
h e a t i n g , w h e r e a s at o t h e r t i m e s o n e w a n t s to let in as m u c h a s p o s s i b l e to p r o v i d e
free h e a t i n g . T h u s o n e w a n t s to h a v e a w i n d o w w h i c h e n a b l e s a d y n a m i c
throughput o f radiant energy. Using established technology, one can w o r k with
m e c h a n i c a l r e g u l a t i o n w i t h m o v a b l e s h a d e s , b l i n d s o r (roller) c u r t a i n s a n d m a n y
d e s i g n s a r e k n o w n ( s e e for e x a m p l e Refs. 16 a n d 1 7 ) . 1 H8o w e v e r a s u p e r i o r s o l u t i o n
to t h e r e g u l a t i o n is to i n v o k e c h r o m o g e n i c m a t e r i a l s , w h i c h offer t h e p o s s i b i l i t y
o f c h a n g i n g t h e i n f l o w o f l u m i n o u s a n d / o r s o l a r r a d i a t i o n in a c c o r d a n c e w i t h
d e m a n d s w h i c h c a n v a r y o v e r t h e d a y o r s e a s o n . D e v i c e s o f this t y p e a r e c a l l e d
s m a r t w i n d o w s ; this c o n c e p t , i n t r o d u c e d a f e w y e a r s a g o b y S v e n s s o n a n d
G r a n q v i s t , 19 s e e m s to h a v e g a i n e d g e n e r a l a c c e p t a n c e as a g e n e r i c t e r m . T h e
regulation can be user operated or automatic. A m o n g the m a n y conceivable
p o s s i b i l i t i e s w e m a y i m a g i n e a s y s t e m in w h i c h a t h e r m o m e t e r s e n s e s t h e i n d o o r
air a n d a c t i v a t e s a l o w - v o l t a g e electric p u l s e to t h e w i n d o w w h i c h sets its s o l a r
t r a n s m i t t a n c e to a d e s i r e d l e v e l . C h r o m o g e n i c f e n e s t r a t i o n is r e a d i l y c o m b i n e d
with g o o d thermal insulation through multiple glazing and low emittance. O n e
c o n c l u d e s , t h a t e n e r g y e f f i c i e n c y is tied to smart windows incorporating materials
which enable the throughput of radiant energy to be controlled between widely
separated limits.
1 I I '1 1 ' 1
6
' 1 ^ Single glass
5 -
1
1 4
ε
Φ
75 3 Double glass -
>
I
1
^
^6——-
^ 4 or5 Triple glass
1
0 ι I ι 1 1 , 1
0 20 40 60 80
Emittance (%)
Fig. 2. C o m p u t e d k - v a l u e s o f v a r i o u s w i n d o w d e s i g n s as
d e t a i l e d in the m a i n text. ( F r o m Ref. 1 4 ) .
G o o d t h e r m a l i n s u l a t i o n i m p r o v e s e n e r g y efficiency a l s o in a m o r e i n d i r e c t w a y
t h a n t h r o u g h a l o w e r i n g o f t h e k - v a l u e . T o s e e this, o n e s h o u l d n o t e t h a t if the
i n s u l a t i o n is g o o d t h e s u r f a c e t e m p e r a t u r e o f t h e i n n e r g l a s s w i l l r e m a i n c l o s e to
that o f t h e i n d o o r air e v e n if t h e o u t d o o r air is v e r y c o l d . T h i s t e n d s to signifi-
c a n t l y d e c r e a s e t h e d o w n w a r d s s t r e a m o f c o l d air a l o n g t h e s u r f a c e o f t h e w i n d o w ,
w h i c h i m p r o v e s t h e c o m f o r t n o t i c e a b l y . It is i m p o r t a n t to o b s e r v e t h a t this
d r a u g h t is n o t c o n n e c t e d w i t h l e a k s at t h e w i n d o w f r a m e b u t is a n i n h e r e n t
p r o p e r t y o f a c o l d g a s . I f d r a u g h t is e l i m i n a t e d , t h e c o m f o r t t e m p e r t u r e c a n b e
d e c r e a s e d b y a f e w ° C , s p a c e utilization c a n b e m o r e r a t i o n a l t h a n if t h e a r e a at the
11 2 Materials Science for Solar Energy Conversion Systems
w i n d o w s must b e avoided, and heating installations can b e simplified. All of

t h e s e effects c l e a r l y c o n t r i b u t e to e n e r g y efficiency. W e p o i n t o u t , finally, that c o l d
d r a u g h t c a n b e e l i m i n a t e d b y e l e c t r i c a l l y h e a t2
e d w i n d o w g l a s s . C o m m e r c i a l triple-
g l a z e d u n i t s a l l o w i n g a p e a k l o a d o f 8 0 W n r at 2 2 0 V e x i s t o n t h e m a r k e t for
l i n e a r s i z e s u p to ~ 2 m . W h e t h e r o r n o t t h e y a r e e n e r g y - e f f i c i e n t d e p e n d s o n the
design o f the overall heating system.
C. Quantitative Performance Parameters for Energy-Efficient W i n d o w s
T h e idealized properties o f energy-efficient w i n d o w s , stated above, cannot b e

o b t a i n e d w i t h p r a c t i c a l m a t e r i a l s , a n d h e n c e t h e r e is a n e e d to specify s u i t a b l e
p e r f o r m a n c e p a r a m e t e r s w h i c h tell h o w far off a w i n d o w is f r o m c e r t a i n d e s i g n
goals. T h e radiative properties comprise the absorptance A, reflectance R,
t r a n s m i t t a n c e Τ a n d e m i t t a n c e E , e a c h s i g n i f y i n g a c e r t a i n fraction o f i n c i d e n t , o r
m a x i m u m e m i t t e d , r a d i a t i v e p o w e r . E n e r g y c o n s e r v a t i o n d i c t a t e s t h a t at e a c h
wavelength one has
Α ( λ ) + R(X) + Τ ( λ ) = 1, (1)
Ε(λ) = Α(λ). (2)
E q u a t i o n ( 2 ) , k n o w n as K i r c h h o f f s l a w , a p p l i e s to m a t t e r in t h e r m o d y n a m i c
equilibrium.
Pertinent wavelength-averaged radiative properties can be defined b y integrating

over the eye's sensitivity curve, which gives the luminous (lum) performance, a
t y p i c a l solar (sol) s p e c t r u m , a n d a b l a c k b o d y s p e c t r u m , w h i c h g i v e s t h e t h e r m a l
(therm) radiative performance. Quantitative data can b e obtained from the
general relation
Χγ(θ) = J dX 0y (λ) Χ ( λ , θ ) / / OX 0γ ( λ ) , (3)
w h e r e Χ is A , R , T , o r Ε ; θ is t h e a n g l e f r o m t h e n o r m a l for t h e i n c i d e n t o r e m i t t e d
r a d i a t i o n ; a n d γ d e n o t e s l u m , sol o r t h e r m . I n p r i n c i p l e , a n g l e - a v e r a g e d p r o p e r t i e s
c a n b e s p e c i f i e d b y i n t e g r a t i o n o v e r Θ.
For 0 i 9
umit is p r o p e r to u s e t h e s t a n d a r d l u m i n o u s efficiency f u n c t i o n (Fig. 1 ) , a n d
for 0 i o n e c a n u s e t a b u l a t e d s p e c t r a a p p r o p r i a t e to a c e r t a i n air m a s s ( A M ) . F o r
so
v e r t i c a l w i n d o w s it is often s u i t a b l e to u s e t h e A M 2 s p e c t r u m , c o r r e s p o n d i n g to
t h e s u n b e i n g 3 0 ° a b o v e t h e h o r i z o n . F o r otherm o n e h a s
5 1
0therm = Q λ ' [exp (ci/Xx) - l]" , (4)
16 2 2
w i t h c i = 3 . 7 4 1 8 χ 1 0 " W m , c = 1.4388 χ 1 0 " m K , a n d τ s i g n i f y i n g a b s o l u t e
2
t e m p e r a t u r e . I n m a n y c a s e s it is c o n v e n i e n t to s p e c i f y t h e n o r m a l ( 6 = 0 )
p r o p e r t i e s ; to g a i n a s i m p l e n o t a t i o n w e t h e n o m i t the a r g u m e n t in t h e i n t e g r a t e d
o p t i c a l p r o p e r t y a n d w r i t e , for e x a m p l e , T i instead o f T i (0). H o w e v e r , the
um um
r a d i a t i o n o f i n t e r e s t for t h e r m a l i n s u l a t i o n t a k e s p l a c e for all d i r e c t i o n s w i t h i n a

h e m i s p h e r e ( S i e g e l a n d H o w e l l 1 9 8 1 ) , s o t h a t E herm s h o u l d b e o b t a i n e d from
t
π/2
^ therm = j d ( s i n 2Θ) E (5)
t hm(Θ).
e r
A d i s t i n c t i v e f e a t u r e o f t h e a m b i e n t r a d i a t i v e p r o p e r t i e s is t h e i r s p e c t r a l s e l e c -
t i v i t y , i.e., t h e i r c o n f i n e m e n t to w e l l - d e f i n e d a n d s o m e t i m e s n o n - o v e r l a p p i n g
w a v e l e n g t h i n t e r v a l s . T h u s it is p o s s i b l e to h a v e a w i n d o w w i t h a T i / T i
s o
s i g n i f i c a n t l y l e s s t h a n u n i t y , as d e s i r e d for a w a r m c l i m a t e , a l a r g e T i a n dum a sratio
mall
s o
Etherm as d e s i r ead for a c o l d c l i m a t e , a n d a v a r i a b l e T i
umo r T s i ot o g e t h e r w i t h a
s m a l l Etherm / s d e s i r e d for a t e m p e r a t e c l i m a t e .
In a n o n - e v a c u a t e d d o u b l e - g l a z e d w i n d o w , h e a t t r a n s p o r t is c o n n e c t e d w i t h r a d i a -
t i v e t r a n s f e r o n l y to r o u g h l y 5 0 % a n d t h e full k - v a l u e is c l e a r l y a m o s t s i g n i f i c a n t
p a r a m e t e r . It e m b r a c e s effects o f c o n d u c t i o n a n d c o n v e c t i o n in t h e s p a c e b e t w e e n
t h e p a n e s . T h e s e latter 22 a1
2s p e c t s o f h e a t transfer a r e n o t e l a b o r a t e d h e r e , a n d w e
refer to t h e l i t e r a t u r e ' for d e t a i l e d treatises.
ΙΠ. SOME NOTES ON THE TRANSMISSION THROUGH

WINDOW GLASS
A. Standard Window Glass
T h e p u r p o s e o f this s e c t i o n is to p r e s e n t a f e w s e l e c t e d o p t i c a l d a t a o n s t a n d a r d
w i n d o w g l a s s i n o r d e r to g i v e a b a s e l i n e for s u b s e q u e n t d i s c u s s i o n s o f m e a n s to
i m p r o v e t h e e n e r g y efficiency.
N o r m a l w i n d o w s a r e m a d e b y the float p r o c e s s in w h i c h t h e g l a s s is s o l i d i f i e d on a
b a t h o f m o l t e n tin. T h e u n i f o r m i t y a n d flatness o f this g l a s s a r e e x c e l l e n t . F i g u r e
3 illustrates s p e c t r a l t r a n s m i t t a n c e in the s o l a r r a n g e for t h r e e t y p e s o f float g l a s s .
It is s e e n that T i
umis l a r g e . T h e t r a n s m i t t a n c e in t h e i n f r a r e d a s w e l l as in t h e ul-
t r a v i o l e t a r e s i g n i f i c a n t a n d d e p e n d e n t o n the g l a s s t y p e . In t h e t h e r m a l infrared -
n o t s h o w n in F i g . 3 - g l a s s is v i r t u a l l y o p a q u e . T h e m a j o r d i f f e r e n c e a m o n g the
g l a s s t y p e s in F i g . 3 is their m e t a l o x i d e c o n t e n t . W i t h r e g a r d to e n e r g y efficiency,
its m o s t s a l i e n t i n f l u e n c e is to p r o d u c e a b r o a d a b s o r p t i o n b a n d c e n t e r e d at λ ~ 1
μιη. I f a m a x i m u m v a l u e o f T i is d e s i r e d , a l o w F e 2 0 3 c o n t e n t is p r e f e r r a b l e ; the
s o
u p p e r c u r v e in F i g . 3 refers to s u c h a g l a s s w h i c h h a s T i
um~ T s i o 9 1 %. T h e
m i d d l e c u r v e in F i g . 3 is v a l i d for a n o r m a l t y p e o f float g l a s s , w h i c h h a s T i
um« 8 7
% a n d T i « 7 8 %. T h e b o t t o m c u r v e , finally, s h o w s t h e t r a n s m i t t a n c e t h r o u g h a
s o
glass with a large metal oxide content. T h e absorption b a n d extends s o m e w h a t
i n t o t h e v i s i b l e a n d g i v e s a g r e e n i s h tint. T h i s g l a s s m a y b e s u i t a b l e for a v o i d i n g
e x c e s s i v e s o l a r h e a t i n g . It is c h a r a c t e r i z e d b y T i m ^ 7 2 % a n d T i ~ 4 7 %. T h u s
U s o
the T i / T i
s o umr a t i o is 0 . 6 5 , w h i c h s e e m s to b e a b o u t the l o w e s t v a l u e o n e c a n r e a c h
in glass coloured b y F e 2 0 3 or similar additives. S o m e of the absorbed energy will
l e a d to a h e a t i n g o f t h e g l a s s a n d a c o n c o m i t a n t r e e m i s s i o n o f t h e r m a l e n e r g y , s o
t h a t t h e total e n e r g y t r a n s m i s s i o n is l a r g e r t h a n T i , p a r t i c u l a r l y for a tinted g l a s s .
s o
F o r t h e n o r m a l float glass a c c o r d i n g to t h e m i d d l e c u r v e in F i g . 3 , t h e total e n e r g y

t r a n s m i s s i o n ( c a l c u l a t e d w i t h c e r t a i n a s s u m p t i o n s ) is 8 3 %.
1
1001 1 1 I ι *~Γ~7
-5 8 0 - \ Low F e 2 o / ~ ^ _
8 60- Il i \ Standard clear
Ito- \\\ \—/ -

- /// H i g h F e 20 3
°1 I ι I ι ι ι ι I ι I
0.3 0.5 1 2
Wavelength (pm)
Fig. 3. S p e c t r a l n o r m a l t r a n s m i t t a n c e for float g l a s s o f t h r e e
different q u a l i t i e s . S p e c i f i c a l l y t h e c u r v e s refer to 6 m m
F l a c h g l a s O p t i w h i t e ( u p p e r ) , 6 m m P i l k i n g t o n float g l a s s
(middle), and 4 m m Flachglas Flag Plus (lower).
W e n o w c o n s i d e r t h e r e f l e c t a n c e o f t h e g l a s s . In t h e s p e c t r a l r a n g e w h e r e t h e
a b s o r p t i o n is w e a k , a n d at n o r2m a l i n c2i d e n c e , e a c h a i r / g l a s s i n t e r f a c e h a s a
reflectance g o v e r n e d b y ( n - l ) / ( n + l ) , with η being the refractive index of the
g l a s s . I n p r a c t i c e η « 1.5, s o that e a c h interface p r o d u c e s ~ 4 % r e f l e c t a n c e . It is
inferred that T i
um< 9 2 % is v a l i d for a s i n g l e p a n e . T h e o v e r a l l t r a n s m i t t a n c e is
further d i m i n i s h e d b y m u l t i p l e g l a z i n g . In t h e t h e r m a l infrared,23t h e r e f l e c t a n c e is
l o w , w h i c h l e a d s to a h i g h e m i t t a n c e - in p r a c t i c e Etherm ~ 8 5 % .
L a m i n a t e d w i n d o w s m a y b e u s e d for safety a n d o t h e r r e a s o n s . T h i s g l a s s c o m -
prises an interlayer of tough and resilient polyvinyl butyral ( P V B ) s a n d w i c h e d
b e t w e e n t w o g l a s s p a n e s a n d b o n d e d u n d e r h e a t a n d p r e s s u r e . T h e m o s t salient
o p t i c a l effect o f t h e P V B lies in t h e u l t r a v i o l e t , w h i c h c a n b e a l m o s t c o m p l e t e l y
r e j e c t e d as a p p a r e n t f r o m Fig. 4.
B. Photochromic glass
A p h o t o c h r o m i c m a t e r i a l is c h a r a c t e r i z e d b y its o p t i c a l p r o p e r t i e s b e i n g a b l e to
change 2 r e v24
5e r s i b l y u p o n i r r a d i a t i o n . T h e p h e n o m e n o n is w e l l k n o w n b o t h in
g l a s s e s ' a n d o t h e r m a t e r i a l s . A s u b s t a n t i a l p h o t o c h r o m i c effect in g l a s s can b e
p r o d u c e d b y a d d i n g s p e c i a l i n g r e d i e n t s to the m e l t a n d b y s u i t a b l e m e l t i n g a n d
h e a t t r e a t m e n t p r o c e d u r e s . In p r i n c i p l e , it is p o s s i b l e to m a k e u s e o f i s o l a t e d
a b s o r p t i o n c e n t e r s in 2+t h e v i t r e o u s m a t r i x a n d p h o t o e l e c t r o n i c p r o c e s s e s ( s u c h as
the reduction of C d to C d + ) , a l t h o u g h it h a s as y e t b e e n difficult to p r e p a r e
Energy-efficient Windows: Present and Forthcoming Technology 11 5
g l a s s e s w h i c h2 a2
6l7l o w a sufficient n u m b e r o f c o l o u r / b l e a c h c y c l e s , i.e., w h i c h a r e
fatigue-free. / A n o t h e r , a n d m o r e p r a c t i c a l , a p p r o a c h to p h o t o c h r o m i c g l a s s e s
rests on i n h o m o g e n e o u s microstructures with phases o f photosensitivite
c o m p o u n d s r a n d o m l y dispersed in the vitreous matrix. Strong p h o t o c h r o m i c
effects c a n b e p r o d u c e d u s i n 2 g 2 4
5e t a l h a l i d e s - n o t a b l y w i t h s i l v e r a n d c o p p e r - as
m
light absorbing s u b s t a n c e s . ' Silver h a l i d e s y s t e m s h a v e r e a c h e d t h e b e s t
technical maturity and are considered next.
100 I ' I ' I ι I ι I
~ 80
Φ
ο
c
(ϋ 60
—
_
Float
glass /
/ PVB
thickness/ / /
II
6mm / 0.4mm^/ / /
ω 40 — 0.8mm-Xy /
- 1.5mm Ί η / γ
20
-
'
0.32
ι I
0.34
ι
0.36 0.38
.1;- 0.40
Wavelength (μπι)
Fig. 4 . S p e c t r a l n o r m a l t r a n s m i t t a n c e t h r o u g h 6 m m float
glass with and without a P V B laminate layer having
the shown thickness. Reproduced from commercial
information supplied by Monsanto Chemical C o m p a n y , U S A .
P h o t o c h r o m i s m b a s e d o n s i l v e r h a l i d e p a r t i c l e s is k n o w n in n u m e r o u s o p t i c a l
g l a s s e s , for e x a m p l e in t h e a l k a l i - a l u m o - b o r o2-5s i l i c a t e s , a l k a l i - b o r a t e s , l e a d - b o r a t e s ,
lanthanum borates, and alumo-phosphates. T h e alkali-alumo-boro-silicates are
m o s t widely used. T h e s e glasses are melted together with silver, chlorine and
b r o m i n e i o n s a d d e d to t h e o r d e r o f s e v e r a l t e n t h s o f a p e r c e n t b y m a s s . T h e
a m o u n t o f h2 a l o g e n i o n s e x c e e d s t h e a m o u n t o f s i l v e r i o n s . C u p r o u s i o n s to the
o r d e r o f 1 0 " % b y m a s s m u s t b e p r e s e n t in the g l a s s m e l t . E s s e n t i a l l y fatigue-free
p h o t o c h r o m i s m c a n e v o l v e w h e n s u c h a g l a s s is h e a t - t r e a t e d a b o v e t h e g l a s s
t r a n s i t i o n t e m p e r a t u r e for a s u i t a b l e t i m e , w h i c h c a n b e as l o n g as s e v e r a l h o u r s .
Silver halide particles containing s o m e C u + are then included in the glass matrix
via a c o m p l i c a t e d p h a s e s e p a r a t i o n p r o c e s s . T h e i r d i a m e t e r s h o u l d b e b e t w e e n 10
a n d 2 0 n m for m a x i m28 u m photochromism, m i n i m u m light scattering, and
acceptable d y n a m i c s .
For p r a c t i c a l p u r p o s e s , t h e o p t i c a l p r o p e r t i e s o f p h o t o c h r o m i c g l a s s a r e g o v e r n e d
b y t h e d a r k e n e d a n d c l e a r e d t r a n s m i t t a n c e a n d b y t h e d a r k e n i n g a n d c l e a r i n g rates.
T h e s e a r e d e p e n d e n t o n t h e g l a s s c o m p o s i t i o n , a n d a c l e a r e d t r a n s m i t t a n c e u p to
9 0 % , o r a d a r k e n e d t r a n s m i t t a n c e d o w n to 5 %, a r e p o s s i b l e . T h e p h o t o c h r o m i s m
is s o m e w h a t t e m p e r a t u r e d e p e n d e n t , a n d a t e m p e r a t u r e r i s e y i e l d s e n h a n c e d
transmittance and dynamics. Figure 5 shows T i

umd u r i n g d a r k e n i n g a n d c l e a r i n g
for t w o different p h o t o c h r o m i c g l a s s e s at t w o t e m p e r a t u r e s . I r r a d i a t i o n is s e e n to
b r i n g d o w n Tium r a p i d l y . G e n e r a l l y , d a r k e n i n g to - 8 0 % o f t h e full r a n g e takes
p l a c e i n 1 m i n u t e , b u t a further m i n o r d a r k e n i n g is m e a s u r a b l e for t i m e s
e x c e e d i n g 1 h. C l e a r i n g in t h e a b s e n c e o f i r r a d i a t i o n p r o g r e s s e s s l o w e r t h a n
d a r k e n i n g a n d is i n c o m p l e t e e v e n after 1 h. F i g u r e 6 s h o w s t y p i c a l s p e c t r a l
t r a n s m i t t a n c e in t h e 0.35 < λ < 1.3 μιη r a n g e for a p h o t o c h r o m i c g l a s s in d a r k a n d
c l e a r s t a t e s . It is i n f e r r e d that t h e p h o t o c h r o m i c m o d u l a t i o n o f T i is s i g n i f i c a n t l y
s o
less t h a n for T i .
u m
T h e c o s t o f p h o t o c h r o m i c g l a s s is s u b s t a n t i a l l y h i g h e r t h a n for s t a n d a r d g l a s s
o w i n g t o t h e m a n u f a c t u r i n g p r o c e s s (rolling, d r a w i n g , f u s i n g ) a n d t h e s p e c i a l h e a t
t r e a t m e n t r e q u i r e d . T h e float p r o c e s s h a s n o t y e t b e e n u s e d for this p r o c e s s , as far
as w e k n o w . A t p r e s e n t ( 1 9 9 1 ) p h o t o c h r o m i c g l a s s is n o t p r o d u c e d for a r c h i t e c -
tural applications.
ι ι I ι ι . . , . ι I ι
6<H Darkening Clearing

Φ
ο
4θΗ
//
3
(Λ
Ο
NÂ25°C
c 20-
ε
3 Β 3°C
ι ι I ι ι ι ι I ι ι I ι
30 60 go 120
Time (minutes)
Fig. 5. L u m i n o u s transmittance vs. time during darkening and
clearing of two photochromic glasses (denoted A and B ) .
T h e g l a s s e s w e r e c l e a r e d o v e r n i g h t p r i o r to m e a s u r e m e n t s .
D a t a w e r e t a k e n at 2 0 ° C R e p r o d u c e d f r o m c o m m e r c i a l
information supplied by Corning Glass Works, U S A .
1 11 1
100Γ Ι Ι Ι — — Ι — — Ι —
Clear
80- / y ^ -
Φ
ο 60- / /
c
I / Dark
c 40- I /
20- //
01 I ι I ι I I « I
0.4 0.6 0.8 1.0 1.2
Wavelength (μητι)
Fig. 6. S p e c t r a l n o r m a l t r a n s m i t t a n c e for a p h o t o c h r o m i c g l a s s
in c l e a r a n d d a r k states. R e p r o d u c e d f r o m c o m m e r c i a l
information supplied by Corning Glass Works, U S A .
IV. COATINGS ON WINDOW GLASS
A. Coating Technology: A Primer
S u r f a c e c o a t i n g s w i t h t h i c k n e s s e s in the r a n g e 0.01 to 1 μιτι c a n m o d i f y t h e

r a d i a t i v e s u r f a c e p r o p e r t i e s o f g l a s s a n d t h e r e b y p r o d u c e e n e r g y efficiency. T w o
t e c h n i q u e s a r e in w i d e s p r e a d u s e for p r e p a r i n g s u c h c o a t i n g s o n t h e s c a l e o f s q u a r e
m e t r e s , v i z . s p u t t e r d e p o s i t i o n a n d s p r a y p y r o l y s i s . A d e t a i l e d d e s c r i p t i o n o f the
t e c h n o l o g i e s is n o t a t t e m p t e d h e r e , b u t their o p e r a t i n g p r i n c i p l e s a n d p r o s a n d
cons will b e outlined.
F i g u r e 7 a s h o w s t h e p r i n c i p l e o f s p u t t e r d e p o s i t i o n . T h e s u r f a c e c o a t i n g is p r e p a -
r e d i n s i d e a v a c u u m c h a m b e r w h i c h c o n t a i n s a n i n e r t g a s ( u s u a l l y a r g o n ) to a
p r e s s u r e o n the o r d e r o f o n e P a s c a l . T h e c h a m b e r h o l d s o n e o r m o r e s p u t t e r
c a t h o d e s w h o s e l o w e r p a r t s c o m p r i s e p l a t e s - k n o w n as t a r g e t s - o f t h e r a w m a t e r -
ial for the c o a t i n g . T h e g l a s s p a s s e s in a n d o u t o f t h e c h a m b e r b y m e a n s o f a l o a d -
l o c k s y s t e m , a n d is t r a n s p o r t e d a f e w c m b e l o w the targets. T h e d e p o s i t i o n p r o c e s s
i n v o l v e s a m a g n e t i c a l l y c o+n f i n e d s e l f - s u s t a i n e d p l a s m a s e t u p in s u c h a w a y that
energetic ions (usually A r ) b o m b a r d the target surface and dislodge atoms via
c o m p l e x m o m e n t u m transfer p r o c e s s e s . T h e s e a t o m s t r a v e l at h i g h s p e e d a n d
stick to t h e g l a s s , w h o s e s u r f a c e b e c o m e s u n i f o r m l y c o a t e d . U s e o f d i r e c t c u r r e n t
to p o w e r t h e p l a s m a is c u s t o m a r y a n d energy-efficient; it r e q u i r e s targets w i t h
s o m e e l e c t r i c a l c o n d u c t i v i t y . R a d i o f r e q u e n c y p o w e r i n g is a n a l t e r n a t i v e for n o n -
c o n d u c t i n g targets. D i e l e c t r i c thin films, for e x a m p l e o f o x i d e s , c a n b e p r e p a r e d b y
r e a c t i v e s p u t t e r i n g in t h e p r e s e n c e o f o x y g e n . A m u l t i l a y e r c o a t i n g is c o n v e n i -
e n t l y p r o d u c e d b y letting t h e g l a s s p a s s u n d e r s e v e r a l c a t h o d e s w h i c h , if c r o s s -
c o n t a m i n a t i o n is f e a r e d , c a n b e p l a c e d in s e p a r a t e c h a m b e r s .
F i g u r e 7 b illustrates s p r a y p y r o l y s i s as a t e c h n i q u e for m a k i n g s u r f a c e c o a t i n g s . A
s o l u t i o n , t y p i c a l l y c o n t a i n i n g a m e t a l c h l o r i d e or a c e t y l a c e t o n a t e , is t r a n s p o r t e d
a n d d i s p e r s e d t h r o u g h a s y s t e m o f n o z z l e s b y m e a n s o f a c a r r i e r g a s (air, n i t r o g e n ,
a r g o n , etc.) a n d , if r e q u i r e d , a r e a c t i v e g a s . A n a e r o s o l is t h u s f o r m e d p n e u m a t i -
cally a n d is s p r a y e d t o w a r d s t h e s u r f a c e o f a h o t g l a s s . T h e a e r o s o l b e c o m e s
v a p o u r i z e d b e f o r e r e a c h i n g the g l a s s , a n d h e n c e s p r a y p y r o l y s i s is a f o r m o f
c h e m i c a l v a p o u r d e p o s i t i o n . A t y p i c a l r e a c t i o n , o f l a r g e s i g n i f i c a n c e for w i n d o w
c o a t i n g s , is t h e h y d r o l y s i s o f tin c h l o r i d e to f o r m tin o x i d e , s h o w n s c h e m a t i c a l l y as
S n C U + 2 H 20 - > S n 0 2 + 4 HC1.
(a) S P U T T E R DEPOSITION
Sputter cathode
^ V a c u u m chamber
L Unheated glass
Sputter plasma
Fig. 7a.
(b) SPRAY P Y R O L Y S I S
Spray n o z z l e
Aerosol
Heated glass
Fig. 7 b . P r i n c i p l e s for sputter d e p o s i t i o n (a) a n d s p r a y p y r o l y s i s
(b) as m e a n s to c o a t surfaces o f g l a s s t r a n s p o r t e d as
i n d i c a t e d b y the h o r i z o n t a l a r r o w s .
S p u t t e r d e p o s i t i o n as w e l l as s p r a y p y r o l y s i s c a n b e c a r r i e d o u t b y fully a u t o m a t i c
e q u i p m e n t u p to w i d t h s o f s e v e r a l m e t r e s . S p u t t e r i n g is n o t a b l e for its v e r s a t i l i t y ,
p o s s i b i l i t i e s to a c c o m p l i s h p r o c e s s c o n t r o l , m u l t i l a y e r facility, a n d l o w s u b s t r a t e
h e a t i n g ( w h i c h m a k e s it p o s s i b l e to c o a t p l a s t i c w e b a n d o t h e r t e m p e r a t u r e s e n s i -
tive materials); on the negative side w e note that high investment costs m a y be
n e e d e d for e q u i p m e n t (of the o r d e r 10 M U S D for l a r g e - s c a l e a r c h i t e c t u r a l c o a -
t i n g s ) . S p r a y p y r o l y s i s l e n d s itself a l m o s t i d e a l l y to t h e p r o d u c t i o n o f e x t r e m e l y
d u r a b l e m e t a l o x i d e b a s e d c o a t i n g s b y d e p o s i t i o n o n t o t h e s u r f a c e o f a h o t g l a s s as
it c o m e s o u t f r o m the tin b a t h o f a float l i n e . M u l t i l a y e r d e p o s i t i o n is p o s s i b l e .
A m o n g t h e a l t e r n a t i v e p r a c t i c a l w i n d o w c o a t i n g t e c h n i q u e s t h e r e is n o t a b l y d i p
c o a t i n g , b y w h i c h t h e g l a s s is i m m e r s e d in a c h e m i c a l b a t h , w i t h d r a w n at a w e l l -
c o n t r o l l e d r a t e ( w h i c h g o v e r n s the c o a t i n g t h i c k n e s s ) , a n d h e a t t r e a t e d . F u r t h e r ,
v a c u u m e v a p o r a t i o n is a n o l d t e c h n i q u e w h i c h c a n b e u s e d for e x a m p l e to m e -
t a l l i z e p l a s t i c w e b . F o r r e s e a r c h o n thin f i l m s , t h e r e a r e m a n y o t h e r a l t e r n a t i v e
c o a t i n g t e c h n i q u e s w i t h specific a d v a n t a g e s a n d d i s a d v a n t a g e s . S u r f a c e c o a t i n g
t e c h n o l o g y is a v a s t subject, w h i c h is c o v e r e d to s o m e d e p t h in Refs. 2 9 - 3 3 .
B. Objects and Materials Options
A s a p r e a m b l e to a d i s c u s s i o n o f t h e specific c h a r a c t e r i s t i c s o f different c o a t i n g s for

e n e r g y - e f f i c i e n t w i n d o w s in s u b s e q u e n t s e c t i o n s , T a b l e 1 s u m m a r i z e s the g e n e r a l
g o a l s o f t h e c o a t i n g s , t h e p r i n c i p l e s o l u t i o n s to fulfill t h e s e , a n d t h e p e r t i n e n t
c o a t i n g m a t e r i a l s . A n a l o g o34
u s t a b l e s for w i n d o w s for a u t o m o t i v e a p p l i c a t i o n s
have been given recently.
D i m i n i s h e d s o l a r h e a t i n g is d e s i r e d for e n e r g y efficiency in a w a r m c l i m a t e .
A b o u t h a l f o f t h e s o l a r e n e r g y c o m e s as infrared r a d i a t i o n a n d c a n b e e x c l u d e d , in
p r i n c i p l e , w i t h n o effect o n T i . N o r m a l float g l a s s h a s a s i g n i f i c a n t t r a n s m i s s i o n
u m
at 0.7 < λ < 3 μιη (cf. F i g . 3 ) , a n d it is c l e a r l y effective to a p p l y a s u r f a c e c o a t i n g
w h o s e r e f l e c t a n c e is h i g h p r e f e r e n t i a l l y at λ > 0.7 μιτι. E x t r e m e l y thin c o n t i n u o u s
l a y e r s o f t h e f r e e - e l e c t r o n ( h e r e r e f e r r e d to as "noble") m e t a l s c o p p e r , g o l d , a n d
silver c a n b e u s e d for this p u r p o s e . T i
umc a n b e b o o s t e d b y e m b e d d i n g t h e m e t a l
l a y e r b e t w e e n h i g h - r e f r a c t i v e - i n d e x d i e l e c t r i c l a y e r s . A l e s s efficient a l t e r n a t i v e is
to start w i t h a tinted g l a s s - s u c h as t h e o n e r e p r e s e n t e d b y t h e l o w e r c u r v e in F i g . 3
- a n d p r e v e n t t h e r m a l r a d i a t i v e i n f l o w b y a c o a t i n g w i t h l o w E herm-
t
Diminished solar heating can also b e obtained b y combining high transmittance
a l o n g a n e a r - h o r i z o n t a l line-of-sight w i t h a l o w t r a n s m i t t a n c e for l i n e s - o f - s i g h t
w h i c h f o r m l a r g e a n g l e s to t h e h o r i z o n . F o r v e r t i c a l w i n d o w s this calls for c o a t -
i n g s w h o s e t r a n s m i t t a n c e falls off m o n o t o n i c a l l y w i t h i n c r e a s i n g a n g l e r e l a t i v e to
t h e s u r f a c e n o r m a l . F o r i n c l i n e d w i n d o w s , s u c h as g l a s s l o u v r e s , it is g e n e r a l l y an
a d v a n t a g e to h a v e o p t i c a l p r o p e r t i e s t h a t a r e a n g u l a r l y s e l e c t i v e . T h e m e a n i n g o f
a n g u l a r s e l e c t i v i t y is clarified in Fig. 8, w h i c h s h o w s l i g h t b e a m s i n c i d e n t at ± θ ]
a n d ± 0 2 to t h e s u r f a c e n o r m a l o f a p l a t e s u c h as a c o a t e d g l a s s w i n d o w . T h e trans-
m i t t a n c e v a l u e s c o r r e s p o n d i n g to ± θ ι a n d ± 0 2 a r e d e n o t e d T + j a n d T , r e s p e c t i -
± 2
v e l y ; t h e n o r m a l t r a n s m i t t a n c e is d e n o t e d T . A n g u l a r s e l e c t i v i t y refers to t h e
0
p r o p e r t y o f h a v i n g different t r a n s m i t t a n c e for l i g h t o f e q u a l a n g l e o f i n c i d e n c e o n
e i t h e r s i d e o f t h e n o r m a l . T h u s a m a t e r i a l w i t h Τ ( + θ ) < Τ(-θ) at a s p e c i f i c
w a v e l e n g t h is s a i d to h a v e a n g u l a r - s e l e c t i v e t r a n s m i t t a n c e a t this w a v e l e n g t h .
T h e a n g u l a r s e l e c t i v i t y c a n b e t a i l o r e d for different p u r p o s e s : for e x a m p l e o n e c a n
h a v e a m o n o t o n i e d e c r e a s e in t r a n s m i t t a n c e (e.g., T > T i > T > T_i > T-2), o r a
2 G
uniformly high transmittance on one side o f the normal and a uniformly low
t r a n s m i t t a n c e o n t h e o t h e r s i d e o f t h e n o r m a l (e.g., T « T i » T-i » T _ ) . In
58l a r s e l e c t i v i t y w i t h m e t2a l c o a t i n g s h a v i n2g o b l i q u e
p r a c t i c e , o n e c a n a c h i e v e a n3g u3
c o l u m n a r m i c r o s t r u c t u r e s , " as w i l l b e d i s c u s s e d in S e c . I V G .
T a b l e 1. G e n e r a l p r o p e r t i e s o f c o a t i n g s for e n e r g y - e f f i c i e n t w i n d o w s .
Goal Principle solution Coating material*
Diminished R e f l e c t a n c e at 0 . 7 < λ < 3 μ ι η "M"OTD/M/D

solar heating
Angular dependent trans- Oblique columnar metal
mittance
Thermal R e f l e c t a n c e at 3 < λ < 5 0 μιη D/M/D,

insulation Sn0 :F; In 03:Sn,
2 2
ZnO:Al,....
Dynamic Absorptance or reflectance L i W 0 , NiO H ,....

x 3 xy
radiation in e l e c t r o c h r o m i c m a t e r i a l in m u l t i l a y e r d e s i g n w i t h
control transparent ion conductor
R e f l e c t a n c e at 0 . 7 < λ < 3 μιη V0 -based

2
in t h e r m o c h r o m i c material
Higher A n t i r e f l e c t a n c e at λ = 0.55 μιη A10 F ,....

xy
transmittance
*M is A g , C u , A u (or A l ) ; D is B i 0 , l n 0 , S n 0 , T i 0 , Z n O o r Z n S .
23 23 2 2
G o o d t h e r m a l i n s u l a t i o n is i m p e r a t i v e in a c o l d c l i m a t e . O r d i n a r y g l a s s is
c h a r a c t e r i z e d b y a h i g h t h e r m a l e m i t t a n c e , a n d it is effective to a p p l y a s u r f a c e
c o a t i n g w i t h h i g h r e f l e c t a n c e at 3 < λ < 5 0 μπα. T w o different t y p e s o f c o a t i n g s c a n
b e u s e d t o p r o v i d e a l o w Etherm- an e x t r e m e l y thin m e t a l film e m b e d d e d b e t w e e n
h i g h - r e f r a c t i v e - i n d e x d i e l e c t r i c l a y e r s w i t h t h i c k n e s s e s c h o s e n s o as to m a x i m i z e
T i , a n d certain h e a v i l y d o p e d o x i d e s e m i c o n d u c t o r l a y e r s . A m o n g t h e latter w e
s o
note S n 0 doped by F or Sb, l n 0 doped by Sn, and Z n O doped b y Al.
2 2 3
A d y n a m i c t h r o u g h p u t o f r a d i a n t e n e r g y is h i g h l y d e s i r a b l e in a t e m p e r a t e
c l i m a t e , w h i c h calls for c o a t i n g s o f c h r o m o g e n i c m a t e r i a l s .1 3 T9w o i m p o r t a n t
a p p r o a c h e s 40 exploit materials exhibiting e l e c t r o c h r o m i s m ' and thermo-
chromism. A n electrochromic m a t e r i a l is c h a r a c t e r i z e d b y its o p t i c a l p r o p e r t i e s
b e i n g a b l e to s h o w a r e v e r s i b l e a n d p e r s i s t e n t c h a n g e u n d e r t h e a c t i o n o f an
e l e c t r i c field. T h e p e r t i n e n t m a t e r i a l s a r e t r a n s i t i o n m e t a l ( t u n g s t e n , n i c k e l , e t c )
o x i d e l a y e r s , w h o s e o p t i c a l p r o p e r t i e s a r e a l t e r e d b y v a r y i n g their c o n t e n t o f s m a l l
Angular selective transmittance
1 2
Fig. 8. Schematic illustrating the principle of angularly selective

transmittance.
+ +
m o b i l e i o n s ( H , L i , e t c ) . A d d i t i o n a l l a y e r s s e r v i n g as t r a n s p a r e n t i o n s t o r a g e , i o n
c o n d u c t o r , a n d e l e c t r i c c o n d u c t o r s a r e r e q u i r e d t o o , as w i l l b e d i s c u s s e d later. A
thermochromic material has optical properties which depend reversibly on the
t e m p e r a t u r e . VC>2-based c o a t i n g s c a n h a v e a t r a n s m i t t a n c e w h i c h d e c r e a s e s u p o n
a c e r t a i n t e m p e r a t u r e b e i n g e x c e e d e d a n d a r e h e n c e o f i n t e r e s t for a u t o m a t i c
r a d i a t i o n c o n t r o l . 41S u r f a c e c o a t i n g s w i t h g o o d p h o t o c h r o m i c p r o p e r t i e s h a v e b e e n
studied recently. P r e s s u r e - d e p e n d e n t o p t i c a l s w i t c h i n g in S m S c o a t i n g 4
s -42
3
p e r h a p s t r i g g e r e d b y t h e r m a l e x p a n s i o n effects - a l s o c a n b e m e n t i o n e d . '
E a c h a i r / g l a s s i n t e r f a c e y i e l d s a ~ 4 % r e d u c t i o n in T i
uma n d T s i .o Still l a r g e r
r e d u c t i o n s can b e c a u s e d b y surface c o a t i n g s , p a r t i c u l a r l y if t h e y c o n s i s t o f
m a t e r i a l s w i t h h i g h refractive i n d i c e s . A d e c r e a s e o f T i is u n d e s i r a b l e in c o l d
s o
a n d , p e r h a p s , t e m p e r a t e c l i m a t e s . A l a r g e Rium m a y l e a d to v i s u a l l y d i s t u r b i n g
effects o f v a r i o u s k i n d s . T h e r e m e d y for these p r o b l e m s is to a p p l y an anti-
reflection c o a t i n g . A s i n g l e l a y e r d e s i g n e d for a n t i r e f l 1 e c2
t i n g g l a s s (refractive i n d e x
n ) for 1 v i2s i b l e l i g h t s h o u l d h a v e a refractive i n d e x o f n / a n d a t h i c k n e s s o f
λ / ( 4 η / ) ~ 0.1 μιη. C e r t a i n n o v e l h i g h - r a t e - s p u t t e r e d m e t a l o x y f l u o r i d e c o a t i n g s
s e e m to 4 4 h6a v e a g r e a t p o t e n t i a l for a n t i r e f l e c t i n g c o a t e d a n d u n c o a t e d w i n d o w
glass. "
F o r c o m p l e t e n e s s w e n o t e that g l a s s c o a t i n g s can a l s o b e u s e d to a c h i e v e g l a r e a n d
c o l o u r , t h u s p r o d u c i n g i n t e r e s t i n g a r c h i t e c h t u r a l effects. A s a n e x a m p l e , Si
c o a t i n g s w i t h h i g h r e f r a c t i v e i n d i c e s c a n y ia e l d na d u r a b l e reflecting g l a s s . T h i s k i n d
o f c o a t i n g h a s a l m o s t n o effect o n Etherm d m a y , in fact, b e d e t r i m e n t a l to e n e r g y
efficiency.
G Noble-Metal Based Coatings
V e r y thin n o b l e - m e t a l c o a t i n g s a r e , at l e a s t in p r i n c i p l e , t h e s i m p l e s t s o l u t i o n for
reaching a significant short-wavelength transmittance c o m b i n e d with long-
w a v e l e n g t h reflectance. T h e b e s t o p t i c a l p r o p e r t i e s a r e o b t a i n 4 a7ble with copper,
silver, a n d g o l d , as s h o w n e x p e r i m e n t a l l y b y V a l k o n e n et a l . Alternative
m a t e r i a l s m a y b e T i N (Refs. 4 8 - 5 1 ) a n d a l u m i n i u m . T h i n s i l v e r c o a t i n g s s t a n d o u t
as t h e s u p e5r i5o2 3r m a t e r i a l o n a c c o u n t o f their l o w a b s o r p t i o n o f l u m i n o u s a n d solar
radiation. ' T h e o t h e r m e t a l s a r e c h a r a c t e r i z e d b y a b s o r p t i o n , w h i c h lies at
λ < 0.5 μπι for c o p p e r , g o l d a n d T i N ( h e n c e their c o l o u r ) , a n d at λ « 0.8 μπα for
a l u m i n i u m . C h e m i c a l a n d m e c h a n i c a l r u g g e d n e s s is a critical i s s u e for all n o b l e -
m e t a l b a s e d w i n d o w c o a t i n g s , a n d r e s u l t s o f l a b o r a t o r y e x p e r i m e n t s a n d field tests
d i c t a t e that t h e c o a t i n g s b e u s e d o n l y o n g l a s s surfaces facing t h e g a s e n c l o s u r e ( s )
i n h e r m e t i c a l l y s e a l e d m u l t i p l5
y - g5
46l a z e d units. T h e r e s u l t s o f s o m e d u r a b i l i t y tests
have been reported r e c e n t l y . " Reviews of metal based window coatings have
b e e n g i v e n in Refs. 4 , 5 7 - 5 9 .
T h e l i m i t i n g p e r f o r m a n c e o f a n o b l e - m e t a6 l b601a s e d s u r f a c e c o a t i n g is r e a d i l y
c o m p u t e d , u s i n g e s t a b l i s h e d t e c h n i q u e s , ' b y r e p r e s e n t i n g it as a p l a n e - p a r a l l e l
s l a b o f t h i c k n e s s t. T h e m e t a l is c h a r a c t e r i z e d b y p a r a m e t e r s - k n o w n as the o p t i c a l
c o n s t a n t s o r t h e c o m p l e x d i e l e c t r6
i2
c function - p e r t i n e n t to a u n i f o r m a n d w e l l -
sa a
crystallized atomic a r r a n g e m e n t . F i g u r e 593 s h o w s c o m p u t e d r e s u l t s o f T i , T i ,
u ms o
R l and E e r m function o f t for s i l v e r . It a p p e a r s that t = 5 n m y i e l d s T i
s o m um«
8 5 %, T i ~ 7 4 % a n d Etherm « 8 %. If p r a c t i c a l l y r e a l i z a b l e , a g l a s s w i t h s u c h a
s o
c o a t i n g w o u l d b e e x c e l l e n t for e n e r g y efficient w i n d o w s . U n f o r t u n a t e l y t h o u g h ,
e x t r e m e l y t h i n n o b l e - m e t a l films c a n n o t b e d e s c r i b e d as p l a n e p a r a l l e l s l a b s , as
w i l l b e c o n s i d e r e d next.
1001 I ι 1 J 1 1 1 1 Γ
s 1o
~ 8 0 - \ \ ^ / ^ "
5. 6 0 - \ \ /
§• 4 0 - / \ \Jlum -
* / Τ
W / ' s o l \ \
x S s
S> 2 0 - / \ \
/ Ε ^ ^»^ *« ^
S therm ^ ^ - ^s^ ^ ^ ^ ^
ol ι I*—ι 1 ι 1 ι 1 ι
0 10 20 30 40 50
T h i c k n e s s (nm)
Fig. 9. Integrated optical properties versus thickness computed
for an i d e a l i z e d p l a n e - p a r a l l e l silver s l a b . R e p l o t t e d from
Ref. 5 3 .
W h e n a m e t a l s u c h as c o p p e r , silver o r g o l d is d e p o s i t e d o n3t6o g l a s s , t h e c o a t i n g
goes through a series o f rather well defined growth stages T h e y are illustrated
s c h e m a t i c a l l y in F i g . 1 0 , w h e r e t h e p e r t i n e n t s t r u c t u r e s a n d t h i c k n e s s s c a l e s a r e
a l s o s h o w n . I n i t i a l l y , m e t a l l i c n u c l e i w i l l b e f o r m e d at c e r t a i n sites o n t h e g l a s s
s u r f a c e . C o n t i n u e d d e p o s i t i o n m a k e s t h e n u c l e i g r o w v i a s u r f a c e diffusion a n d
direct impingement. T h e metal islands thus formed u n d e r g o coalescence growth
so that larger and m o r e irregular islands appear. T h e growing coating then goes
t h r o u g h l a r g e - s c a l e c o a l e s c e n c e s o that a n e x t e n d e d m e t a l l i c n e t w o r k is f o r m e d .
Subsequently the voids between the metallic paths b e c o m e smaller and m o r e
regular. Finally, a uniform layer m a y b e formed. T h e corresponding structures
( w i t h m e t a l s h o w n as b l a c k ) a r e s k e t c h e d . T h e s i z e o f t h e i s l a n d s b e f o r e l a r g e - s c a l e
c o a l e s c e n c e is ~ 10 n m . C l e a r l y , t h e o r e t i c a l m o d e l s b a s e d o n a p l a n e - p a r a l l e l
s t r u c t u r e c a n b e c o r r e c t o n l y for t h e later g r o w t h s t a g e s . T h e o r e t i c a l m o d e l s o f the
o p t i c a l p r o p e r6t i 6
e4
5s a r e a l s o k n o w n for t h i c k n e s s e s w e l6l6 b e l o w l a r g e - s c a l e 61 7 - 7
c o a l e s c e n c e , ' w e l l a b o v e l a r g e s c a l e c o a l e s c e n c e , a n d at t h e c r o s s o v e r
E x c e p t at c r o s s o v e r , effective m e d i u m t h e o r i e s o f t h e k i n d i n t r o d u c e d i n t h e
c h a p t e r o n O p t i c a l P r o p e r t i e s o f I n h o m o g e n e o u s T w o - C o m p o n e n t M a t e r i a l s are
o f g r e a t v a l u e . T h e a b s o l u t e t h i c k n e s s s c a l e for t h e g r o w t h d e p e n d s o n m a n y
p a r a m e t e r s s u c h as t h e d e p o s i t e d s p e c i e s , t h e specific s u b s t r a t e m a t e r i a l , t h e
p r e s e n c e o f (artificially a d d e d ) n u c l e a t i o n c e n t e r s , t h e s u b s t r a t e t e m p e r a t u r e ,
v a c u u m c o n d i t i o n s , the p r e s e n c e o f e l e c t r i c fields, a n d o t h e r s . F i g u r e 1 0 s h o w s
t w o t y p i c a l s c a l e s referring to t h e d e p o s i t i o n o f g o l d o n t o g l a s s b y c o n v e n t i o n a l
evaporation + ( c e . ) a n d b y e v a p o r a t i o n in t h e p r e s e n c e o f an o p t i m i z e d flux o f
e n e r g e t i c A r i o n s (i.e., i o n - a s s i s t e d e v a p o r a t i o n , d e n o t e d i.a.) D e p o s i t i o n b y
s p u t t e r t e c h n o l o g y is b e l i e v e d to h a v e an i n t e r m e d i a t e t h i c k n e s s s c a l e . C u r r e n t l y
t h e r e is a t r e n d in s p u t t e r t e c h n o l o g y t o w a r d s t h e u s e o f " u n b a l a n c e d " m a g n e t r o n
c a t h o d e s , w h i c h g i v e a c o n t r o l l e d ion b o m b a r d m e n t o f the s u b s t r a t e . T h e m o s t
i m p o r t a n t c o n c l u s i o n is that n o b l e - m e t a l films a r e r e a s o n a b l y u n i f o r m o n l y at
t > 10 nm.
G r o w t h stage Structure T h i c k n e s s
(nm)
Metal nuclei
ce, i.a.
Irregular metal islands 3H
Large-scale coalescence
10J
3
Non-uniform film 6
Continuous metal film 20-^ 9
Fig. 10. Survey over growth stages, structures, and thickness
s c a l e s for thin g o l d films d e p o s i t e d o n t o g l a s s b y u s e o f
conventional evaporation ( c e . ) and ion-assisted
e v a p o r a t i o n (i.a.). ( F r o m Ref. 6 6 ) .
It is n o w p o s s i b l e to a p p r e c i a t e t h e s p e c t r a l o p t i c a l p r o p e r t i e s as a f u n c t i o n o f t for
films o f c o p p e r , silver, g o l d , etc., d e p o s i t e d47o n t o g l a s s a n d s i m i l a r m a t e r i a l s .
F i g u r e 1 1 , r e p l o t t e d f r o m V a l k o n e n et a l . , s h o w s s u c h d a t a at 0 . 3 5 < λ < 16 μιη
for c o n v e n t i o n a l l y e v a p o r a t e d s i l v e r l a y e r s . A t t = 6 n m o n e finds t h a t Rtherm is
l o w , a n d h e n c e Etherm is h i g h . T h i s c a n b e r e c o n c i l e d w i t h t h e o c c u r r e n c e o f a n
i s l a n d s t r u c t u r e ; if t h e l a y e r w e r e c o n t i n u o u s , Etherm i n s t e a d w o u l d h a v e b e e n
l o w as i n f e r r e d f r o m F i g . 9. It a p p e a r s that a c o n t i n u o u s s i l v e r l a y e r is f o r m e d
o n l y at t > 9 n m . T h e s e latter c o a t i n g s y i e l d a h i g h i n f r a r e d r e f l e c t a n c e c o m b i n e d
w i t h a s i g n i f i c a n t T i / a n d h e n c e t h e y a r e o f i n t e r e s t for e n e r g y efficient w i n d o w s .
u m
Expectedly, T i a n d T i d e c r e a s e w i t h i n c r e a s i n g t.
um s o
T h i s t e n d e n c y for thin n o b l e - m e t a l l a y e r s to f o r m a g g l o m e r a t e s t r u c t u r e s at s m a l l
t h i c k n e s s e s g i v e s a s i g n i f i c a n t l i m i t a t i o n to t h e i r p e r f o r m a n c e as w i n d o w
c o a t i n g s . I f h i g h infrared r e f l e c t a n c e is r e q u i r e d4 ,7o n e is c o n f i n e d to T j < 50% and
Tsol< 4 0 % 6 6 l a y e r s p r o d u c e d b y e v a p o r a t7i2o n . B y o p t i m i z e d i o n - a s sum
for isted
d e p o s i t i o n or special sputter t e c h n o l o g y one can reach T i
um~ T s i o< 60%. If a
still h i g h e r t r a n s m i t t a n c e is d e s i r e d o n e m u s t u s e a m u l t i l a y e r c o a t i n g .
1001 ι I ι ι Μ ι 1 ι I I I ι ιιι 1 1—ι \
2 50 - \ V
1 ~ \ V V ^ t=6nm
2 - \ \ V ?
ω - \\42\.
* ot _ J
100 w^mmm
ο - I// ^ //
t= 6 n m ^ ^ - — '
ΟΙ ι I ι ι ι 11 I ι ι I ι ι ι ι I I ι « I I
0.5 1 2 5 10 20 50
Wavelength (μπι)
Fig. 11. Spectral normal transmittance and near-normal
r e f l e c t a n c e m e a s u r e d for g l a s s c o a t e d w i t h s i l v e r t o t h e
shown thicknesses by means of convectional evapora-
tion. T h e r e f l e c t a n c e p e a k at λ « 11 μ ι η for t h e t h i n n e s t
coating stems from the glass substrate. Replotted from
Ref. 4 7 .
T h e l i m i t e d t r a n s m i t t a n c e t h r o u g h r e a s o n a b l y u n i f o r m n o b l e - m e t a l l a y e r s is
c a u s e d l a r g e l y b y reflection at t h e s u r f a c e s , a n d h e n c e it is p o s s i b l e to i m p r o v e the
t r a n s m i t t a n c e b y a d d i t i o n a l l a y e r s w h i c h act so as to a n t i r e f l e c t t h e m e t a l . O n e is
t h e n l e d to c o n s i d e r d i e l e c t r i c / m e t a l a n d d i e l e c t r i c / m e t a l / d i e l e c t r i c m u l t i l a y e r s .
D i e l e c t r i c s w i t h h i g h refractive i n d i c e s - s u c h as Βΐ2θ3, ΠΊ2Ο3, S n 0 2 , T1O2, Z n O a n d
Z n S - give the largest e n h a n c e m e n t o f the transmittance. B y selecting the thick-
n e s s e s o f t h e t h r e e - l a y e r c o n f i g u r a t i o n p r o p e r l y , o n e c a n o p t i m i z e for a w a r m
c l i m a t e ( m a x i m u m r e f l e c t a n c e for 0.7 < λ < 3 μπι) o r a c o l d c l i m a t e ( m a x i m u m
T o i ; m i n i m u m Etherm)- T h e o p t i m i z a t i o n c a n1 b55 e3 g u i d e d b y c o m p u t a t i o n s w h i c h
S
a s s u m e t h a t t h e m e t a l is a p l a n e - p a r a l l e l s l a b ' o6r6, m o r e r e a l i s t i c a l l y , that t h e
metal has thickness-dependent optical p r o p e r t i e s .
F i g u r e 1 2 d e p i c t s m e a s u r e d t r a n s m i t t a n c e s p e c t r a , c o m p i l e d f r o m different
s o u r c e s , o f c o a t i n g s o f the T i 0 / A g / T i 0 2 t y p e o n g l a s s . T h e s e d a t a a r e
2
c h a r a c t e r i s t i c for w h a t o n e c a n a c h i e v e b y e x p l o i t i n g t h e t h r e e - l a y e r d e s i g n ( s e e
a l s o Ref. 7 3 ) . It is i n f e r r e d that T i > 8 0 % a n d Etherm « 2 0 % a r e v a l i d for all
um
1001—ι I ι ι ι » I 1 1—1 I ι Μ 1 j 1 1—Γ-Γ
Φ - ίh \ \
5g -jl: \ \ g l a s s / T i 0 2/ A g / T i 0 2_
50-ί/·' \ \
I _jr \ \ 1mm/18/18/18nm_
co -jf \χ \ 1 mm/33/13/33nm -
5-1 \ · χ 4mm
f
I X
< K . _:
100"— ^'^^ZCillJi^'—
S / ./
S so-- / :/
— Λ· / */
*φ 7 '.
~\ 1 '/
\ J y
Ol • iVi ιιI Wavelength
I ι i l (μιη) i i l l
Fig. 12. S
0.5p e c t r a l 1n o r m a l 2t r a n s m i t t 5
a n c e a n10
d n e a r20
- n o r m a l r50
eflectance
m e a s u r e d for T i 0 2 / A g / T i 0 2 b a s e d c o a t i n g s o n g l a s s .
P e r t i n e n t t h i c k n e s s e s for t h e g l a s s a n d for t h e c o n s t i t u e n t
l a y e r s o f t h e c o a t i n g s a r e s h o w n . T h e s o l i d c u r v e s t e m s from
a c o m m e r c i a l l y p r o d u c e d s a m p l e ( G l a v e r b e l S u p e r l i g h t ) , the
d o t t e d c u r v e f r o m J a r v i n e n (Ref. 7 4 ) , a n d t h e d a s h e d c u r v e
f r o m F a n a n d B a c h n e r (Ref. 5 2 ) . T h e latter c o a t i n g w a s
o r i g i n a l l y d e v i s e d to i m p r o v e t h e l u m i n o u s e f f i c i e n c y o f
i n c a n d e s c e n t light s o u r c e s , b u t it is e q u a l l y a p p l i c a b l e a s a
w i n d o w c o a t i n g in a w a r m c l i m a t e .
c o a t i n g s . T h e d a s h e d c u r v e p e r t a i n s to a c o a t i n g w i t h m a x i m u m i n f r a r e d
r e f l e c t a n c e ; it y i e l d s T i ~ 5 0 % a n d R i ~ 4 2 %. T h e d o t t e d c u r v e c o r r e s p o n d s to
s o s o
Tsol^ 6 7 % a n d R i « 2 6 %. C l e a r l y , it is feasible to c o n s t r u c t c o a t i n g s for different
s o
c l i m a t e s s i m p l y b y a l t e r i n g t h e t h i c k n e s s e s . T h e s o l i d c u r v e w a s m e a s u r e d for an
o p t i m i z e d c o m m e r c i a l c o a t i n g o n float g l a s s o f t h e t y p e r e p r e s e n t e d b y t h e m i d d l e
c u r v e in F i g . 3. T h i s latter c o a t i n g y i e l d s T i
um« 8 7 % a n d T s i o-72%. C o a t i n g s o f
t h e t y p e T i 0 2 / T i N / T i 0 2 h a v e b e e n s t u d i e d in Refs. 5 0 , 5 1 , 5 6 . N o b l e - m e t a l b a s e d
t h r e e - l a y e r c o a t i n g s c a n b e p r o d u c e d , u s2ing large-scale automatic sputter
e q u i p m e n t , at a cost o f a b o u t 1 0 U S D / m in the c a s e o f T i C > 2 / A g / T i C > 2 , p r o v i d e d
t h a t t a r g e t u t i l i z a t i o n is o p t i m i z e d .
D. Doped Oxide Semiconductor Coatings
D o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s offer an a l t e r n a t i v e to t h e e a r l i e r d i s c u s s e d
noble-metal based coatings. T h e t w o classes o f coatings have specific advantages
and disadvantages. T h e semiconductor must be characterized b y a wide bandgap,
s o that is a l l o w s g o o d t r a n s m i s s i o n in t h e l u m i n o u s a n d s o l a r r a n g e s . F u r t h e r it
m u s t a l l o w d o p i n g to a l e v e l w h i c h m a k e s the m a t e r i a l m e t a l l i c a n d h e n c e
i n f r a r e d r e f l e c t i n g a n d e l e c t r i c a l l y c o n d u c t i n g . T h e m a t e r i a l s w h i c h a r e k n o w n to
b e u s e f u l a r e all o x i d e s b a s e d o n z i n c , c a d m i u m , i n d i u m , tin, t h a l l i u m a n d l e a d
a n d a l l o y s o f these. T h e r e q u i r e d d o p i n g is often a c h i e v e d b y t h e a d d i t i o n o f a
foreign element; particularly g o o d properties have been obtained with S n 0 2 : F ,
S n 0 2 : S b , I n 2 0 3 : S n a n d Z n O : A l . A n o t h e r p o s s i b i l i t y is to p r o v i d e d o p i n g v i a a
m o d e r a t e o x y g e n deficiency. If prepared properly, the m e n t i o n e d coatings can b e
v i r t u a l l y n o n - a b s o r b i n g for l u m i n o u s a n d s o l a r r a d i a t i o n . A s p e c i f i c a n d
i m p o r t a n t a d v a n t a g e o f t h e d o p e d o x i d e s e m i c o n d u c t o r s is their e x c e l l e n t
c h e m i c a l a n d m e c h a n i c a l d u r a b i l i t y , w h i c h a l l o w s their u s e o n g l a s s s u r f a c e s
e x p o s e d to the air. A s a n e x t r e m e e x a m p l e , w e n o t e t h a t p y r o l y t i c S n 0 2 : F c o a t i n g s
have 7 b5e e n s u c c e s s f u l l y a p p l i e d to t h e front s i d e o f "antifrost" w i n d s c r e e n s o n
cars. R e v i e w s o n d o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s a n d their u s e s as
t r a n s p a r e n t i n f r a r e d r e f l e c t o r s a n d t r a n s p a r e n t c o n d u c t o r s h a v e b e e n g i v e n in
Refs. 4 , 5 7 - 5 9 , 7 6 - 8 1 .
F i g u r e 13 illustrates t h e p r i n c i p l e s b y w h i c h t h e m e t a l l i c p r o p e r t i e s a r e r e a c h e d in
at l e a s t m o s t o f t h e d o p e d o x i d e s e m i c o n d u c t o r s . T h e u n d o p e d c r y s t a l (for
example Ιη2θβ) comprises a uniform arrangement of oxygen atoms and metal
a t o m s . W h e n d o p a n t a t o m s (tin) a r e a d d e d , t h e y r e p l a c e s o m e o f t h e i n d i u m . If
their d e n s i t y is sufficient, e a c h d o p a n t a t o m c a n b e s i n g l y i o n i z e d b y g i v i n g off an
e l e c t r o n w h i c h - t o g e t h e r w i t h o t h e r l i b e r a t e d e l e c t r o n s - m a k e s t h e m a t e r1i9
al - 3
21 -3
m e t a l l i c . T h e o n s e t o f m e t a l l i c p r o p e r t i e s o c c u r s at a d o p i n g l e v e l o f ~ 1 0 c m .
E l e c t r o n d e n s i t i e s u p to ~ 1 0 c m c a n b e a c h i e v e d b y m a x i m u m d o p i n g , w h i c h
i m p l i e s t h a t a f e w p e r c e n t o f t h e m e t a l a t o m s in t h e o x i d e h a v e b e e n s u b s t i t u t e d
by dopant atoms. F 22o r c -o m3p a r i s o n , m e t a l s s u c h as A g a n d A u h a v e a n e l e c t r o n
d e n s i t y o f ~ 6 χ 1 0 c m . A t t e m p t s to i n c r e a s e t h e d o p i n g still further l e a d s to the
f o r m a t i o n o f different a b s o r b i n g c o m p l e x e s w h i c h d i m i n i s h t h e t r a n s m i t t a n c e .
T h e infrared reflectance and the electrical conductance are governed b y the
s c a t t e r i n g w h i c h81t h e e l e c t r8
o n8s2
3u n d e r g o . It h a s r e c8e4n t l y b e e n s h o w n b y H a m b e r g
a n d G r a n q v i s t , J i n et a l . ' a n d H a i t j e m a et a l . t h a t for p r o p e r l y p r o d u c e d
h \ 2 0 3 : S n , Z n O : A l a n d S n 0 2 : F c o a t i n g s the s c a t t e r i n g is d o m i n a t e d b y t h e i o n i z e d
85
i m p u r i t i e s . T h e s a m e is t r u e for n o n - s t o i c h i o m e t r i c tin o x i d e . T h i s s c a t t e r i n g is
an unavoidable result of the doping, and h e n c e Fig. 13 provides a unified picture
of the basic processes which determine the infrared-optical and electrical
• •
properties of heavily doped oxide semiconductors.
,^- Oxygen
ο ο
ο • ο • - Indium
• ο
e" ^ Tin
• •
S η*
Fig. 1 3 .
ο Ο
O v e r s i m p l i f i e d c r y s t a l s t r u c t u r e a n d d o p i n g m o d e l for
I n 0 3 : S n . T h e a c t u a l c r y s t a l s t r u c t u r e o f Ι η Ο β is r a t h e r
2 2
c o m p l i c a t e d (cf. Ref. 8 6 ) .
A d e t a i l e d t h e o r e t i c a l u n d e r s t a n d i n g o f t h e d o p i n g m e c h a n i s m m a k e s it w o r t h -
w h i l e to p e r f o r m q u a n t i t a t i v e m o d e l l i n g o f t h e s p e c t r a l a n d i n t e g r a t e d o p t i c a l
p r o p e r t i e s as a f u n c t i o n o f c o a t i n g t h i c k n e s s a n d d o p i n g c o n c e n t r a t i o n (or, m o r e
p r e c i s e l y , e l e c t r o n d e n s i t y8)1. F i g u r e s 1 4 - 1 6 c o n t a i n d a t a for I n 2 0 3 : S n c o a t i n g s
prepared by evaporation. D i s r e g a r d i n g fine d e t a i l s , the r e s u l t s c a n a p p l y e q u a l l y
w e l l to o t h e r d e p o5s i8 t8i o2
n 87 t-e c h
8n o4l o g i e s a n d to a l t e r n a t i v e d o p e d o x i d e s e m i c o n -
ductor c o a t i n g s . ' ' F i g u r e 14 s h o w s s p e c t r a l t r a n s m i t t a n c e a n d 20 reflectance
21 3
for a 0 . 2 ^ m - t h i c k c o a t i n g w h o s e e l e c t r o n d e n s i t y n lies b e t w e e n 1 0 a n d
e
1 0 c m * . T h e20o n s e-3 t o f infrared r e f l e c t a n c e d e p e n d s critically o n n a n d it is s e e n
e
that n = 6 x l 0 c m y i e l d s h i g h T l a n d h i g h Rtherm (i.e., l o w E herm)- H i 2 g1h T -i 3
e s o t um
t o g e t h e r w i t h h i g h r e f l e c t a n c e at λ > 0.7 μιη w o u l d d e m a n d that n « 3 x 1 0 cm ,
e
b u t s u c h a d o p i n g l e v e l is i n a c c e s s i b l e , as r e m a r k e d a b o v e . O n e c o n c l u d e s that
d o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s a r e useful for e n e r g y efficient w i n d o w s to b e
a p p l i e d in a c o l d c l i m a t e b u t n o t in a w a r m c l i m a t e ( u n l e s s a n e l a b o r a t e m u l t i l a y e r
c o n f i g u r a t i o n is i n v o k e d ; cf. R e f . 8 8 ) .
I n t e g r a t e d o p t i c a l p r o p e r t i e s are i l l u s t r a t e d in F i g . 1 5 . It is i n f e r r e d that T i
um~ 8 0 %
is a t y p i c a l v a l u e , that T i d e c r e a s e s s i g n i f i c a n t l y w i t h i n c r e a s i n g n a n d / o r t, a n d
s o e
that a l o w Etherm c a n b e o b t a i n e d o n l y at t > 0.2 μπι. T h e i m p o r t a n t r e l a t i o n s h i p
b e t w e e n T i , Etherm a n d t is further e l a b o r a t e d in F i g . 1 6 . R e q u i r i n g that Etherm =
s o
0.2 r e s u l t s in a m a x i m u m T i o f ~ 7 8 % at t = 0.2 μιη. D e m a n d i n g a l o w e r Etherm
s o
l e a d s to a s i g n i f i c a n t d r o p in T i , w h i l e a l l o w i n g a l a r g e r E herm o n l y g i v e s a 20
-3 s o t
m i n o r r i s e in T i . It is c o n c l u d e d that 0 . 2 ^ m - t h i c k films w i t h 4 < n < 6 x l 0
s o e
c m y i e l d a n o p t i m u m p e r f o r m a n c e w i t h Etherm ~ 2 0 % a n d T i ~ 7 8 %. S u c h
s o
p r o p e r t i e s c a n b e a c h i e v e d in c o a t i n g s c o n s i s t i n g o f I n 2 0 3 : S n , Z n O : A l a n d S n O : F ,
and similar substances.
T h e r e q u i r e d c o a t i n g t h i c k n e s s e q u a l s a fraction o f the w a v e l e n g t h for v i s i b l e

light, a n d it f o l l o w s t h a t o p t i c a l i n t e r f e r e n c e effects m u s t b e g i v e n s e r i o u s
c o n s i d e r a t i o n . I n p a r t i c u l a r , m i n o r v a r i a t i o n s in t m a y c a u s e s i g n i f i c a n t
i r i d e s c e n c e , i.e., a r a i n b o w e x h i b i t i o n o f c o l o u r s at different p a r t s o f t h e c o a t e d
w i n d o w . S u c h effects a r e n o t i m p o r t a n t for n o b l e - m e t a l b a s e d l a y e r s o w i n g to
I ' I ι ι II| I | | I | M i l l ι I I ι
100
τ
f" :
£ 0.2pm. j • Ι .lnoO«:Sn
w
φ
υ \ \ N \ Π Η Β Ι substrate
£
c ~ il
50 — ml
\ \
\ \
* \
\
\
\
\
Ιι •τ 2 0_
3
E
* \ \
~ RL 10\ \6 \ 3 η =1 x 1 0 c m - -
\ \ \
-il ^. ν^ν—•
I ι I ι ι ι ιI . 1 l i l i l I ι
0.3 0.5 1 2 3 5 10 20 30 50
Wavelength (μιτι)
I ι I M i i | ι ι ι ι ι ι ι 111—r—ι—ι—π
100
R
/ f
S / A
I 50- / / f ^ ^ ^ ^ ~
ο — ^
II ι I M i l l ι I I ι I ι ι ι ιI ι I l i
0.3 0.5 1 2 3 5 10 20 30 50
W a v e l e n g t h (um)
Fig. 1 4 . Spectral normal transmittance (upper part) and reflectance
( l o w e r p a r t ) c o m p u t e d f r o m a q u a n t i t a t i v e m o d e l for t h e
optical properties of h ^ C ^ S n . The shown values of
electron density ( n ) and coating thickness were used.
e
(From Ref. 81).
t h e i r h i g h e r n "s w h i c h a l l o w t « 0.2 μιη. I r i d e s c e n t w i n d o w s a r e g e n e r a l l y

e
c o n s i d e r e d a e s t h e t i c a l l y u n p l e a s a n t , a n d it is c o n c l u d e d that e x t r e m e t h i c k n e s s
control m u s t b e exercised during practical manufacturing o f the coated glass. O n e
p o s s i b i l i t y to a v o i d i r i d e s c e n c e is t o w o r k w i t h t ~1 μιη. S u c h t h i c k c o a t i n g s y i e l d
n u m e r o u s i n t e r f e r e n c e - i n d u c e d p e a k s a n d d i p s o f t h e t r a n s m i t t a n c e a n d reflec-
t a n c e a c r o s s t h e 0.4 < λ < 0.7 μ ι η i n t e r v a l . A t h i c k n e s s - d e p e n d e n t d i s p l a c e m e n t o f
these peaks w o u l d not be recognized b y the eye, which h e n c e senses a uniform
colouration. H o w e v e r , the use o f a m u c h larger thickness than the o n e d e m a n d e d
for a l o w Etherm is c l e a r l y inefficient in t e r m s o f m a t e r i a l s u t i l i z a t i o n , c o a t i n g t i m e ,
a n d cost. Further, thick oxide s e m i c o n d u c t o r coatings can display s o m e light
s c a t t e r i n g , s o m e t i m e s r e f e r r e d to as h a z e . T h i s p h e n o m e n o n is a8s s90 9
ociated with
t h e o c c u r r e n c e o f l a r g e c r y s t a l l i t e s as w e l l as s u r f a c e r o u g h n e s s . '
1001 ι ι Γ-τ-τη 1 1 ι ι ι
2Cà lum
, Mum)
S ' * ^ Ν ? \ " ° "
I - . \ V 0.2 .
Ι SO- y 0.3 -
-J 1
ol 1 I ι ι ι I 1 ι ι ι I
Electron density (cm )
1001 ι ι 1—πτη j 1—rrj
m ) t (
I - 1 χ\\ H -
N 1 0 ,
1 ~ 50
1 \ \ "
~ -
2 ~
Hillllll
* Il
T s
3ln 0 :Sn \
23
substrate
o \Λ ~*Λ
o -
n
I - j ' \ 0.5 -
oLJ I ι ι ι I I . 3. . I
Electron density (cm" )
r 1
601 1 Γ 1—I Π 1 — ~H E
\ . therm , n
\ \ * Τ ΐ β ^ 2°3:Sn _
2 \ \ τ^^^M substrate
φ 40- \ \
I - ν\\ \ t( m)
H -
Ε 20- \ \ \ V/0.3
ol I I ι ι I I ι ιI
10 10 3 10
ι
20 1 ι
2 2
Electron density (cm" )

Fig. 15. Luminous transmittance (upper part), solar transmittance

(middle part) and thermal emittance (lower part) computed
f r o m a q u a n t i t a t i v e m o d e l for t h e o p t i c a l p r o p e r t i e s o f
I n 0 3 : S n . The used values of electron density and coating
2
t h i c k n e s s (t) a r e s h o w n . T h e s u b s t r a t e w a s r e p r e s e n t e d b y
p r o p e r t i e s p e r t i n e n t to p u r e S i 0 (i.e., a g l a s s w i t h n o F e 0
2 23
c o n t e n t ) . ( F r o m Ref. 8 1 ) .
1001 ι ι ι ι ι ι ι ι ι ι I
£ ~ ~
2
I " therm=°- 5
s so- — · -
g £ 0.20
ι ' J * — — —
I - -jr 21 3
0 1 5
-
» 60- * n e> 1 0 c m -
_] I ι I ι I ι l ι I ι
0 0.2 0.4 0.6
Film thickness (μιη)
Fig. 16. N o r m a l s o l a r t r a n s m i t t a n c e v s . c o a t i n g t h i c k n e s s for
three values of hemispherical thermal emittance com-
p u t e d for I n 0 : S n in the s a m e w a y as in F i g s . 1 4 a n d
23
15. T h e21 s h a d e3d a r e a refers to h y p o t h e t i c a l c o a t i n g s w i t h
n > 1 0 cm" . (From Ref. 81).
e
F i g u r e 1 7 s h o w s t r a n s m i t t a n c e a n d r e f l e c t a n c e s p e c t r a as m e a s u r e d for t h r e e
different d o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s . T h e c u r v e s s h o w r a t h e r h i g h T i ,
u m
m o d e r a t e l y h i g h T i , a n d i n d i c a t e l o w E herm- T h e u p p e r p a r t refers t o a810.41 μιη
s o t
t h i c k I n 0 : S n c o a t i n g p r e p a r e d for r e s e a r c h b y e v a p o r a t i o n t e c h n o l o g y . This
23
c o a t i n g m a t c h e s the t h e o r e t i c a l p r e d i c t i o n s for a n o p t i m i z e d m a t e r i a l v e r y w e l l .
T h e m i d d l e p a r t c o n c8e 8 r2
3n s a 0 . 3 0 μπ\ t h i c k Z n O : A l c o a t i n g p r e p a r e d for r e s e a r c h b y
sputter t e c h n o l o g y . ' B o t h o f t h e s e c o a t i n g s w e r e p u t o n C a F s u b s t r a t e s that a r e
2
t r a n s p a r e n t for 0.3 < λ < ΙΟμπι; t h e d a t a w o u l d h a v e b e e n v e r y s i m i l a r for c o a t i n g s
b a c k e d b y g l a s s . T h e b o t t o m p a r t w a s r e c o r d e d for a S n 0 : F c o a t i n g p r o d u c e d
2
c o m m e r i c a l l y b y s p r a y p y r o l y s i s o n t o 4 m m s t a n d a r d floatglass. T h e latter c o a t i n g
is c o n s i d e r a b l y t h i c k e r than the o t h e r t w o , as e v i d e n c e d b y t h e d e n s e l y s p a c e d
p e a k s i n t h e s p e c t r a . It h a s T i
um« 7 4 % , w h i c h is l o w e r t h a n for t h e I n 20 3: S n a n d
Z n O : A l c o a t i n g s , a n d T i ~ 7 7 %. C o m m e r c i a l p r o d u c t s w i t h s o m e w h a t b e t t e r
s o
d a t a h a v e b e c o m e a v a i l a b l e r e c e n t l y .73S o m e d a t a o n d o p e d S n 0 c o a t i n g s h a v e
2
been summarized by Karlsson et a l .
U l t r a v i o l e t r e j e c t i o n is o f i m p o r t a n c e for p r e v e n t i n g b l e a c h i n g o f t e x t i l e s ,
d e g r a d a t i o n o f p o l y m e r s , etc. C h o i c e o f p r o p e r g l a s s (Fig. 3 ) as w e l l a s l a m i n a t i o n
(Fig. 4 ) a r e i m p o r t a n t for this p u r p o s e . Z n O c o a t i n g s offer a n o t h e r p o s s i b i l i t y , as
1001 ι ι I ι ι ιιι ι ι ι I ι ι ii| I ι ι Γ
- U- V ι
J Τ ^\ 0.41 pm 1n 20 3:Sn
Γ \ / 1mm C a F 2 substrate -
v v
oLi_ ^ x / V J
S 1001
I : / v /
^ :
ο I / \ 0.30μιη ZnO:AI
5j 50— \ / 1 mm C a F 2 s u b s t r a t e -
I - Λ Λ " X -
t o b z ^ v ^ W V . :
φ ,
g 100Γ ^
m 4 m
S 5o_ / \ / floatglass
I ι ι I ι ι ι ιI I ι ι I ι ι ι ιI I . . I I
0.2 0.5 1 2 5 10 20 50
Wavelength (μηι)
Fig. 17. Spectral normal transmittance and near-normal reflectance
m e a s u r e d for h ^ C ^ - . S n o n 1 m m C a F , Z n O . A l o n 1 m m
2
C a F , a n d S n 0 : F o n 4 m m floatglass ( G l a v e r b e l C o m f o r t
2 2
G l a s s ) . C o a t i n g a n d s u b s t r a t e t h i c k n e s s e s a r e as g i v e n . P a r t l y
c o m p i l e d f r o m Refs. 8 1 - 8 3 .
s h o w n in F i g . 1 8 . It a p p e a r s that a 0.3 μιη thick Z n O l a y e r is sufficient for

a b s o r b i n g m o s t o f t h e u l t r a v i o l e t r a d i a t i o n w h i c h is o t h e r w i s e a b l e t o p a s s
o r d i n a r y floatglass. H e a v y d o p i n g , for e x a m p l e b y A l , shifts the a b s o r p t i o n to
smaller wavelengths, and the ultraviolet absorption b e c o m e s insignificant. 9 T h91
2i s
p h e n o m e n o n - k n o w n as a b a n d g a p shift - is t h e o r e t i c a l l y w e l l u n d e r s t o o d . '
C o a t i n g s b a s e d o n Ι η Ο β a n d S n 0 a r e n o t useful for u l t r a v i o l e t a b s o r p t i o n .
2 2
T a n d e m c o a t i n g s o f Z n O / Z n O : A l a r e a b l e to c o m b i n e l a r g e T i
9 93
4 uma n d T s i ow i t h l o w
Etherm a n d u l t r a v i o l e t rejection. C e 0 c o a t i n g s m a y b e a p p l i c a b l e for t h e s a m e
2
purpose. '
1
1001—ι—'— —ι—I—ι—ι—ι—ι—I—«—ι—«—r
£ ZnOiAI \
I "50
y /
Οι ι—ι ι ι 1 ι ι ι ι \ \ \ \ \
0.3 0.35 0.40 0.45
Wavelength (μηι)
Fig. 1 8 . S p e c t r a l n o r m a l t r a n s m i t t a n c e in t h e u l t r a v i o l e t m e a s u r e d
for 0.3 μ ι η thick Z n O a n d Z n O + 2 at.% A l c o a t i n g s o n 1 m m
CaF .
2
T h e c o s t for l a r g e - s c a l e d o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s is d e p e n d e n t o n
p r o d u c t i o n t e c h n o l o g y , as w e l l as m a t e r i a l , a n d is difficult to e s t i m a t e . W i t h
r e g a r d to t e c h n o l o g y , it s h o u l d b e p o i n t e d o u t that s e v e r a l g l a s s m a n u f a c t u r e r s
h a v e h a d s u c c e s s in their d e v e l o p m e n t o f S n 0 - b a s e d c o a t i n g s p r e p a r e d b y s p r a y
2
p y r o l y s i s d i r e c t l y o n t o t h e h o t g l a s s o n a float line. T h i s t e c h n o l o 2 gy holds promise
for v e r y i n e x p e n s i v e c o a t i n g s , h a v i n g c o s t s o f o n l y a f e w U S D / m . W i t h r e g a r d to
m a t e r i a l , w e n o t e that i n d i u m is m u c h m o r e s c a r c e a n d e x p e n s i v e t h a n z i n c a n d
tin. H e n c e I n 0 3 : S n c o a t i n g s s h o u l d b e u s e d o n l y w h e n t h e u l t i m a t e in e l e c t r i c a l
2
c o n d u c t i v i t y o r infrared r e f l e c t a n c e a r e r e q u i r e d . C a d m i u m a n d t h a l l i u m b a s e d
coatings m a y cause heath hazards.
E. Electrochromic Coatings
E l e c t r o c h r o m i s m is a m u l t i - f a c e t t e d p h e n o m e n o n w h i c h is w e l l k n o w n in
transition metal oxides based on tungsten, vanadium, nickel, m o l y b d e n u m ,
t i t a n i u m , i r i d i u m etc., a n d in n u m e r o u s o r g a n i c s u b s t a n c e s . T h e c h a n g e in t h e
o p t i c a l p r o p e r t i e s is c a u s e d b y t h e injection o r e x t r a c t i o n o f m o b i l e i o n s . A
m a t e r i a l that c o l o u r s u n d e r injection ( e x t r a c t i o n ) o f i o n s is r e f e r r e d to a s c a t h o d i c
( a n o d i c ) . A b s o r p t a n c e m o d u l a t i o n as w e l l as r e f l e c t a n c e m o d u l a t i o n a r e feasible.
E l e c t r o c h r o m i s m h a s b e e n s t u d i1 e d98s15i n0c0e the e a r l y 1 9 7 0 ' s for h i g h c o n t r a s t n o n -
emissive display a p p l i c a t i o n s . ' " S i n c e the m i d - 1 9 8 0 ' s , r e s e a r c h a n d
d e v e l o p m e n t o n t r a n s p a r e n t e l e c t r o c h r o m i c m a t e r i a l s a n d d e v i c e s for1 s1m 83a9r 1
t910
w i n d o w a p p l i c a t i o n s h a v e s o a r e d b o t h in a c a d e m i a a n d in i n d u s t r y . ' ' '
A n electrochromic coating must include several layers. Figure 19 sketches a basic

five-layer c o n f i g u r a t i o n w h i c h is c o n v e n i e n t for d i s c u s s i n g t h e o p e r a t i n g
p r i n c i p l e s . It c o m p r i s e s t w o o u t e r t r a n s p a r e n t e l e c t r i c a l c o n d u c t o r s , r e q u i r e d for
s e t t i n g u p a d i s t r i b u t e d e l e c t r i c field, a n e l e c t r o c h r o m i c l a y e r , a n i o n c o n d u c t o r ,
and an ion storage. Colouration and bleaching are accomplished w h e n ions are
m o v e d from the ion storage, via the ion conductor, into the electrochromic layer,
o r w h e n t h e p r o c e s s is r u n in r e v e r s e . T h e i o n s t o r a g e c a n b e a n o t h e r e l e c t r o -
c h r o m i c l a y e r , p r e f e r r a b l y a n o d i c if t h e b a s e e l e c t r o c h r o m i c l a y e r is c a t h o d i c , o r
vice versa. O n e m a y also c o m b i n e the ion conductor and storage m e d i a into one
l a y e r o f e l e c t r o l y t e . F u r t h e r , it+ is p o s s i b l e to e x c l u d e t h e i o n s t o r a g e a n d i n s t e a d
rely on a replenishment of H ions (protons), originating from the dissociation of
w a t e r m o l e c u l e s diffusing in f r o m a n a m b i e n c e w i t h c o n t r o l l e d h u m i d i t y ;
o b v i o u s l y this r e q u i r e s a s u b s t a n t i a l a t o m i c p e r m e a b i l i t y o f t h e o u t e r t r a n s p a r e n t
conductor. B y use of a purely ionic conductor, o n e can obtain an o p e n circuit
m e m o r y , i.e., t h e e l e c t r i c field h a s to b e a p p l i e d o n l y w h e n t h e o p t i c a l p r o p e r t i e s
a r e t o b e altered. T h e d e s i g n in F i g . 1 9 h a s a l o w v a l u e o f Etherm b e c a u s e o f t h e
e x t e r n a l t r a n s p a r e n t c o n d u c t o r . A l t e r n a t i v e l y , t h e e l e c t r o c h r o m i c c1o a2t0
ing can be
combined with a lamination material which joins two glass p a n e s ; in this c a s e
a n a d d i t i o n a l t r a n s p a r e n t a n d infrared-reflecting c o a t i n g is r e q u i r e d to o b t a i n a
l o w Etherm-
Fig. 19. B a s i c d e s i g n o f a n e l e c t r o c h r o m i c c o a t i n g for s m a r t w i n d o w s .

(From Ref. 19).
W e n o w c o n s i d e r t h e m a t e r i a l s in t h e different c o m p o n e n t s o f t h e e l e c t r o c h r o -
m i c s - b a s e d c o a t i n g a n d first l o o k at t h e a c t u a l e l e c t r o c h r o m i c l a y e r ( s ) . T u n g s t e n
o x i d e w a s t h e first d i s c o v e r e d e l e c t r o c h r o m i c m a t e r i a l a n d is b y far t h e m o s t
w i d e l y s t u d i e d o n e . " I n a m o r p h o u s state it p e r m i t s t h e a b s o r p t a n c e to b e
m o d u l a t e d b e t w e e n w i d e1limits.
05 3 -I n1c r 0 y s t a l l i n e s t a t e it a l l o w s a fair d e g r e e o f
reflectance m o d u l a t i o n . T h e degree o f crystallinity depends on the glass
t e m p e r a t u r e d u r i n g t h e c o a t i n g p r o c e s s . H y d r a t e d n i c k e l o x i d e is a r a t h e r r e c1 e n t0l 0
y6 - 1 2
discovered electrochromic material which allows absorptance m o d u l a t i o n .
Its d u r a b i l i t y s e e m s to b e s u p e r i o r to t h a t o f t u n g s t e n o x i d e . T h e m e c h a n i s m s for
colouration and bleaching of the mentioned electrochromic materials have been

given as
colour
+
xM + xe- + W 0 ^ M W0
3 x 3
bleach
and
colour
+
Ni(OH) ~* NiOOH + H + e"
2
bleach
+ + + +
w h e r e M d e n o t e s H , L i , N a , etc. H e n c e t u n g s t e n o x i d e c o l o u r s u n d e r ion
insertion whereas hydrated nickel oxide colours under ion extraction. This opens
t h e p o s s i b i l i t y o f w o r k i n g w i t h a n o p t i c a l l y efficient " c o m p l e m e n t a r y " d e s i g n
i n c o r p o r a t i n g l a y e r s o f b o t h m a t e r i a l s as " e l e c t r o c h r o m i c m a t e r i a l " a n d "ion
s t o r a g e " , r e s p e c t i v e l y . It is also 1t1
e2
c h n i c a l l y p o s s i b l e to o p e r a t e t u n g s t e n o x i d e a n d
i r i d i u m o x i d e in c o n j u n c t i o n .
18
T h e ion conductor can also b e of m a n y m a t e r i a l s . Disregarding liquid electro-
l y t e s - w h i c h a r e not p1r a c0 1t i2c5
2a l for w i n d o w s - it is p o s s i b l e to e m p l o y L i F , L1AIF4,
LiNbC>3 1 0 a1n d21the1
2 4l i3
2k e ' as w e l l as l a y e r s o f t r a n s p a r e n t p o l y m e r i c i o n c o n d u c -
tors. ' ' ' In d e v i c e s w h i c h r e l y o n a m b i e n t h u m i d i t y , l a y9e r1s9 o2f8i5o n-- 1 2
permeable SiO and M g F coatings have been used s u c c e s s f u l l y . ' The
2
t r a n s p a r e n t c o n d u c t o r o n the g l a s s s u r f a c e can b e o f I n 0 3 : S n o r a s i m i l a r d o p e d
2
oxide semiconductor. T h e outer transparent electrode can consist of the same
m a t e r i a l o r - if a t o m i c p e r m e a t i o n is r e q u i r e d - o f an e x t r e m e l y thin g o l d layer.
T h e v o l t a g e r e q u i r e d for t h e d i s t r i b u t e d e l e c t r i c field is o n t h e o r d e r o f a f e w volts
a n d n e e d s o n l y b e a p p l i e d w h e n the o p t i c a l p r o p e r t i e s a r e to b e altered.
F i g u r e 2 0 illustrates the c h a r a c t e r i s t i c features o f a b s o r p t a n c e - m o d u l a t e d

electrochromic coatings based on amorphous tungsten oxide and hydrated nickel
o x i d e in fully b l e a c h e d s t a t e , fully c o l o u r e d state, a n d at i n t e r m e d i a t e c o l o u r a t i o n .
T h e u p p e r p a r t refers to a d e v i c e w i t h t w o In C>3:Sn-coated g l a s s s u b s t r a t e s , o n e o f
2
them being overcoated 1 w9i2t h t u n g s t e n o x i d e , a n d an i n t e r v e n i n g l i q u i d L i + -
containing electrolyte. T h e l o w e r p a r t w a s o b t a i n e d for o n e I n 0 3 : S n - c o a t e d
2
glass with a hydrated nickel oxide overlayer m a d e b y radio frequency sputtering;
1 2 1
t h e c o l o u r i n g w a s a c c o m p l i s h e d in a p o t a s s i u m h y d r o x i d e e l e c t r o l y t e p r i o r to the
optical m e a s u r e m e n t s . Both devices s h o w pronounced electrochromism with
t h e t u n g s t e n o x i d e a b s o r b i n g e s p e c i a l l y s t r o n g l y in t h e infrared a n d t h e h y d r a t e d
n i c k e l o x i d e a b s o r b i n g e s p e c i a l l y s t r o n g l y for v i s i b l e light. N o d a t a a r e s h o w n for
λ > 1.2 μιη o w i n g to t h e i n f l u e n c e o f t h e In C>3:Sn l a y e r s (cf. u p p e r p a r t o f F i g . 1 7 ) .
2
F i g u r e 21 s h o w s q u a n t i t a t i v e r e s u l t s for t h e m o d u l a t i o n o f T i m a n d T i b y a glass
U s o
plate with low Fe2U3 content overcoated with moderately conducting I n 2 0 3 : S n
and with electrochromic hydrated nickel oxide prepared by radio frequency
s p u t t e r i n g . It is s e e n that Tium c a n v a r y b e t w e e n 8 0 a n d 10 % a n d that T i c a n
s o
1001 ι I ι I ι ! I I ι I I I I I I I I I I I
2 ο — ^ '
2 ioo| 1
^^^^^^^^^^^^^^^^
ol ι I ι I ι I ι I ι I ι I ι I ι I ι I ι
0.4 0.6 0.8 1.0 1.2
Wavelength (pm)
Fig. 2 0 . S p e c t r a l n o r m a l t r a n s m i t t a n c e m e s u r e d for r e s e a r c h - t y p e
devices incorporating an electrochromic layer o f tungsten
oxide (upper part) and hydrated nickel oxide (lower part).
C o m p i l e d f r o m Refs. 1 1 2 a n d 1 2 9 .
2
v a r y b e t w e e n 8 0 a n d 2 0 % w h e n a c h a r g e d e n s i t y u p to 2 0 m C / c m is i n j e c t e d .
A n a l o g o u s e l e c t r o c h r o m i c c o a t i n g s m1a6d1e b y d i r e c t c u r r e n t s p u t t e r i n g h a v e n o t y e t
g i v e n r e s u l t s that a r e q u i t e as g o o d .
I n p r i n c i p l e , r e f l e c t a n c e m o d u l a t i o n is s u p e r i o r t o a b s o r p t a n c e m o d u l a t i o n , s i n c e
t h e c o a t e d g l a s s d o e s n o t b e c o m e h e a t e d to a c o m p a r a b l e e x t e n t . F i g u r e 2 2 s h o w s
r e f l e c t a n c e s p e c t r a for+a 0 . 2 3 ^ m - t h i c k c r y s t a l l i n e W O 315l 0a y e+r o n In2C>3:Sn-coated
g l a s s o p e r a t e d in a L i - c o n t a i n i n g l i q u i d e l e c t r o l y t e . L i i n j e c t i o n is s e e n to g i v e
+
reflection, p a r t i c u l a r l y in the infrared, u p to - 7 0 % at λ = 2.5 μ ι η . E x t r a c t i o n o f the
L i i o n s b r i n g s b a c k t h e initial l o w r e f l e c t a n c e . T h e o r e t i c a l m o d e l l i n g o f t h e
e l e c t r o c h r o m i c r e f l e c t a n c e m o d u l a t i o n h a s b e e n p e r f o r m8e 1d17b2y u s i n g t h e t h e o r y for
the optical properties o f doped oxide s e m i c o n d u c t o r s . ' T h e limiting optical
p e r f o r m a n c e - o b t a i n e d w i t h s e v e r a l s i m p l i f y i n g a s s u m p t i o n s - is t h a t m o d uβ lation
can b e a c c o m p l i s h e d b e t w e e n a state with T i « 8 2 %, T i
s o um« 7 4 % a n d Rjum 2 6 %
and another state with T i - 35 %, T i
s o um- 6 3 % a n d R i um- 5 %. T h e t h e o r e t i c a l
u n d e r s t a n d i n g o f a b s o r p t a n c e - m o d u l a t e d e l e c t r o c h r o m i c m a t e r i a l s is y e t t o o
fragmentary to p e r m i t quantitative modelling.
1 1
1001—«— —ι— —ι—ι—«—ι—ι—
g \ N i O xH y
Z ~ \ l n 20 3: S n ,,,,,,,,,,,,,,,„,.,,,.,,.,
1 - glass
2 so- \ V t T
• X T
5) \^ ^^^^
Φ - „ ^
Ξ τ, :
lu m ^--^^^^
01 l I I I I I I I ι
10 20
2
Charge (mC/cm )
Fig. 2 1 . I n t e g r a t e d t r a n s m i t t a n c e v s . c h a r g e d e n s i t y for e l e c t r o -
c h r o m i c c o a t i n g s o f t h e t y p e s h o w n in t h e inset. ( F r o m
Ref. 1 1 2 ) .
In t h e r e m a i n d e r o f this s e c t i o n o n e l e c t r o c h r o m i c s - b a s e d c o a t i n g s , s o l i d - s t a t e
c o n f i g u r a t i o n s a r e f o c u s e d o n , s i n c e t h e s e a r e t h e o n l y o n e s o f c o n c e r n for p r a c t i c a l
w i n d o w a p p l i c a t i o n s . F i g u r e 2 3 s h o w s t r a n s m i t t a n c e s p e c t r a for a m u l t i l a y e r
d e s i g n w i t h 0.15 μιη o f W O 3 ~ 0.1 μιη o f M g F , a n d 0 . 0 1 5 μιτι o f g o l d . T h i s t y p e o f
/ 2
d e v i c e w a s o r i g i n a l l y d e v e l o p e d b y D e b " a n d h a s s i n c e b e e n w o r k e d o n b y others.
It relies o n a m b i e n t w a t e r , w h i c h is c a t a l y t i c a l l y d e c o m p o s e d at t h e A u e l e c t r o d e
and driven via the M g F layer into the amorphous electrochromic W O 3 layer by a
2
v o l t a g e b e t w e e n the A u a n d In C>3:Sn e l e c t r o d e s . T h e d a t a in F i g . 2 3 c o r r e s p o n d to
2
a m o d u l a t i o n o f T i b e t w e e n 2 5 a n d 3 %. It is n o t p o s s i b l e to o b t a i n T i » 2 5 %
s o s o
b e c a u s e o f r e f l e c t a n c e at t h e A u e l e c t r o d e . T h e d e v i c e s b e c o m e n o n - f u n c t i o n a l in
a d r y a m b i e n c e b u t r e g a i n t h e i r e l e c t r o c h r o m i s m in a h u m i d a t m o s p h e r e .
T h e state-of-the-art ( 1 9 9 1 ) in e l e c t r o c h r o m i c s m a r t w i n d o w s is b e l i e v e d to b e
r e p r e s e n t e d in F i g . 2 4 . T h e i n v e s t i g a t e d d e v i c e i n c o r p o r a t e s t w o g l a s s e s w i t h l o w
Fe C>3 c o n t e n t , e a c h h a v i n g a t r a n s p a r e n t c o n d u c t i n g l a y e r a n d a n e l e c t r o c h r o m i c
2
layer, laminated together by a solid transparent polymeric ion conductor. O n e of
t h e e l e c t r o c h r o m i c l a y e r s is a n o d i c a n d the o t h e r is c a t h o d i c . T h e d e v i c e is
mechanically rugged and permits extended colour-bleach cycling. Absorptance
modulation yields T i
umb e t w e e n 6 8 a n d 9.5 % a n d T s i ob e t w e e n 6 3 . 5 a n d 7.5%. A
l o w Etherm c a n b e o b t a i n e d b y h a v i n g a l a y e r o f S n 0 : F , for e x a m p l e , o n e i t h e r o f
2
the exterior glass surfaces.
100
"Γ"ι ι ι—τη—ι—ι—ι—ι—ι—ι—ι—ι—τη—ι—ι—ι—r
ννο3
l n 20 3: S n
φ
υ
S 50
Ο
φ
φ
J I I L
0.5 1 1.5 2 2.5
W a v e l e n g t h (μιτι)
Fig. 2 2 . S p e c t r a l n e a r - n o r m a l r e f l e c t a n c e m e a s u r e d for t h e
e l e c t r o c h r o m i c d e v i c e s h o w n in t h e i n s e t at m a x i m u m
i n f r a r e d r e f l e c t a n c e . ( F r o m Ref. 1 0 5 ) .
1 1 1
1 ' I ι ι ι ι I ι ι ι ι I 1 1 1 1
\ 1
- y» wo 3
-
mm l n 20 3: S n ^ — '
r 1 1 1 1_ J L i 1 1 1 1 1 1 1 1 I ι l 1
0.5 1 1.5 2 2.5
Wavelength (μπι)
Fig. 2 3 . S p e c t r a l n o r m a l t r a n s m i t t a n c e m e a s u r e d for t h e e l e c t r o -
c h r o m i c d e v i c e s h o w n in t h e i n s e t in fully b l e a c h e d s t a t e ,
in fully c o l o u r e d state, a n d at i n t e r m e d i a t e c o l o u r a t i o n .
Replotted from Ref. 19.
100Γ
ι ι ι ι ι ι I I { ι ι ι ι ι ι ι ι ι ι I I I
80
φ
υ 60
c
(0
g 40|
20h
0 I ιι I r ^ ^ ^ ^ ι ι I ι ι'"ΤΤΤΤ"'| ι ι I i ^ i 7"
0.5 1 1.5 2 2.5
Wavelength (μπι
Fig. 2 4 . S p e c t r a l n o r m a l t r a n s m i t t a n c e m e a s u r e d for a r e s e a r c h -
t y p e e l e c t r o c h r o m i c s m a r t w i n d o w in fully b l e a c h e d a n d
fully c o l o u r e d states.
T h i s s e c t i o n is c o n c l u d e d w i t h s o m e p r a c t i c a l c o n s i d e r a t i o n s for s m a r t w i n d o w s .
T h e t i m e for g o i n g f r o m fully b l e a c h e d to fully c o l o u r e d s t a t e , h e r e c a l l e d t h e
r e s p o n s e t i m e r, is o f o b v i o u s s i g n i f i c a n c e . T h e r e q u i r e d t i m e s c a l e is set b y t h e
e y e ' s ability to a c c o m o d a t e , w h i c h is o n t h e o r d e r o f m i n u t e s . W e n o t e , in p a s s i n g ,
that a s m a l l d i s1p0 l a3y e l e2m e n t s h o u l d h a v e r « 1 s. F o l l o w i n g a n a n a l y s i s b y
V i e n n e t et a l . , a i m \ V O 3 - b a s e d e l e c t r o c h r o m i c l a y e r c a n h a v e a r e s p o n s e time
o n t h e o r d e r o f o n e m i n u t e . T h e m a g n i t u d e o f r is critically d e p e n d e n t o n t h e
electrical r e s i s t a n c4e in the8t r1a11 n s3p a r e n t c o n d u c t o r ( s ) ; t h e l o w e s t r e s i s t i v i t y for
I n 2 Û 3 : S n is ~ ΙΟ" Ω c m . ' T h e t e m p e r a t u r e d e p e n d e n c e o f r is1e2l 3 u c i d a t e d in
Fig. 2 5 w i t h r e g a r d to t h e b l e a c h i n g o f a s m a l l W U 3 - b a s e d s a m p l e . It is s e e n that
r rises at l o w t e m p e r a t u r e s , b u t t h e effect is o f little p r a c t i c a l s i g n i f i c a n c e for an
e l e c t r o c h r o m i c c o a t i n g p l a c e d o n t h e i n n e r g l a s s o f a d o u b l e - g l a z e d w i n d o w . Full
c o l o u r u nai f o nr m i t y o v e r an e x t e n d e d s u r f a c e c a n n o t b e e x p e c t e d d u r i n g c h a n g e s o f
Tium d T l / b u t the u n e v e n e s s can b e m a d e i n v i s i b l e at t h e e x p e n s e o f a l o n g
s o
r e s p o n s e t i m e . I r i d e s c e n c e m a y b e a c o n c e r n , j u s t as for d o p e d o x i d e s e m i c o n -
d u c t o r c o a t i n g s , for e l e c t r o c h r o m i c m u l t i l a y e r c o a t i n g s p l a c e d o n a s i n g l e g l a s s
s u r f a c e . E l e c t r o c h r o m i c c o a t i n g s o p e r a t e d in a l a m i n a t e c o n f i g u r a t i o n a r e e x p e c t e d
to b e less p r o n e to s h o w i r i d e s c e n c e o w i n g to t h e m a t c h i n g o f refractive i n d i c e s for
adjacent layers.
It is n o t p o s s i b l e to g i v e e v e n a c o a r s e e s t i m a t e o f t h e c o s t o f a p r a c t i c a l s m a r t
w i n d o w . H o w e v e r , it s h o u l d b e n o t i c e d t h a t i n h e r e n t l y c h e a p t e c h n i q u e s a r e
b e i n g d e v e l o p e d for efficient d e p o s i t i o n o f e l e c t r o c h r o m i c l a y e r s b y c h e m i c a l
S 1
φ
ε
c
ο 0.5
φ
φ
œ
0
-20 0 20 40
Temperature (°C)
Fig. 2 5 . B l e a c h i n g t i m e vs. t e m p e r a t u r e for a n e l e c t r o c h r o m i c
d e v i c e w i t h a W 0 layer. ( F r o m Ref. 1 3 2 ) .
1 2
1 8
3
1 43 3 1 3
165
3
vapour d e p o s i t i o n ' ' and dip c o a t i n g . ' Plasma enhanced chemical
vapour deposition and high-rate sputterin 18g a r e o t h e r t e c h n o l o g i e s t h a t m a y b e
u s e d for p r a c t i c a l l a r g e - s c a l e p r o d u c t i o n . T h e e l e c t r i c a l p o w e r n e e d e d for
operating an electrochromic smart w i n d o w can b e assessed from the relation
b e t w e e n c h a r g e d e n s i t y a n d c o l o u r a t i o n (cf. F i g . 2 1 ) . A s i m p l e a n a l y s i s y i e l d s that
t h e e l e c t r i c a l e n e r g y r e q u i r e m e n t is as l o w as « 1 k W h p e r y e a r a n d s q u a r e m e t r e
w i n d o w area.
F. Thermochromic Coatings
T h e r m o c h r o m i s m is w e l l k n o w n for i n o r g a n1i c187 m3a t e r i a l s i n t h e l i q u i d a n d s o l i d

s t a t e as w e l l as in m a n y 1 o8
r g3a n i c m a t e r i a l s . ' A m o n g the m a n y thermochromic
transition metal o x i d e s , v a n a d i u m4 d1i0o x3i 2
d e9 s t-a n1
d s 4o u t as p a r t i c u l a r l y i n t e r e s t i n g
for a p p l i c a t i o n s o n s m a r t w i n d o w s . ' V O 2 u n d e r g o e s a structural trans-
f o r m a t i o n a t a "critical" t e m p e r a t u r e t , b e l o w w h i c h t h e m a t e r i a l is s e m i c o n d u c -
c
ting a n d r e l a t i v e l y n o n - a b s o r b i n g in t h e infrared, a n d a b o v e w h i c h t h e m a t e r i a l is
m e t a l l i c a n d i n f r a r e d reflecting. A w i n d o w w i t h a V O 2 c o a t i n g h e n c e h a s a T l
s o
w h i c h d r o p s at τ > x , i.e., t h e w i n d o w is c a p a b l e o f a n a u t o m a t i c c o n t r o l o f the
c
throughput of radiant energy. This control m a y b e achieved b y use of a single
l a y e r , i.e., w i t h a c o a t i n g d e s i g n w h i c h is s i m p l e r t h a n t h e o n e in a n e l e c t r o -
c h r o m i c s m a r t w i n d o w . H o w e v e r , t h e c o n t r o l is b u i l t i n t o t h e m a t e r i a l a n d is n o t
e a s i l y m o d i f i e d b y an o p e r a t o r .
C r y s t a l s o f V O 2 a r e c h a r a c t e r i z e d b y x ~ 68° C , w h i c h is t o o h i g h for 4n1 o02 4al

rm
c
w i n d o w applications, but t can be depressed by several t e c h n i q u e s ' s u c h as b y
c
replacement of s o m e vanadium b y tungsten, m o l y b d e n u m , niobium or rhenium,
b y r e p l a c e m e n t o f s o m e o x y g e n b y fluorine, o r b y i n t r o d u c i n g s t r e s s e i t h e r b y u s e
o f a s u i t a b l e s u b s t r a t e o r b y a p p l y i n g a n o v e r l a y e r . F o r t h e latter o p t i o n , t h e
o v e r l a y e r c a n s e r v e a l s o s o as to antireflect the V O 2 c o a t i n g .
Figure 2 6 illustrates the t h e r m o c h r o m i s m o n e can obtain in a 0 . 1 3 ^ m - t h i c k

v a n a d i u m o x y f l1u3o4r i d e l a y e r p r e p a r e d b y s p u t t e r d e p o s i t i o n o n t o g l a s s w i t h l o w
Fe2C>3 c o n t e n t . T h e c o a t i n g is c h a r a c t e r i z e d b y x « 5 2 ° C (as o b t a i n e d f r o m
c 144
electrical conductance), T i
um» 2 8 % i r r e s p e c t i v e o f t e m p e r a t u r e , a n d T s i or a n g i n g
f r o m 3 5 % a t 2 5 ° C t o 2 8 % at 7 0 ° C T i is i n c r e a s e d b y t h e f l u o r i n a t i o n , as
um
apparent from Fig. 27; however the limited magnitude o f T i
um m a y still b e a n
o b s t a c l e for m a n y w i n d o w a p p l i c a t i o n s . T h e s i t u a t i o n c a n b e i m p r o v e d b y u s e o f
a n o v e r l a y e r , t h o u g h . F i g u r e 2 8 s h o w s s p e c t r a l t r a n s m i t t a n c e a t τ « x a n d τ » x124
c c
for a g l a s s c o a t e d b y 0.05 μπ\ o f V O 2 , m a d e b y e v a p o r a t i o n , a n d 0.11 μπ\ o f S n C > 2 .
T h e double-layer has T « 49 °C , T i
c um« 4 5 %, a n d T s i o« 5 3 % a t 2 5 ° C a n d
Tsoi « 4 6 % at 8 0 ° C . T h e b a r e V O 2 l a y e r h a s Τ « 3 5 %.
ί ηυ Γ
T h e r m o c h r o m i c VC>2-based c o a t i n g s s t u d i e d s o far h a v e a n u n d e s i r a b l y l a r g e A i m /
U
which tends to m a k e the modulation o f T i rather small. Nevertheless,
s o
t h e r m o c h r o m i c smart w i n d o w s are o f considerable potential interest, a n d basic
m a t e r i a l s r e s e a r c h in this a r e a is b e i n g p u r s u e d .
100 ι ι I ι ι ι ι J ι ι—ι—ι—I—ι—ι—ι—ι—I—ι—ι—ι—ι—
80-
S> ~ v o xF y mm,mm
I 60- 9 , a S S
,ΓΓ 1
25^0^
I 40- ^ - β ^ -
f _ / ^ βο -
01 J ^ l 1 I—L_J I I L_J I l_J I I I L_J L_J I i

0.5 1 1.5 2
Wavelength (urn)
Fig. 2 6 . S p e c t r a l n o r m a l t r a n s m i t t a n c e m e a s u r e d for a r e s e a r c h - t y p e
thermochromic smart w i n d o w with a vanadium oxyfluoride
c o a t i n g at t h e s h o w n s i x t e m p e r a t u r e s . ( F r o m R e f . 1 4 3 ) .
80|—ι 1—' ι ι ι ιιι 1 1—ι ι I
F V
60- ° x y -
. \ vo2
•
\
\
\
Ε
(0
20-
• C> -
V
ο ^ -
I . II I. I• I I I I I .
20 50 100 200 500
Thickness (nm)
Fig. 2 7 . L u m i n o u s t r a n s m i t t a n c e v s . t h i c k n e s s for c o a t i n g s o f V O F
x y
and V O 2 . T h e values o f χ and y are likely to vary somewhat
a m o n g t h e s a m p l e s o w i n g to d i f f e r e n c e s i n p r e p a r a t i o n c o n -
d i t i o n s .11C u r1v e1s w1e r e1 d1r1a w1n for 1 1c o1n v e n1i e 1
n1c e . 1( F r o m R e f . 1 4 4 )
10OI I I I I '
Γ SnO, ι 1 ~
8 _0 V02 K B
glass! I
"T
g - 2O^C^ _
Φ 60- "
g 40- I/ -
È - / ^ ^ ^ ^ 8 0
20- / "
nl ι 1 1 ι ι ι ι I ι ι ι ι I ι ι ι ι I ι 1 1 1
0.5 1 1.5 2 2.5
Wavelength (μιη)
Fig. 2 8 . S p e c t r a l n o r m a l t r a n s m i t t a n c e for a r e s e a r c h - t y p e t h e r m o -
chromic smart window with a vanadium oxide/tin oxide
t a n d e m c o a t i n g at t w o t e m p e r a t u r e s . ( F r o m R e f . 1 4 2 ) .
G. Coatings with Angularly Dependent Transmittance
This section contains some examples of computed and measured transmittance

through uniform and non-uniform metal-based coatings. For the case of uniform
c o a t i n g s , t h e t r a n s m i t t a n c e is n o n - s e l e c t i v e , i.e. Τ ( θ ) = Τ(-θ), b u t t h e a n g u l a r
d e p e n d e n c e c a n b e s t r o n g for s u i t a b l y d e s i g n e d m u l t i l a y e r s t a c k s . P a r t3
i5c u l a r l y
i n t e r e s t i n g d a t a a r e o b t a i n e d b y i n v o k i n g m o r e t h a n o n e m e t a l l a y e r , in w h i c6 h1
c a s e t h e c o a t i n g d e s i g n b e c o m e s s o m e w h a t a k i n to that o f a F a b r y - P e r o t é t a l o n .
F i g u r e 2 9 s h o w s t w o e x a m p l e s o f T i (Θ) for five-layer c o a t i n g s c o n s i s t i n g o f 62 two
s o
1 2 - n m - t h i c k silver l a y e r s a n d t h r e e S1O2 l a y e r s . T a b u l a t e d o p t i c a l c o n s t a n t s
p e r t i n e n t to t h e b u l k m a t e r i a l s w e r e u s e d in t h e c o m p u t a t i o n s . W h e n t h e S1O2
t h i c k n e s s is 1 2 0 n m , t h e r e is a m o n o t o n i e d e c r e a s e o f T i w i t h i n c r e a s i n g Θ. F o r
s o
1 7 0 - n m - t h i c k S1O2 l a y e r s , t h e a n g u l a r d e p e n d e n c e is m o r e i n t e r e s t i n g a n d g o e s
f r o m ~ 2 3 % at n o r m a l i n c i d e n c e to as m u c h as ~ 5 8 % at 6 0 ° a n g l e o f i n c i d e n c e .
F u r t h e r w o r k is n e e d e d to e x p l o r e t h e limits o f t h e a n g u l a r l y d e p e n d e n t o p t i c a l
properties in multilayer w i n d o w coatings with m o r e than o n e metal layer.
100 L
> I ι I ι
I ' I ' I ' ι• ι
80
\- t =120nm
• ^
φ
υ
c
φ
40 / \ #
- t=170nm / Λ
ο ° LJ
|>Ag(12nm)
Ν / · ι
τ7|
0 I ι I ι I ι I • I ι I ι I ι I ι
ο 30 60 90
Incidence angle (deg.)
Fig. 2 9 . C o m p u t e d a n g u l a r l y d e p e n d e n t s o l a r t r a n s m i t t a n c e for
S i 0 2 / A g / S i C > 2 / A g / S i 0 c o a t i n g s w i t h t w o v a l u e s o f the
2
S1O2 t h i c k n e s s (t). T h e c o a t i n g c o n f i g u r a t i o n is s h o w n in
the inset. O p e n a n d filled circles s h o w c o m p u t e d d a t a .
C u r v e s w e r e d r a w n o n l y for c o n v e n i e n c e . ( F r o m R e f . 3 5 ) .
A n g u l a r s e l e c t i v i t y , c a n o c c u r if a c o a t i n g - o r m o r e g e n e r a l l y at l e a s t o n e o f the
l a y e r s in a m u l t i l a y e r s t a c k - is n o n - h o m o g e n e o u s a n d h a s a n o p t i c a l a x i s w h i c h
d e v i a t e s from t h e n o r m a l to t h e c o a t i n g . In o r d e r to b e m o r e specific, a n d p o i n t
o u t s o m e g e n e r a l r e s u l t s for a n g u l a r s e l e c t i v i t y , w e c o n s i d e r a c o l l i m a t e d l i g h t
b e a m i n c i d e n t o n t o a flat u n i f o r m s u b s t r a t e w i t h a c o a t i n g o f a m a t e r i a l c h a r a c -
t e r i z e d b y a u n i q u e o f f - n o r m a l o p t i c a l axis. T h e s i t u a t i o n is i l l u s t r a t e d s c h e m a t i -
cally i n F i g . 3 0 . T h e c o a t i n g is t a k e n to c o n s i s t o f i d e n t i c a l c y l i n d r i c a l c o l u m n s . A
m i c r o s t r u c t u r e a p p r o a c h i n g this m o d e l c a n b e r e a l i z e d i n s a m p l e s p r o d u c e d b y
s p e c i a l v a c u u m d e p o s i t i o n t e c h n i q u e s , as w i l l b e d i s c u s s e d s h o r t l y .
! /
Fig. 3 0 . T h e left-hand p a r t defines t h e g e o m e t r y for a l i g h t b e a m

i n c i d e n t o n t o a c o a t i n g o f a u n i a x i a l m a t e r i a l . T h e right-
h a n d p a r t s h o w s a s c h e m a t i c m o d e l for a c o l u m n a r
m i c r o s t r u c t u r e . ( F r o m Refs. 3 5 a n d 1 4 5 ) .
T h e o p t i c a l p r o p e r t i e s a r e c o n v e n i e n t l y d e s c r i b e d w i t h r e g a r d to a v e c t o r α in the
s u r f a c e p l a n e . O n e c a n t h e n specify t h e i n c i d e n t l i g h t b e a m b y its p o l a r a n g l e θ
a n d its a z i m u t h a l a n g l e 0. T h e v e c t o r α is c h o s e n s o that Τ ( θ , o = 9 0 ° ) =
Τ ( θ , o = 2 7 0 ° ) ; o t h e r o r i e n t a t i o n s o f t h e light b e a m y i e l d Τ ( θ , ο ) Φ Τ ( θ , 0 + 1 8 0 ° ) .
In g e n e r a l , t h e d i f f e r e n c e b e t w e e n t h e t r a n s m i t t a n c e v a l u e s in t h e i n e q u a l i t y is
l a r g e s t at 0 = 0, i.e., for light i n c i d e n t in t h e p l a n e s p a n n e d b y α a n d t h e s u r f a c e
n o r m a l . T h i s p a r t i c u l a r c o n f i g u r a t i o n l e a d s to a s i m p l e c r i t e r i o n for a n g u l a r
s e l e c t i v i t y , w h i c h c a n b e w r i t t e n for s p o l a r i z a t i o n (electric field v e c t o r p e r p e n d i -
c u l a r to t h e i n c i d e n c e p l a n e ) a n d ρ p o l a r i z a t i o n (electric field v e c t o r in t h e
i n c i d e n c e p l a n e ) as T ( 0 ) = T (-Θ) a n d T (θ) Φ T (-Θ). H e r e t h e s i g n c o n v e n t i o n
s s p p
+ θ (-Θ) d e n o t e s l i g h t h a v i n g a p r o p a g a t i o n v e c t o r w i t h a c o m p o n e n t o p p o s i t e
( p a r a l l e l ) to α . It is e v i d e n t that a n g u l a r s e l e c t i v i t y is m o s t p r o n o u n c e d for light
with predominant ρ polarization.
E x p e r i m e n t a l l y it is p o s s i b l e to a c h i e v e a m i c r o s t r u c t u r e r e s e m b l i n g t h e o n e in t h e
right-hand part of Fig. 30 by special etching techniques and, m o r e interestingly, by
v a c u u m deposition with the impinging b e a m having an angle α that deviates
f r o m t h e s u b s t r a t e n o r m a l . T h i s e x p e r i m e n t a l c o n f i g u r a t i o n is r 3e f e35
r r3
e7d18to4
16 as54
o b l i q u e a n g l1e7d 4e p o s i t i o n a n d is p o s s i b l e b o t h w i t h e v a p o r a t i o n ' ' ' ' and
sputtering. T h e r e l a t i o n b e t w e e n 1d8e4p o s i t i o n a n g l e a n d c o l u m n o r i e n t a t i o n is
often g i v e n b y a "tangent rule", v i z .
tan β = ( 1 / 2 ) tan a , (6)
w h e r e β is t h e a n g l e b e t w e e n the s u b s t r a t e n o r m a l a n d t h e s y m m e t r y d i r e c t i o n for
t h e c o l u m1
ns 4
(i.e.,9 t h e c o l u m n tilt). T h e g e n e r a l v a l i d i t y o f E q . ( 6 ) is q u e s t i o n a b l e ,
though. ^
S t u d i e s o f a n g u l a r l y s e l e c t i v e t r a n s m i t t a n c e t h r o u g h3 o15 b5l4
iquely evaporated
chromium coatings have been conducted r e c e n t l y . ' F i g u r e 31 s h o w s that b o t h
Tium (Θ) a n d T i (Θ) i n c r e a s e m o n o t o n i c a l l y w i t h i n c r e a s i n g a n g l e u n t i l θ « + 6 0 °
s o
is r e a c h e d . B e y o n d this a n g l e t h e i n t e g r a t e d t r a n s m i t t a n c e d r o p s . S p e c i f i c a l l y ,
Tium g o e s f r o m ~ 21 % at θ = - 6 0 ° to - 3 2 % at θ = + 6 0 ° , a n d T i g o e s f r o m - 2 7 % at
s o
θ = - 6 0 ° to - 3 7 % at θ = + 6 0 ° . T h e s e r e s u l t s s h o w c l e a r l y that a n g u l a r l y s e l e c t i v e
t r a n s m i t t a n c e , o f i n t e r e s t for e n e r g y - e f f i c i e n c y , c a n i n d e e d b e o b t a i n e d . D a t a for
a l u m i n i u m a n d t a n t a l u m c o a t i n g s a r e g i v e n in R e f . 3 8 .
ι ι ι ι ι ι ι ι ι ι ι ι ι ι 1
50 I-
£ 40 \ -
υ j
i 20 - I I·/
σ> - Cr I / I 54nm _
Φ glass " 7 f
s ίο-
T
lum,sol
0 l ι I ι ι I ι ι I • ι I • ι l • I
-60 -30 0 +30 +60
Incidence angle, θ (deg.)
Fig. 3 1 . Angularly dependent luminous and solar transmittance
d e t e r m i n e d as s k e t c h e d in t h e inset. ( F r o m R e f s . 3 5 a n d 1 4 5 ) .
H. Antireflection Treatments
It w a s p o i n t e d o u r e a r l i e r that e a c h s u r f a c e o f a n o r d i n a r y w i n d o w g l a s s p r o d u c e s
- 4 % reflection, a n d that c o a t e d g l a s s s u r f a c e s , in g e n e r a l , h a v e a reflection that is
e v e n h i g h e r . T h i s reflection is often u n d e s i r a b l e b o t h in t e r m s o f e n e r g y efficiency
a n d s i n c e it c a n c a u s e v i s u a l l y d i s t u r b i n g effects. A s o l u t i o n to this p r o b l e m is to
apply an antireflection (AR) treatment, which can invoke a layer o f refractive
i n d e x - 1.4 a n d t h i c k n e s s - 0.1 μιη o n t o p o f t h e ( c o a t e d ) g l a s s . O t h e r s o l u t i o n s can
b e o b t a i n e d b y e m p l o y i n g a c h e m i c a l e t c h i n g o f the g l a s s s u r f a c e o r b y h a v i n g thick
polymeric coatings.
D i e l e c t r i c A R l a y e r s o f M g F etc. h a v e b e e n p r o d u c e d 31 by evaporation and used on

2
l e n s e s a n d o t h e r o p t i c a l c o m p o n e n t s for m a n y y e a r s . These layers are hard and
c h e m i c a l l y i n e r t b u t d o n o t l e n d t h e m s e l v e s to efficient l a r g e - s c a l e s p u t t e r
d e p o s i t i o n . In fact, u n t i l r e c e n t l y t h e r e w e r e n o d u r a b l e l o w - r e f r a c t i v e - i n d e x
c o a t i n g s w h i c h c o u l d b e a p p l i e d b y h i g h - r a t e s p u t t e r i n g . C u r r e n t l y t h e situation is
c h a n g i n g , a n d a r a n g e o f 4n e 4w1 l y1
- 5d4e v 6
eloped metal oxyfluoride coatings have shown
very promising r e s u l t s . '
A l u m i n i u m o x y f l u o r i d e l a y e r s h a v e b e e n4p4 r4
5o d u c e d b y h i g h - r a t e s p u t t e r i n g o n t o
glass with and without surface c o a t i n g s . ' T h i s t y p e o f A R l a y e r is s t a b l e in a
h u m i d a t m o s p h e r e , u n d e r u l t r a v i o l e t i r r a d i t i o n , a n d d u r i n g h e a t i n g to h i g h
t e m p e r a t u r e s in air. F i g u r e 3 2 s h o w s s p e c t r a l t r a n s m i t t a n c e a n d r e f l e c t a n c e for a
1 m m t h i c k g l a s s w i t h a n d w i t h o u t a n A R l a y e r o n o n e s i d e . It is s e e n that T i m is
U
i n c r e a s e d b y a f e w p e r c e n t a n d that R i m is s t r o n g l y d e c r e a s e d b y t h e a l u m i n i u m
U
o x y f l u o r i d e . F i g u r e 3 3 r e p o r t s o n a n o t h e r a p p l i c a t i o n in w h i c h a 0 . 0 8 μ ι η t h i c k
a l u m i n i u m o x y f l u o r i d e A R l a y e r is p u t o n 4 m m f l o a t g l a s s h a v i n g a c o m m e r c i a l
T
B i 2 0 3 / A g / B i 2 0 3 c o a t i n g . T h e full m u l t i l a y e r s t r u c t u r e is c h a r a c t e r i z e d b y
l u m « 8 4 %, T i « 6 7 % a n d R i
s o um« 4 %. B e f o r e t h e A R l a y e r w a s a p p l i e d , t h e
« 7 7 %, T i « 61 % a n d R i
coated glass had T i
um s o um- 11 %. H e n c e t h e A R
treatment enhances T i b y 7 % a n d T i b y 6 %, a n d d e c r e a s e s R i b y 7 %.
um s o um
* 100|
Τ
90
•Ό
C
Φ AR coated
uncoated -
φ
υ
c
φ
+·*
ο
φ
Η— _L _L _L
Φ
0.4 0.5 0.6 0.7 0.8
Wavelength (μπι)
Fig. 3 2 . Spectral normal transmittance (T) and near normal
r e f l e c t a n c e ( R ) m e a s u r e d for u n c o a t e d ( d a s h e d c u r v e s )
and aluminium oxyfluoride coated (solid curves) glass.
(From Ref. 44).
A l u m i n i u m o x y f l u o r i d e c a n b e u s e d a l s o for A R t r e a t m e n t o f d o p e d o x i d e
s e m i c o n d u c t o r c o a t i n g s . H o w e v e r , for s p u t t e r - d e p o s i t e d c o a t i n g s o f t h o s e
m a t e r i a l s it m a y b e m o r e c o n v e n i e n t to a n t i r e f l e c t b y a n o x y f l u o r i d e b a s e d o n the
s a m e m a t e r i a l as t h e o n e in t h e o x i d e . A r e c e n t l y s t u d i e d e x a m p l e is a n In2C>3:Sn
100
pφ 80|
ο
c AR coated
<° base coated
S 60|-
I floatglass
φ
c
(0
12
* 4h
«•-
φ
ce
•0.3 0.4 0.5 0.6 0.7 0.8

Wavelength (μιη)
Fig. 3 3 . S p e c t r a l n o r m a l t r a n s m i t t a n c e ( T ) a n d n e a r n o r m a l réflec-
t a n c e ( R ) m e a s u r e d for u n c o a t e d floatglass ( d o t t e d c u r v e ) , for
the s a m e g l a s s w i t h a B i 0 3 / A g / B i 0 3 c o a t i n g ( d a s h e d
2 2
c u r v e s ) a n d after a p p l i c a t i o n o f a final a l u m i n i u m o x y f l u o r i d e
l a y e r (solid c u r v e s ) . T h e b a s e c o a t e d g l a s s c o r r e s p o n d s to t h e
product I plus Neutral, supplied by Interpane, Germany.
(From Ref. 4 4 ) .
115
coating with an antireflecting indium-tin oxyfluoride o v e r l a y e r . The AR
treatment increased T i f r o m 8 2 to 8 9 % a n d d e c r e a s e d R i from 13 to 5 %.
um um
D i e l e c t r i c A R l a y e r s t e n d to e n h a n c e Etherm for n o b l e - m e t a l b a s e d a s w e l l as for
d o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s , b u t t h e effect is o n t h e ~ 1 % l e v e l , w h i c h is
o f little p r a c t8 i c1a1l2s5i g n i f i c a n c e . F u r t h e r , t h e A R l a y e r s can b e u s e d to a v o i d
iridescence ' 135
- p a r t i c u l a r l y for specified v i e w i n g c o n d i t i o n s - a n d t o m a k e light
s c a t t e r i n g ( h a z e ) less a p p a r e n t .
A n o t h e r p o s s i b i l i t y to antireflect g l a s s is b y e t c h i n g its s u r f a c e s w i t h fluosilicic a c i d

so that a p o1r o u5s7 silica 4 - 1l a y5e r , w i t h l o w refractive i n d e x a n d w e l l - d e f i n e d t h i c k n e s s ,
is f o r m e d . F i g u r e 3 4 s h o w s r e f l e c t a n c e o f 3 - m m - t h i c k floatglass w i t h a n d
w i t h o u t a d o u b l e - s i d e d A R t r e a t m e n t . It is s e e n that t h e r e f l e c t a n c e c a n b e v e r y
l o w o v e r a l a r g e p a r t o f t h e l u m i n o u s s p e c t r a l r a n g e . T h e silica l a y e r is a l m o s t
n o n - a b s o r b i n g , a n d h e n c e t h e r e is a c o n c o m i t a n t i n c r e a s e in T i . T h e A R l a y e r s
u m
can b e created by liquid-phase and vapour-phase etching; potentially both o f these
a r e l o w - c o s t t e c h n i q u e s s u i t a b l e for l a r g e - a r e a w i n d o w s .
101 ι I ι I ι I 1 1 1 1
^ J " " • * · . . . . . . . Floatglass

e
g I /AR coated
Φ I /
1 Χ
Φ I /
φ 1 /
ce 1 /
Θ! ι Ι ^ Λ 1
0 0.5 1 1.5 2 2.5
Wavelength (μιη)
Fig. 3 4 . S p e c t r a l n e a r - n o r m a l r e f l e c t a n c e for f l o a t g l a s s ( d o t t e d
c u r v e ) , a n d for s u c h g l a s s e t c h e d in fluosilicic a c i d ( s o l i d
c u r v e ) . ( F r o m Ref. 1 5 6 ) .
V. MATERIALS INTERPOSED BETWEEN THE W I N D O W PANES
A. Gases
H e r m e t i c a l l y s e a l e d d o u b l y , o r m u l t i p l y , g l a z e d w i n d o w s m a k e it p o s s i b l e to
i n c o r p o r a t e a g a s o t h e r t h a n air b e t w e e n t h e g l a s s p a n e s . In this w a y o n e c a n alter
t h e h e a t transfer b y t h e r m a l r a d i a t i o n , c o n d u c t i o n a n d c o n v e c t i o n a n d t h e r e b y
e n h a n c e t h e e n e r g y efficiency. T h e p o s s i b l e i m p r o v e m e n t s a r e i l l u s t r a t e d in
F i g u r e 3 5 , w h i c h g i v e s k - v a l u e s m e a s u r e d as a function o f t h e d i s t a n 1 c e85b e t w e e n
2
t w o g l a s s e s for air a n d five different c h e m i c a l l y w e l l s p e c i f i e d g a s e s . T h e data
w e r e r e c o r d e d at the c e n t e r o f a ~ 0.6 m vertical s q u a r e test w i n d o w w i t h g a s
s p a c i n g s o f 6, 9 , 1 2 , 16 a n d 2 0 m m . T h e u p p e r set o f c u r v e s refers to n o r m a l
u n c o a t e d g l a s s w i t h Etherm ~ 8 5 %. F o r air, a r g o n ( A r ) , a n d c a r b o n d i o x i d e ( C 0 2 ) ,
t h e r e is a m o n o t o n i e d r o p in t h e k - v a l u e w i t h i n c r e a s i n g s p a c i n g s, w h e r e a s for
sulfur h e x a f l u o r i d e ( S F é ) , F r e o n 1 2 (CI2CF2) a n d sulfur d i o x i d e (SO2), t h e k - v a l u e
is m u c h less d e p e n d e n t o n s. A t s = 12 m m , w h i c h is a c o m m o n v a 2 l u e _for1 s e a l e d
w i n d o w s , air, a r g o n , a n d C O 2 yield k - v a l u e s o f 3.0, 2 . 8 a n d 2.6 W n r K ,
r e s p e c t i v e l y . H e n c e the i m p r o v e m e n t g i v e n b y t h e g a s is o n t h e ~ 10 % l e v e l for
uncoated glass.
ι 1 1 1 1 1 1 1 1 1
Air -
Ar
SF
E
• Y . co2
- J \ CI CF -
2 2
. J . so2
rT- 3- « \ *' · . -
. o
a>
(0
i » \ \
JC \ ·
2— «J .^T * -
O) \ \
x *.·.
N
S . \
<
1 - 1 · Kr
ι ι 1 1 ι ι ι 1 ι I
0 10 20
Width of g a s slab (mm)
Fig. 3 5 . k - v a l u e v s . g l a s s s p a c i n g m e a s u r e d for d o u b l e g l a z e d test

windows. Variously dashed and dotted curves refer to the
s h o w n g a s e s u s e d as fillings b e t w e e n t h e g l a s s p a n e s . T h e
u p p e r set o f c u r v e s w a s r e c o r d e d w i t h u n c o a t e d g l a s s . T h e
l o w e r s e t o f c u r v e s c o r r e s p o n d s t o o n e o f t h e g l a s s surfaces
h a v i n g a g o l d c o a t i n g . A s i n g l e d a t a p o i n t is s h o w n for
k r y p t o n g a s . ( F r o m Ref. 1 5 8 ) .
G a s fillings a r e c o n v e n i e n t l y c o m b i n e d w i t h l o1 w -5 1e 9
m8
5i t t a n c e c o a t i n g s b a s e d o n
noble metals or doped oxide s e m i c o n d u c t o r s . ' T h e lower part o f Fig. 3 5
s h o w s r e s u l t s o b t a i n e d w i t h a w i n d o w for w hβi c h o n e o f t h e s u r f a c e s f a c i n g the g a s
e n c l o s u r e w a s g o l d c o a t e d a n d h a d Etherm 6.5 %. W h e n t h e r a d i a t i v e c o m p o n e n t
to t h e h e a t transfer is m i n i m i z e d , t h e c h o i c e o f a g a s w i t h l o w t h e r m a l c o n d u c t i o n
a n d c o n v e c t i o n b e c o m e s critical, a n d t h e r e l a t i v e i m p r o v e m e n t p o s s i b l e b y s e l e c -
ting a p r o p e r g a s b e c o m e s e n l a r g e d . It is f o u n d that t h e k - v a l u e d r o p s w i t h i n c r e a -
s i n g s for air a n d a r g o n , a n d that t h e o t h e r g a s e s g i v e a m o r e c o m p l i c a t e d b e h a -
v i o u r o r e v e n a r i s e-2o f _t1h e k - v a l u e w i t h i n c r e a s i n g s. A t s = 1 2 m m o n e finds a2 1
k - v a l u e o f 1.8 W m K for air - in g o o d a g r e e m e n t w i t h F i g . 2 - a n d 1.5 W m ~ K "
for a r g o n . T h u s a n i m p r o v e m e n t o n t h e 2 0 % l e v e l c a n b e o b t a i n e d b y g a s filling
together with l o w emittance coated glass. For krypton (Kr) gas the k-value can b e
as l o w a s 0 . 9 8 W m -2K _1a t s = 1 2 m m . X e n o n ( X e ) is e x p e c t e d t o b e e v e n b e t t e r .
G a s m i x t u r e s a r e a l s o o f i n t e r e s t for o b t a i n i n g l o w k - v a l u e s . 185F i g u r e 3 6 s h o w s
t h a t a c o m b i n a t i o n o f a r g o n a n d S F Ô c a n g i v e 2.7 W m ^ K -1at ~ 3 0 v o l . % S F 6 in
t h e c a s e o f u n c o a t e d g l a s s a n d s = 1 2 m m . F o r g o l d - c o a t e d g l a s s , t h e k - v a l u e is
a l m o s t u n a f f e c t e d b y S F é m i x t u r e s u p to ~ 2 0 v o l . %. A m i x i n g o f S F 6 a n d air c a n
a l s o b e o f a d v a n t a g e . T h e a d d i t i o n o f S F 6 l e a d s to b e t t e r s o u n d i n s u l a t i o n , w h i c h
is a n o t h e r b e n e f i t J 60
3
L>N Uncoated glass
2.5
Ar-SF6
CM Air-SF6
Ε
φ
>
X ,<y ;
/ Au-coated glass
1.5- /
0 50 100
SF^ content (vol.%)
6
Fig. 3 6 . k - v a l u e v s . r e l a t i v e S F ^ c o n t e n t m e a s u r e d for A r - S F ^
g a s m i x t u r e s . ( F r o m Ref. 1 5 8 ) .
R e c e n t l y a t t e m p t s h a v e b e e n m a d e 1t 1
o 6d e c r e a s e t h e r a d i a t i v e h e a t t r a n s f e r in w i n -
dows b y infrared-absorbing g a s e s . M a n y gases - including the earlier mentioned
S F 6 a n d CI2CF2 - h a v e s t r o n g b u t n a r r o w a b s o r p t i o n b a n d s in t h e 3 < λ < 5 0 μπι
range, and b y combining several component gases one can minimize the heat
transfer. A l o w e s t p o s s i b l e Ttherm (0) o f - 7 0 % w a s o b t a i n e d a c r o s s a 1 0 m m g a s
l a y e r . F i g u r e 3 7 s h o w s the infrared t r a n s m i t t a n c e s p e c t r u m for a m i x t u r e o f four
different freons a n d SF^. A n a l o g o u s r e s u l t s c a n b e o b t a i n e d b y n o n - c h l o r i n a t e d
g a s e s , w h i c h a r e n o t h a r m f u l to a t m o s p h e r i c o z o n e .
T h e c o s t o f g a s e s is r o u g l y 0.01 for a r g o n , 0.1 for sulfur h e x a f l u o r i d e , 1 for k r y p t o n

a n d 10 for x3e n o n in u n i t s o f U S D p e r litre a n d a s s u m i n g a n a n n u a l c o n s u m p t i o n
o f < 1 0 0 0 m at t h e filling site. F o r k r y p t o n a n d x e n o n , g l o b a l a v a i l a b i l i t y p r e c l u -
d e s l a r g e - s c a l e uses. T h e c o s t o f i n f r a r e d - a b s o r b i n g g a s is ~ 0.2 U S D p e r litre. T h e
filling c o s t for a s t a n d a r d w i n d o w is ~ 0.25 U S D o n t h e p r o d u c t i o n l i n e a n d ~1
U S D o f f t h e p r o d u c t i o n line.
1 1 1 1—j 1 1 1—r
i o o { Λ Λ Ν Λ Γ Ν Γ\\ ~7T lf\—/
« - τΐ i l
1 40-
g -
Freon 12
Freon 13
γ |
I
I
•
:
2 20- Freon 22 I
I I I I I I I I L J J
*~ 25 vol. % of each J L
5 6 7 8 9 10 20 50
Wavelength (μιη)
Fig. 3 7 . Spectral normal transmittance through a 10-mm-thick
layer o f a gas mixture with the s h o w n composition.
(From Ref. 161).
B. Solid Transparent Insulation Materials
T h e r e is a w i d e r a n g e o f s o l i d m a t e r i a l s w h i c h c a n b e i n t e r p o s e d b e t w e e n g l a s s
p a n e s in o r d e r to i m p r o v e t h e t h e r m a l i n s u l a t i o n o f w i n d o w s . T h e e a r l i e r
c h a p t e r o n T r a n s p a r e n t I n s u l a t i o n M a t e r i a l s c o v e r s this s u b j e c t i n d e t a i l , a n d the
p r e s e n t b r i e f d i s c u s s i o n is i n c l u d e d o n l y for c o m p l e t e n e s s . F i g u r e 3 8 g i v e s a
c o n v e n i e n t s u b d i v i s i o n i n t o four g r o u p s o f (i) thin flexible p o l y m e r foils, (ii)
p o l y m e r h o n e y c o m b m a t e r i a l s , (iii) b u b b l e s , f o a m s a n d fibres, a n d (iv) i n o r g a n i c
m i c r o p o r o u s m a t e r i a l s , e s p e c i a l l y silica a e r o g e l s . I f t h e h o n e y c o m b c r o s s - s e c t i o n is
s m a l l c o m p a r e d to the cell l e n g t h , o n e m a y s p e a k o f a c a p i l l a r y s t r u c t u r e .
M a t e r i a l s (i) a n d (iv) c a n b e a l m o s t i n v i s i b l e to t h e e y e , w h e r e a s m a t e r i a l s (ii) a n d
(iii) c a u s e s t r o n g r e f l e c t i n g effects. H e n c e t h e " m a c r o p o r o u s " h o n e y c o m b s ,

b u b b l e s , f o a m s a n d fibres d o n o t g i v e a g o o d v i s u a l i n d o o r - o u t d o o r c o n t a c t , b u t
12a6p p l i c a t i o n is t h o u g h t t o b e in
t h e y m a y b e u s e d to p r o v i d e l i g h t i n g ; t h e i r m a i n
innovative solar collectors and wall c l a d d i n g s . M a t e r i a l s (ii) a n d (iv) a l l o w , in
principle, very high solar energy throughput. Detailed 1 r e3p6 o r t s o n s o l i d14 6
trans-
parent insulation materials have been given b y P f l u g e r and Platzer, as w e l l
as in a n e a r l i e r c h a p t e r o f this b o o k .
F l e x i b l e foils c a n b e m o u n t e d b e t w e e n g l a s s p a n e s b y u s e o f f r a m e s w h i c h m a i n -
t a i n t h e m a t e r i a l i n p e r m a n e n t t e n s i o n . F o i l s h a v e t h e i r m a i n a p p l i c a t i o n as a
carrier for a c o a t i n g d e v i s e d for g i v i n g a h i g h T i m / T o l r a t i o , a s r e q u i r e d for a
U S
w a r m c l i m a t e , o r for g i v i n g a h i g h T i t o g e t h e r w i t h a l o w Etherm/ as r e q u i r e d for
s o
a c o l d c l i m a t e . T h u s o n e c a n c r e a t e a l i g h t - w e i g h t m u l t i p l e g l a z i n g in c o n j u n c t i o n
w i t h e n e r g y efficient c o a t i n g s b y i n c o r p o r a t i n g o n l y t w o p a n e s o f u n c o a t e d g l a s s .
C l e a r p o l y e s t e r foil w i t h l o w s u r f a c e r o u g h n e s s is w e l l s u i t e d a s a s u b s t r a t e
m a t e r i a l for n o b l e - m e t a l b a s e d a n d d o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s . S p u t t e r
t e c h n o l o g y is often a p p l i e d in s u c h a w a y that a n e n t i r e roll o f p l a s t i c w e b is p l a c e d
in t h e v a c u u m t a n k a n d is w o u n d o v e r to a n o t h e r roll s o that t h e m a t e r i a l p a s s e s
u n i f o r m l y n e a r t h e t a r g e t ( s ) . T h e t e c h n i q u e is r e f e r r e d to a s "roll c o a t i n g " .
N o r m a l p l a s t i c s m u s t r e m a i n at < 1 0 0 ° C d u r i n g t h e c o a t i n g p r o c e s s .
Material
between
window panes:
s,
$^ ί p„m 109^ foam
-
^ Foil —^ÔfW
I^Ç&I—~~ fibres
Microporous
- 4 = k ^ J n i material
(aerogel)
\g—^*<2 ^ Honeycomb g. %
Fig. 3 8 . P r i n c i p l e s o f four different t y p e s o f s o l i d t r a n s p a r e n t

insulation materials placed between two glass panes.
A r r o w s signify light r a y s . R e f l e c t i o n s at t h e g l a s s s u r f a c e s
are not shown. T h e classification follows Platzer and
W i t t w e r (Ref. 1 6 5 ) .
F i g u r e 3 9 s h o w s t r a n s m i t t a n c e a n d r e f l e c t a n c e for p o l y e s t e r foil 166w i t h t h r e e t y p e s o f

c o a t i n g s . T h e u p p e r p a r t refers to a S n 0 2 / A g / S n 0 2 c o a t i n g , w h o s e properties
a r e s i m i l a r t o t h o s e for T i C > 2 / A g / T i C > 2 r e p o r t e d i n F i g u r e 1 2 . S i l v e r - b a s e d 1c7o6 atings
with t w o chemically prepared dielectric layers have also been d e v e l o p e d . T h e1 8 6
m i d d l e a n d l o w e r p a r t s o f F i g . 3 9 s h o w d a1t9 a6for d o p e d ΠΊ2Ο3 f r o m H o w s o n et a l .
a n d d o p e d Z n O from J i n a n d G r a n q v i s t , r e s p e c t i v e l y . G e n e r a l l y s p e a k i n g , the
p r o p e r t i e s a r e s i m i l a r , t h o u g h n o t q u i t e as g o o d , as for a n a l o g o u s c o a t i n g s o n glass
(cf. F i g1u r e7 1 11707) . L o w - t e m p e r a t u r e t e c h n i q u e s a r e a v a i l a b l e a l s o for d o p e d
Sn02- ' T h e c o s t for c o a t i n g p l a s t i c foil is c o m p a r a b l e to t h e o n e for c o a t i n g
g l a s s p a n e s , at l e a s t for n o b l e - m e t a l b a s e d l a y e r s .
100 I ι ι ιι ι ~l I I I I M I
S n 0 2/ A g / S n 0 2
50
ol
100
ο
Φ
Φ
oc / \ / Doped ln 90~
•ο 50h
c
CO
ο
c ol
CO*
Φ 1001
ICO
c
50
_ι ι I ι ι ι 11 J ι ι I ι ι ill
0.2 0.5 1 2 5 10 20 50
Wavelength (μπι)
Fig. 3 9 . Spectral n o r m a l transmittance and near-normal reflec-
t a n c e m e a s u r e d for c l e a r p o l y e s t e r foil c o a t e d w i t h
S n 0 2 / A g / S n 0 2 , d o p e d Π Ι 2 Ο 3 , a n d Z n O : A l . C o m p i l e d from
Refs. 1 6 6 , 1 6 8 a n d 1 6 9 .
W e n o w t u r n to t h e c l a s s o f m a c r o p o r o u s m a t e r i a l s , i n c l u d i n g h o n e y c o m b s ,
c a p i l l a r i e s , f oda m s , b u b b l e s , fibres, etc. T r a n s m i t t a n c e for diffuse s o l a r i r r a d i a n c e ,
d e n o t e d T i , a n d k - v a l u e h a v e b e e n r e p o r t e d for n u m e r o u s c o n f i g u r a t i o n s in
s o
Refs. 1 7 2 a n d 1 7 3 . H o n e y c o m b s o f different t y p e s - m a d e d of polystyrol, polyamide,
p o l y v i n y l c h l o r i d e a n d p o l y c a r b o n a t e - t y p i1
cally g a v e T i b e t w e e n 71 and 4 5 %
s o
a n d k - v a l u e s b e t w e e n 1.3 a n d 0.9 W m ^ K * w h e n the t h i c k n e s s w a s ~ 1 0 c m .
F i g u r e 4 0 r e p1 o r2t 6
s s p e c t r a l t r a n s m i t t a n c e at diffuse i r r a d i a t i o n for t h e p o l y c a r b o n a t e
h o n edy c o m b . T h e t r a n s m i t t a n c e is l a r g e at 0.4d< λ < 1.6 μ ι η , w h i c h y i e l d s
T o l ~ 71 %. T h e t h i c k n e s s d e p e n d e n c e o f T i is o f o b v i o u s i n t e r e s t for
S s o
w i n d o w s . F i g u r e 4 1 s h o w s r e p r e s e n t a t i v e r e s u l t s for p o l y c a r b o1n3a7 te capillaries
d
w i t h 1.7 m m d i a m e t e r a n d for p o l y m e t h y l m e t h a c r y l a t e f o a m . For the capillary
m a t e r i a l s , T i is s e e n t o d r o p f r o m - 7 3 % at s 2 m a_
l1l t h i c k n e s s to - 6 0 % at 10 c m
s 12 o7
t h i c k n e s s ; t h e k - v a l u e s w e r e 1.45 a n d 0 . 7 9 W n r K at 6 a n d 1 0 c m t h i c k n e s s ,
r e s pd ectively. T h e foam layers display a m u c h stronger thickness dependence of
T o l / w h i c h d r o p s b e l o w 5 0 % w h e n the t h i cdk n e s s e x c e e d s ~ 2.5 c m . A t 1.6 c m
S
t h i c k n e s s , different f o a m t y p1e s1s h2o 7 wed T i between 60 and 4 8 % and k-values
s o
b e t w e e n 3.1 a n d 3.6 W m * .
1 11 11 1 1 1 1 1 1
1 0 0 ι I ι ι I ' Π I '
Φ
υ
c
(D
1 50
C
φ
0.5 1 1.5 2.5

Wavelength (μπι)
Fig. 4 0 . S p e c t r a l t r a n s m i t t a n c e for diffuse i r r a d i a n c e m e a s u r e d
for a 1 0 - m m - t h i c k r e c t a n g u l a r p o l y c a r b o n a t e h o n e y c o m b
c o n s t r u c t e d f r o m foil o f 6 0 μιη a v e r a g e t h i c k n e s s . ( F r o m
Refs. 1 6 2 a n d 1 7 4 ) .
B y g o i n g f r o m a m a c r o p o r o u s to a m i c r o p o r o u s s t r u c t u r e - w i t h i n h o m o g e n e i t i e s
m u c h less t h a n t h e w a v e l e n g t h s o f v i s i b l e light - 1o5n7e c a n a c h i e v e a t r a n s p a r e n t
solid material with superior thermal i n s u l a t i o n . A p a r t i c u l a r l y i n t1e r e7
1s7t i67n g
m a t e r i a l c a n b e o b t a i n e d b y s u p e r c r i t i c a l d r y i n g o f c o l l o i d a l silica g e l . ' The
e n s u i n g s u b s t a n c e , c a l l e d a silica a e r o g e l , c o n s i s t s o f silica p a r t i c l e s o f s i z e ~ 1 n m
i n t e r c o n n e c t e d s o that a l o o s e l y p a c k e d s t r u c t u3 r e w i t h p o r e s i z e s o f 1 to 1 0 03n m is
f o r m e d . T h e a e r o g e l d e n s i t y is 7 0 to 2 7 0 k g n r , c o m p a r e d w i t h 2 2 0 0 k g n r for
~ 100 : ι ι " f ι — ι — ι — ι — ' — ι
! \ "
p - _ Capillaries
c \^
2 50 - \
I ^^^^ Foam
φ
CO - ^ ^ • « ^ ^
- * ^ ^ ^ ^
3 """"" —
«*- _ _
û
ol , I ι I
Thickness (cm), I , I ι
0 2 4 6 8 10
Fig. 4 1 . T r a n s m i t t a n c e for diffuse s o l a r i r r a d i a t i o n v s . t h i c k n e s s
m e a s u r e d for m a t e r i a l s c o m p r i s i n g p o l y c a r b o n a t e c a p i l l a r i e s
and polymethylmethacrylate foam. (From Ref. 173).
n o n - p o r o u s silica g l a s s , i m p l y i n g 1a8p
7o r o s i t y u p to 9 7 %. M a n y p r o p e r t i e s o f silica
aerogels are compiled by F r i c k e . L a r g e - s c a l e p r o d u c t i o n is d i s c u s s e d i n Refs. 1 7 9
a n d 1 8 0 . Silica a e r o g e l c a n b e p r e p a r e d b o t h as t r a n s p a r e n t tiles a n d as a
translucent granular material.
a n
A high T i d T i t o g e t h e r w i t h a l o w k - v a l u e m a k e s silica a e r o g e l o f g r e a t
1um
i n t e r e s t for 8e1n5e18r g y -se f of i c i e n t w i n d o w s w i t h a n d w i t h o u t l o w - e m i t t a n c e
coating. " F u r t h e r , the m e c h a n i c a l r i g i d i t y p e r m i t s its u s e as a s p a c e r in
evacu 1a3t8e d w i n d o w s . F i g u r e 4 2 illustrates s p e c t r a l t r a n s m i t t a n c e for a 4 m m thick
tile. T h e t r a n s m i t t a n c e e x c e e d s 8 0 % at 0.6 < λ < 2 . 2 μιη b u t d r o p s at λ < 0.6 d u e
to s c a t t e r i n g f r o m d e n s i t y v a r i a t i o n s . T r a n s m i t t a n c e s p e c t r a for g r a n u l a r a e r o g e l s
h a v e b e e n r e p o r t e d in R e f . 1 8 2 . F i g u r e 4 3 s h o w s t h e t h i c k n e s s d e p e n d e n c e o f the
t r a n s m i t t a n c e , at d i r e c t a1n d7 1248
diffuse s o l a r i r r a d i a t i o n , t h r o u g h w i n d o w s filled w i t h
g r a n u l a r silica a e r o g e l . ' A s e x p e c t e d , t h e t r a n s m i t t a n c e falls off w i t h
i n c r e a s i n g t h i c k n e s s ; at 1 c m o n e finds T i « 6 9 % a n d T i d « 5 5 %. T h e k - v a l u e
s o s o
o f this k i n d o f m a t e r i a l is s h o w n in F i g . 4 4 as a function o f t h e g a s p r e s s u r e in 1 the48
a e r o g e l a n d for t w o m a g n i t u d e s o f t h e e m i t t a n c e o f t h e s u r r o u n d i n g s u r f a c e s .
T h e m e a s u r e m e n t s w e r e d o n e at ~ 24 0_°1C . W i t h n i t r o g e n g a s at a t m o s p h e r i c
p r e s s u r e , t h e k - v a l u e is ~ 1.8 W m ~ K for a 1.5 c m t h i c k l a y e r o f g r a n u l e s . D e c r e a -
sing the gas pressure m a k e s the k-value drop. For pressures b e l o w 1 m b a r the
r a d i a t i v e h e a t e x c h a n g e b e c o m e s o f s i g n i f i c a n c e - p a r t i c u l a r l y at 3 < λ < 5 μιη 3 - and
hence an enclosure with low emittance yields a depressed k-value. A t 10~ mbar,
t h e k - v a l u e is ~ 0.9 for a n e m i t t a n c e o f 0.9 ( r e p r e s e n t a t i v e o f u n c o a t e d g l a s s ) a n d
~ 0.6 for a n e m i t t a n c e o f 0.05 ( r e p r e s e n t a t i v e o f l o w 1-4e8m i t t a n c e - c o a t e d g l a s s ) . F o r
0°C o n e c a n e x t r a p o l a t e f r o m d a t a b y F r i c k e et a l . that t h e c o r r e s p o n d i n g
k - v a l u e s w o u l d b e 0.7 a n d 0.5, r e s p e c t i v e l y . G r a n u l a r silica a e r o g e l p r o d u c e d in
l a r g e q u a n t i t i e s is e x p e c t e d to c o s t a p p r o x i m a t e l y 1.8 U S D p e r litre.
1001 ι ι ι ι ι ι ι ιι
φ _ /
2 50 - /
ε _ /
CO /
c /
η - I
' Ql / ι 1 ι ι ι ι I ι ι ι ι I ι ι ι ι I ι ι ι ι I ι ι\» ι I ι
0.5 1 1.5 2 2.5 3
Wavelength (μιη)
Fig. 4 2 . S p e c t r a l t r a n s m i t t a n c e m e a s u r e d for a 4 m m t h i c k s i l i c a
a e r o g e l tile. T h e m a t e r i a l w a s h e a t t r e a t e d at 5 0 0 ° C in o r d e r
to e n h a n c e t h e t r a n s m i t t a n c e b y t h e r e m o v a l o f o r g a n i c
r e s i d u e s a n d w a t e r . ( F r o m Ref. 1 8 3 ) .
100 Τ
τ
φ
ο
ε so Direct
(0
c
φ
Diffuse
JL
Thickness (cm)
Fig. 4 3 . S o l a r t r a n s m i t t a n c e v s . t h i c k n e s s m e a s u r e d for
g r a n u l a r silica a e r o g e l s a m p l e s . T h e c u r v e s refer to
d i r e c t i n c i d e n c e (i.e., T i ) a n d diffuse i n c i d e n c e
s o
(i.e., T d ) . ( F r o m Refs. 1 7 4 a n d 1 8 2 ) .
s o l
I n s t e a d o f h a v i n g a e r o g e l s p a c e r s in e v a c u a t e d w i n d o w s , it is p o s s i b l e to u s e s m a l l
s p h e r i c a l g l a-3
s s s u p p o r t s . S u c h a w i n d o w , w i t h l o w e m1i t t a n c e c o a t i n g a n d e v a c u -
a t e d to < 1 0 m b a r , c a n y i e l 2 d a k - v a l u e1o f880.6
7 6 W m ^ K " in a c o m p a c t ( < 1 c m thick)
1
a n d l i g h t - w e i g h t (~ 1 4 k g n r ) d e s i g n . ^8 8 Laser edge sealing o f the evacuated
w i n d o w is a p r o m i s i n g t e c h n i q u e .
I ' I ' I ' I—^1
^ 2-
-Φ "
E..
therm
=0.9 X
/S/
1 ~ ^ ^ ^ / θ . 0 5
- 4 - 2 0 2
10 10 10 10
Gas pressure (mbar)
Fig. 4 4 . k - v a l u e v s . p r e s s u r e o f n i t r o g e n g a s for a 1.5 c m t h i c k l a y e r o f
silica a e r o g e l . T h e c u r v e s refer to t h e s h o w n m a g n i t u d e s o f
t h e t h e r m a l e m i t t a n c e for t h e s u r f a c e s s u r r o u n d i n g t h e
areogel; they w e r e d r a w n through individual data points and
m a y b e s o m e w h a t u n c e r t a i n as r e g a r d s 3d e t a i l s . T h e a e r o g e l is
c h a r a c t e r i z e d b y a d e n s i t y o f 2 3 0 k g m~ a n d a g r a n u l e s i z e o f
3 m m . (From Ref. 184).
C Chromogenic Materials
C h r o m o g e n i c coatings on glass were discussed a b o v e with a focus on electrochro-

mics-based and thermochromic smart windows. This section discusses some
r e c e n t w o r k o n "thick" m a t e r i a l s w h i c h a l l o w d y n a m i c t h r o u g h p u t o f r a d i a n t
energy w h e n interposed between w i n d o w panes. Specifically, covered are
photochrom 18i c , t h e r m o c h r o m i c , a n d e l e c t r i c a l l y c o n t r o l l e d l i q u i d - c r y s t a l - b a s e d
materials.
P l a s t1
ic 8 s1h0e9e t o r foil w i t h photochromic a d d i t i v e s offer i n t e r e s t i n g p o s s i b i l i -
tés, ' a n d d e t a i l e d results h a v e b e e n g i v e n for s p i r o o x a z i n e in a h o s t o f
cellulose acetate butyrate. T h e material can b e produced b y injection molding.
Figure 4 5 shows darkening and clearing dynamics of T i
umfor a 1.5 m m thick sheet
at 2 0 ° C. It is s e e n that solar e x p o s u r e m a k e s T i
umd r o p f r o m 8 2 to 2 3 % in a b o u t
o n e m i n u t e . C l e a r i n g is s l o w e r , a n d it takes a b o u t 2 0 m i n u t e s to r e g a i n full
t r a n s m i t t a n c e . T h e d y n a m i c s a r e m u c h m o r e r a p i d t h a n for p h o t o c h r o m i c g l a s s
(cf. F i g . 5 ) . S p e c t r a l t r a n s m i t t a n c e in the 0.35 < λ < 0.75 μιη r a n g e is illustrated in
F i g . 4 6 for t h e s h e e t in fully c l e a r e d a n d in p a r t i a l l y d a r k e n e d states. D a r k e n i n g is
a s s o c i a t e d w i t h a b s o r p t i o n at 0.5 < λ < 0.7 μιη, w h i c h is a n a l o g o u s to t h e a b s o r p -
t i o n i n p h o t o c h r o m i c g l a s s (cf. F i g . 6 ) . T h e s p i r o o x a z i n e - i n d u c e d p h o t o c h r o m i s m
is t e m p e r a t u r e d e p e n d e n t to an u n d e s i r a b l e e x t e n t , a n d at 3 0 a n d 4 0 ° C t h e fully
d a r k e n e d state for the m a t e r i a l o f Fig. 4 5 c o r r e s p o n d s to T i
um« 4 0 a n d 7 0 %,
respectively.
1001 ι ι 1 1 1 1
Darkening Clearing
80- ^ -
φ /
I 60- /
ε /
COc -
//
Φ Ι
Φ* ι Ι
S 40- /
c II
Ë I
u I
20-
θΙ ι I ι I ι I
0 10 20 30
Time (minutes)
Fig. 4 5 . L u m i n o u s transmittance vs. time during darkening and

clearing o f a plastic sheet with photochromic additives.
(From Ref. 189).
Thermochromic c o n t r o l o f r a d i a t i o n t h r o uM
g h p u t c a n b e a c c o m p l i s h e d b y different 1 93 1 - 1 9
kinds of materials. P o l y m e r i c "cloud gels are well k n o w n in this c o n t e x t .
C l o u d i n g - i.e., transition to a diffusely s c a t t e r i n g s t a t e - c a n set i n a b o v e a c e r t a i n
t e m p e r a t u r e d u e to a r e v e r s i b l e t h e r m o c h e m i c a l d i s s o l u t i o n a n d a t h e r m a l l y
i n d u c e d m o d i f i c a t i o n in t h e l e n g t h o f the p o l y m e r m o l1 e3c u9l e s . T h e c l o u d p o i n t
can b e r e g u l a t e d to w i t h i n 1.5°C in t h e 9 to 9 0 ° C r a n g e . Figure 47 shows
transmission of direct plus scattered radiation through a 1 m m thick cloud gel
layer interposed b e t w e e n two glass panes. Both the luminous and the solar
t r a n s m i t t a n c e d r o p b y ~ 5 0 % w h e n t h e c l o u d p o i n t is e x c e e d e d . T h e m a t e r i a l has2
to b e u s e d in a s e a l e d w i n d o w . Its cost in a w i n d o w c a n b e less t h a n 1.80 U S D / m .
O n t h e n e g a t i v e s i d e , w e n o t e that if t h e r m a l g r a d i e n t s e x i s t o v e r a c l o u d - g e l -
c o n t a i n i n g w i n d o w t h e s e m a y m a n i f e s t t h e m s e l v e s as a r e a s w i t h c l e a r a n d c l o u d y
a p p e a r a n c e s . A p a r t f r o1m 49c l o u d g e l s , t h e r m o c h r o m i c l i q u i d / f i b r e c o m p o s i t e s h a v e
been studied r e c e n t l y .
1 0 0 | 1 1 1 1 1 1
Clear
80- ^ ^ f
S 6 0 - \ Dark /
| 40— / \ / —
20- / \ y
Ol L_J ι I ι I ι l
0.4 0.5 0.6 0.7
W a v e l e n g t h (μιη)
Fig. 4 6 . S p e c t r a l n o r m a l t r a n s m i t t a n c e for a p l a s t i c s h e e t w i t h p h o t o -
c h r o m i c a d d i t i v e s in c l e a r a n d d a r k states. ( F r o m R e f . 1 8 9 ) .
1001 ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι I I II
φ 60
υ
c
CO
Ε
g 40
CO Clouded
20
ι I ι ι ι ι 1 ι ι ι ι I ι ι ι
0.5 1 1.5 2.5
W a v e l e n g t h (μπι)
Fig. 4 7 . S p e c t r a l total (direct a n d s c a t t e r e d ) t r a n s m i t t a n c e t h r o u g h

a c l o u d g e l l a y e r b e t w e e n g l a s s p a n e s . T h e c u r v e s refer to
a low-temperature clear state and a high-temperature
c l o u d e d state. ( F r o m Ref. 1 9 3 ) .
E l e c t r i c a l l y c o n t r o l l e d liquid-crystal-based materials can switch b e t w e e n a transpa-

r e n t s t a t e a n1 d a9 1h6i5 9
g h l y s c a t t e r i n g s t a t e in a w a y p r i n c i p a l l y s i m i l a r to t h e o n e for
cloud g e l s . ' A material which recently has been commercialized consists of a
p o l y m e r l a y e r w i t h m i c r o m e t r e - s i z e d c a v i t i e s c o n t a i n i n g a n e m a t i c l i q u i d crystal.
T h i s l a y e r is l a m i n a t e d b e t w e e n t w o I n 2 0 3 : S n - c o a t e d p o l y e s t e r foils s e r v i n g as
e x t e n d e d e l e c t r o d e s . A p p l y i n g a v o l t a g e o v e r t h e e l e c t r o d e s , o n e c a n a l i g n the
l i q u i d c r y s t a l m o l e c u l e s a n d t h e r e b y o b t a i n r e f r a c t i v e - i n d e x - m a t c h i n g b e t w e e n the
inclusions and the surrounding polymer matrix. This represents the transparent
s t a t e o f t h e m a t e r i a l . I n t h e a b s e n c e o f an e l e c t r i c field, t h e l i q u i d c r y s t a l m o l e c u l e s
b e c o m e randomly oriented, which creates refractive-index-mismatch and hence
strong scattering. Figure 48 shows transmission of direct and scattered radiation
t h r o u g h this t y p e o f m a t e r i a l in t h e u n p o w e r e d s t a t e a n d w h e n a 6 0 H z 1 0 0 V
s q u a r e w a v e is a p p l i e d . A s w i -2 t c h i n g b e t w e e n 8 2 a n d 6 2 % t r a n s m i s s i o n is p o s s i b l e .
A n e l e c t r i c p o w e r o f < 2 0 W i n is n e e d e d for o p e r a t i n g t h e w i n d o w .
1 1
1 ι ι ι ι ι 1 1 1 1 J 1 1 I 1 I 1 1
Powered
50
Unpowered
—£ γ
J ι 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ι I ι .
0.5 1 1.5 2
Wavelength (μπι)
Fig. 4 8 . S p e c t r a l total (direct a n d s c a t t e r e d ) t r a n s m i t t a n c e t h r o u g h a
liquid-crystal-based material laminated onto 3.2-mm-thick
w i n d o w g l a s s . T h e c u r v e s refer to u n p o w e r e d ( o p a q u e ) a n d
p o w e r e d ( t r a n s p a r e n t ) states. ( F r o m R e f . 1 9 6 ) .
VI. CONCLUSIONS AND OUTLOOK
T h i s c h a p t e r h a s e m b r a c e d a l a r g e n u m b e r o f p o s s i b i l i t i e s for a c h i e v i n g t h e
e n e r g y efficiency o f a r c h i t e c t u r a l w i n d o w s . T h i s m u l t i p l i c i t y o f o p t i o n s is e a s i l y
understood since
(i) e n e r g y efficiency m e a n s different t h i n g s in different c l i m a t e s ,

(ii) t h e r e a r e s e v e r a l p r i n c i p l e a p p r o a c h e s to e n e r g y efficiency w h i c h c a n b e
u t i l i z e d e i t h e r s e p a r a t e l y o r in c o n j u c t i o n , a n d
(iii) m a n y different m a t e r i a l s m a y b e useful for e a c h c l i m a t e a n d a p p r o a c h to
e n e r g y efficiency.
A n e n e r g y efficient w i n d o w m u s t i n c l u d e at l e a s t t w o glass p a n e s . F l o a t g l a s s is a
r a t h e r s t a n d a r d i z e d p r o d u c t b u t it s h o u l d b e k e p t in m i n d t h a t s p e c i a l q u a l i t i e s
w i t h l o w Fe2U3 c o n t e n t c a n y i e l d a s i g n i f i c a n t i m p r o v e m e n t o f t h e s o l a r e n e r g y
transmission.
T h i n coatings c a n m o d i f y t h e r a d i a t i v e p r o p e r t i e s o f t h e g l a s s s u r f a c e s in m a n y
different w a y s . T h u s o n e c a n u s e n o b l e - m e t a l b a s e d c o a t i n g s for b l o c k i n g t h e
t r a n s m i s s i o n o f infrared s o l a r r a d i a t i o n t h e r e b y c u t t i n g d o w n t h e h e a t i n g , o r o n e
can u s e n o b l e - m e t a l b a s e d o r d o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s for c o m b i n i n g
high transmission of solar radiation with l o w emission o f thermal radiation.
T h e s e c o a t i n g s a r e p r o d u c e d c o m m e r c i a l l y o n a l a r g e scale. N o b l e - m e t a l b a s e d
c o a t i n g s m u s t b e u s e d in h e r m e t i c a l l y s e a l e d e n v i r o n m e n t s , w h e r e a s d o p e d o x i d e
s e m i c o n d u c t o r s are i n e r t a n d r u g g e d . I r i d e s c e n c e a n d h a z e m a y b e p r o b l e m s for
d o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s , albeit n o t u n s u r m o u n t a b l e o n e s . C o a t i n g s
w i t h d y n a m i c p r o p e r t i e s - to b e u s e d in s m a r t w i n d o w s - a r e s u b j e c t to v i g o r o u s
r e s e a r c h efforts a n d are r a p i d l y a p p r o a c h i n g a s t a g e w h e r e c o m m e r c i a l i z a t i o n is
feasible. A l l - s o l i d - s t a t e e l e c t r o c h r o m i c s - b a s e d c o a t i n g s a r e o f p a r t i c u l a r interest.
L a b o r a t o r y s t u d i e s i n d i c a t e t h a t their t r a n s m i t t a n c e o f v i s i b l e light a n d s o l a r
e n e r g y c a n b e a l t e r e d g r a d u a l l y a n d r e v e r s i b l y b e t w e e n - 1 0 a n d - 8 0 % b y electric
p u l s e s ; t h e e n e r g y r e q u i r e m e n t is v e r y s m a l l . T h e r m o c h r o m i c c o a t i n g s is
a n o t h e r , m o r e r e m o t e , p o s s i b i l i t y . N o v e l a n t i r e f l e c t i o n c o a t i n g s s e e m to b e a b l e to
increase the transmittance and decrease the reflectance o f w i n d o w glass with and
w i t h o u t v a r i o u s types o f c o a t i n g s .
Materials interposed between the window panes can diminish the heat transfer
d u e to c o n d u c t i o n a n d c o n v e c t i o n . G a s e s , p a r t i c u l a r l y a r g o n a n d S F 6 , a s w e l l as
l o w - e m i t t a n c e - c o a t e d p o l y m e r foils a r e w e l l u n d e r s t o o d in this c o n t e x t . L o w -
d e n s i t y silica a e r o g e l tile is a n o v e l m a t e r i a l c a p a b l e o f g i v i n g an e x t r e m e l y l o w
h e a t transfer.
T h e k - v a l u e is o n e o f t h e p a r a m e t e r s w h i c h g o v e r n e n e r g y efficiency. It is
i l l u s t r a t i v e to f o l l o w its d e c r e a s e t h r o u g h t h e f o l l o w i n g s e r i e s o f m e a s u r e m e _
n t s2
._ 1
S t a r t i n g w i t h a s i n g l y g l a z e d w i n d o w a p e r t u2r e_o n1e h a s a k - v a l u e o f ~ 6 W m K ;
i n t r o d u c i n g d o u b2l e g1l a z i n g l e a d s to ~ 3 W m " K ; a d d i n g a l o w e m i t t a n c e c o a t i n g
gives - 1 . 8 W n r K 2 " _, a1n d a d d i n g a s u i t a b l e g a s in t h e s p a c e b e t w e e n t h e p a n e s
y i e l d s ~ 1.5 W m ~ K . W i t h a m o d e r a t e v a c u u m b e t w e e n t h e p a n e s , w h i c h
r e q u i r e s a s p a c e r 1o f for e x a m p l e silica a e r o g e l , o n e m a y r e a c h a n u l t i m a t e k - v a l u e
o f - 0.5 W m ^ K - .
C u r r e n t r e s e a r c h a n d d e v e l o p m e n t o n e n e r g y efficient w i n d o w s is l i k e l y to l e a d to
s i g n i f i c a n t c h a n g e s in f e n e s t r a t i o n . A n a s s e s s m e n t o f t h e s e m u s t b e a s u b j e c t i v e
o n e - b u t will n e v e r t h e l e s s b e a t t e m p t e d . N o b l e - m e t a l b a s e d c o a t i n g s a r e p r e s e n t l y
p r o d u c e d w i t h p r o p e r t i e s a p p r o a c h i n g the t h e o r e t i c a l o p t i m u m . R e s e a r c h o n
t e c h n o l o g i e s for m a k i n g t h i n n e r c o n t i n u o u s m e t a l l a y e r s t h a n t h o s e n o w
a v a i l a b l e m a y l e a d to a m a r g i n a l i m p r o v e m e n t in t r a n s m i t t a n c e a n d d r o p in cost.
D o p e d o x i d e s e m i c o n d u c t o r c o a t i n g s , p r o d u c e d b y l a r g e - a r e a t e c h n i q u e s , d o n o t yet
h a v e o p t i c a l p r o p e r t i e s w h i c h q u i t e m a t c h the t h e o r e t i c a l l i m i t s . R e f i n e m e n t s in
d e p o s i t i o n t e c h n o l o g y , p a r t i c u l a r l y in a d v a n c e d s p r a y p y r o l y s i s , m a y l e a d to l o w -
c o s t c o a t i n g s w i t h < 1 % l u m i n o u s a b s o r p t a n c e , n o4 d i s c e r n i b l e h a z e , l o w t h e r m a l
e m i t t a n c e , a n d e l e c t r i c a l r e s i s t i v i t y d o w n to ~ 1 0 ~ Ω c m . N o v e l Z n O - b a s e d
coatings are of interest since they can block s o m e o f the ultraviolet solar radiation
w h i c h m a y o t h e r w i s e c a u s e d e g r a d a t i o n o f plastics a n d textiles. E l e c t r o c h r o m i c s -
b a s e d c o a t i n g s w i l l r e m a i n as s u b j e c t s for i n t e n s e r e s e a r c h , a n d s e v e r a l n e w
transition metal oxide coatings and solid electrolytes (particularly polymeric ones)
a r e b e i n g i n v e s t i g a t e d . T h i s w i l l g i v e a b r o a d b a s i s for s e l e c t i n g a n o p t i m u m
device construction. Designs with two glasses, each having a two-layer coating,
laminated together b y a transparent polymeric electrolyte are easier to accomplish
t h a n five-layer d e s i g n s . R e c e n t r e s u l t s w i t h l a m i n a t e d d e v i c e s (cf. F i g u r e 2 4 ) p o i n t
t o w a r d s future l a r g e s c a l e e l e c t r o c h r o m i c s - b a s e d s m a r t w i n d o w s . H o w e v e r , a final
a s s e s s m e n t o f their u s e f u l n e s s m u s t a w a i t l o n g - t e r m e n v i r o n m e n t a l t e s t i n g w i t h
a f o c u s o n i r r e v e r s i b l e p h o t o c h r o m i c effects. F o r t h e r m o c h r o m i c c o a t i n g s t h e r e is
a n e e d for m o r e b a s i c r e s e a r c h . L o w - r e f r a c t i v e - i n d e x a n t i r e f l e c t i o n c o a t i n g s will b e
s t u d i e d w i t h a f o c u s o n t h e o p t i m i z a t i o n o f s p u t t e r c o n d i t i o n s for v a r i o u s m e t a l
o x y fluor i d e s .
G a s fillings w h i c h p r o d u c e a l o w h e a t transfer a r e w e l l k n o w n a n d w i d e l y u s e d .
J u d g i n g f r o m their p h y s i c a l a n d c h e m i c a l p r o p e r t i e s , k r y p t o n a n d x e n o n a r e the
b e s t , b u t g l o b a l a v a i l a b i l i t y p r e c l u d e s l a r g e - s c a l e u s e s . Silica a e r o g e l is o f
c o n s i d e r a b l e interest, b u t r e s e a r c h i n t o l o w - c o s t t e c h n o l o g i e s for l a r g e - s c a l e
p r o d u c t i o n o f t r a n s p a r e n t tiles o r p l a t e s is n e e d e d b e f o r e its p r a c t i c a l i t y c a n b e
ascertained.
T h e m o s t f a r - r e a c h i n g i m p l i c a t i o n o f t h e r e s e a r c h is that t h e r o l e o f t h e w i n d o w
m a y change. Instead of being a passive building component, which commonly
lets i n o r o u t t o o m u c h e n e r g y , it c a n b e c o m e an a c t i v e p a r t w h i c h r e g u l a t e s t h e
i n f l o w o f r a d i a n t e n e r g y in r e s p o n s e to d y n a m i c n e e d s w h i l e r e m a i n i n g t h e r m a l l y
w e l l i n s u l a t e d . S u c h a d e v e l o p m e n t is in k e e p i n g w i t h t o d a y ' s t e n d e n c i e s t o w a r d s
"intelligent buildings" e q u i p p e d with a d v a n c e d m e a s u r i n g a n d control
technologies.
Acknowledgement: M a n y p e o p l e h a v e r e a d t h e m a n u s c r i p t o f this p a p e r in its

v a r i o u s v e r s o n s . In p a r t i c u l a r w e a c k n o w l e d g e t h e helpful c o m m e n t s b y D r . G . A .
Niklasson, Chalmers University of Technology and Univeristy of Gothenburg,
Sweden, Dr. C.-G. Ribbing, University of Uppsala, Sweden, Dr. J.S.E.M. Svensson,
C o A T A B , S w e d e n , a n d D r . V . W i t t w e r , F r a u n h o f e r I n s t i t u t fur S o l a r e
Energiesysteme, Germany.
REFERENCES
1. C . G . G r a n q v i s t , in Physics of Non-Conventional Energy Sources

and Material Science for Energy, e d i t e d b y G . F u r l a n , N . A . M a n c i n i , A . A . M .
S a y i g h a n d B . O . S é r a p h i n ( W o r l d Scientific, S i n g a p o r e , 1 9 8 7 ) , p. 2 1 7 .
2. C . G . G r a n q v i s t , in Physics and Technology of Solar Energy, edited
b y H . P . G a r g et.al. ( R e i d e l , D o r d r e c h t , T h e N e t h e r l a n d s , 1 9 8 7 ) , V o l . 2 , p . 1 9 1 .
3. C . G . G r a n q v i s t , in Electricity: Efficient End-Use and New Generation
Technologies, and Their Planning Implications, edited by T.B. Johansson,
B. Bodlund and R.H. Williams (Lund University Press, Lund, Sweden,
1 9 8 9 ) , p. 8 9 .
Applications (SPIE Optical Engineering Press, Bellingham, U S A , 1989).
5. C . G . G r a n q v i s t , in Material Science and the Physics of Non-Conven-

tional Energy Sources, e d i t e d b y G . F u r l a n , D . N o b i l i , A . A . M . S a y i g h a n d
B . O . S é r a p h i n ( W o r l d Scientific, S i n g a p o r e , 1 9 8 9 ) , p . 1.
6. C M . L a m p e r t , i n Physics of Non-Conventional Energy Sources and
Materials Science for Energy, e d i t e d b y G . F u r l a n , N . A . M a n c i n i , A . A . M .
S a y i g h a n d B . O . S é r a p h i n ( W o r l d Scientific, S i n g a p o r e , 1 9 8 7 ) , p. 1 4 3 .
7. C M . L a m p e r t , in Materials Science and the Physics of Non-Conven-
tional Energy Sources, e d i t e d b y G . F u r l a n , D . N o b i l i , A . A . M . S a y i g h a n d
B . O . S é r a p h i n ( W o r l d Scientific, S i n g a p o r e , 1 9 8 9 ) , p. 4 5 .
8. K . Y a . K o n d r a t y e v , Radiation in the Atmosphere (Academic, N e w
York, 1969).
9. M . P . T h e k a e k a r a , in Solar Energy Engineering, edited by A.A.M.
S a y i g h ( A c a d e m i c , N e w Y o r k , 1 9 7 7 ) , p. 3 7 .
10. T.S. Eriksson and C.G. Granqvist, Appl. Opt. 2 1 , 4381 (1982).
11. G . W y s z e c k i a n d W . S . Stiles, Color Science, s e c o n d e d i t i o n ( W i l e y , N e w
Y o r k , 1 9 8 2 ) , p. 2 5 6 .
12. K . M . H a r t m a n n , in Biophysik, edited by W . H o p p e , W . L . L o h m a n n , H.
M a r k l a n d H . Z i e g l e r ( S p r i n g e r , Berlin, 1 9 7 7 ) , p. 2 1 4 .
13. C G . G r a n q v i s t , A p p l . O p t . 2 0 , 2 6 0 6 (1981).
14. M . R u b i n , R. C r e s w i c k a n d S. S e l k o w i t z , in Proc. Fifth National Passive
Solar Conf. ( P e r g a m o n , N e w Y o r k , 1 9 8 0 ) , p . 9 9 0 .
15. B . K a r l s s o n , T. K a r l s s o n a n d C.-G. R i b b i n g , J . T h e r m a l I n s u l a t i o n 7, 1 1 1
(1983).
16. E . B o l l i n a n d J . S c h m i d , in Advances in Solar Energy Technology, edited by
W . H . B l o s s a n d F . Pfisterer ( P e r g a m o n , O x f o r d , 1 9 8 8 ) , p. 3 5 0 3 .
17. B . K u n z a n d M . K u n z , in Advances in Solar Energy Technology, edited by
W . H . B l o s s a n d F . Pfisterer ( P e r g a m o n , O x f o r d , 1 9 8 8 ) , p. 3 5 4 5 .
18. C M . L a m p e r t a n d C . G . G r a n q v i s t , e d i t o r s , Large-Area Chromogenics:
Materials and Devices for Transmittance Control (SPIE Optical Engineering
Press, Bellingham, 1990).
19. J . S . E . M . S v e n s s o n a n d C . G . G r a n q v i s t , S o l a r E n e r g y M a t e r . 1 2 , 3 9 1 (1985).
20. R . S i e g e l a n d J . R . H o w e l l , Thermal Radiative Heat Transfer, second edition
(McGraw-Hill, N e w York, 1981).
21. F . K r e i t h a n d W . Z . B l a c k , Basic Heat Transfer ( H a r p e r & R o w , N e w Y o r k ,
1980).
22. W . M . R o h s e n o w , J . P . H a r t n e t t a n d E . N . G a n i c , Handbook of Heat Transfer
Fundamentals, second edition (McGraw-Hill, N e w York, 1985).
23. J. Lohrengel, Glastechn. Ber. 4 3 , 493 (1970).
24. R J . Araujo, C o n t e m p . Phys. 2 L 77 (1980).
25. H . J . H o f f m a n , in Photochromic Materials and Systems, e d i t e d b y H . D u r r
and H. Bouas-Laurent (Elsevier, Amsterdam, 1990).
26. E.L. Swarts and J. Pressau, J. A m . Ceram. Soc. 4 8 , 333 (1965).
27. G.S. Meiling, Phys. C h e m . Glasses 1 4 , 1 1 8 (1973).
28. G . G l i m e r o t h a n d K . - H . M a d e r , A n g e w . C h e m . I n t e r n a t . Edit. 9 , 4 3 4 ( 1 9 7 0 ) .
29. L . I . M a i s s e l a n d R . G l a n g , e d i t o r s , Handbook of Thin Film Technology
(McGraw-Hill, N e w York, 1970).
30. J . L . V o s s e n a n d W . K e r n , Thin Film Processes (Academic, N e w York, 1978).
31. H . K . P u l k e r , Coatings on Glass ( E l s e v i e r , A m s t e r d a m , 1 9 8 4 ) .
32. L . E c k e r t o v a , Physics of Thin Films, s e c o n d e d i t i o n ( P l e n u m , N e w Y o r k ,
1986).
33. W . D . W e s t w o o d , Phys. Thin Films 14, 1 (1989).

34. C . G . G r a n q v i s t , in Solar Optical Materials, edited by M.G. Hutchins
(Pergamon, Oxford, 1988), p. 59.
35. G. M b i s e , G.B. Smith, G.A. Niklasson and C.G. Granqvist, Proc. Soc.
Photo-Opt. Instrum. Engr. 1 1 4 9 , 1 7 9 (1989).
36. G . B . S m i t h , O p t . C o m m u n . 71, 2 7 9 ( 1 9 8 9 ) .
37. G . M b i s e , T . O t i t i a n d R . T . K i v a i s i , in Energy and Environment into the
1990s, e d i t e d b y A . A . M . S a y i g h ( P e r g a m o n , O x f o r d , 1 9 9 0 ) , V o l . 3, p. 1 4 1 1 .
38. G . B . S m i t h , R . J . D i t c h b u r n a n d M . W . N g , in Energy and Environment into
the 1990s, e d i t e d b y A . A . M . S a y i g h ( P e r g a m o n , O x f o r d , 1 9 9 0 ) , V o l . 3, p. 1 4 0 6 .
39. C M . Lampert, Solar Energy Mater. Π , 1 (1984).
40. S.M. Babulanam, T.S. Eriksson, G.A. Niklasson and C.G. Granqvist, Solar
E n e r g y M a t e r . 1 6 , 3 4 7 (1987).
41. H. Marquez, J.M. Rincon and L.E. Celaya, Thin Solid Films 189, 139 (1990).
42. M.R. Jacobson, P.D. Hillman, A.L. Phillips and U.J. Gibson, Proc. Soc.
Photo-Opt. Instrum. Engr. 4 2 8 , 5 7 (1983).
43. C F . H i c k e y a n d U . J . G i b s o n , J. A p p l . P h y s . 6 2 , 3 9 1 2 (1987).
44. G.L. Harding, Solar Energy Mater. 1 2 , 169 (1985).
45. G . L . H a r d i n g , I. H a m b e r g a n d C . G . G r a n q v i s t , S o l a r E n e r g y M a t e r .
1 2 , 1 8 7 (1985).
46. G.L. Harding, Thin Solid Films 1 3 8 , 279 (1986).
47. E . V a l k o n e n , B . K a r l s s o n a n d C.-G. R i b b i n g , S o l a r E n e r g y 3 2 , 2 1 1 ( 1 9 8 4 ) .
48. C - G . Ribbing and E. Valkonen, Proc. Soc. Photo-Opt. Instrum. Engr.
6 5 2 , 1 6 6 (1986).
49. E . V a l k o n e n , C.-G. R i b b i n g a n d J . E . S u n d g r e n , P r o c . S o c . P h o t o - O p t .
I n s t r u m . E n g r . 6 5 2 , 2 3 5 (1986).
50. A . G . S p e n c e r , M . G e o r g s o n , C . A . B i s h o p , E. S t e n b e r g a n d R . P . H o w s o n ,
S o l a r E n e r g y M a t e r . 1 8 , 8 7 (1988).
51. Y . Claeson, M. Georgson, A. Roos and C.-G. Ribbing, Solar Energy Mater.
2 0 , 4 5 5 (1990).
52. J . C C F a n a n d F.J. B a c h n e r , A p p l . O p t . 1 5 , 1 0 1 2 ( 1 9 7 6 ) .
53. E. Valkonen and B . Karlsson, Energy Res. Π , 397 (1987).
54. E . K u s a n o , J . K a w a g u c h i a n d K . Enjouji, J . V a c . S c i . T e c h n o l . A 4 , 2 9 0 7
(1986).
55. S.J. N a d e l , J . V a c . S c i . T e c h n o l . A 5, 2 7 0 9 ( 1 9 8 7 ) .
56. M . G e o r g s o n , A . R o o s a n d C.-G. R i b b i n g , to b e p u b l i s h e d .
57. J.L. Vossen, Phys. Thin Films 9, 1 (1977).
58. H. Kôstlin, Festkôrperprobleme 2 2 , 229 (1982).
59. P . M . B e r n i n g , A p p l . O p t . 2 2 , 4 1 2 7 (1983).
60. O . S . H e a v e n s , Optical Properties of Thin Solid Films ( D o v e r , N e w Y o r k ,
1965).
61. M . B o r n a n d E . W o l f , Principles of Optics, 6 t h e d i t i o n ( P e r g a m o n , O x f o r d ,
1980).
62. E . D . P a l i k , e d i t o r , Handbook of Optical Constants of Solids ( A c a d e m i c ,
N e w York, 1985).
63. K . L . C h o p r a , Thin Film Phenomena (McGraw-Hill, N e w York, 1969).
64. F. Abeles, Y . Borensztein and T. Lopez-Rios, Festkôrperprobleme 2 4 , 93
(1984).
65. S. N o r r m a n , T . A n d e r s s o n , C . G . G r a n q v i s t a n d O . H u n d e r i , P h y s . R e v .
Β 1 8 , 674 (1978).
66. G.B. Smith, G.A. Niklasson, J.S.E.M. Svensson and C.G. Granqvist, J.
Appl. Phys. 5 9 , 571 (1986).
67. P. G a d e n n e , A . B e g h d a d i a n d J . Lafait, O p t . C o m m u n . 6 5 , 1 7 ( 1 9 8 8 ) .
68. Y . Y a g i l a n d G . D e u t s c h e r , A p p l . P h y s . Lett. 5 2 , 3 7 3 ( 1 9 8 8 ) .
69. M . G a d e n n e , J . Lafait a n d P . G a d e n n e , O p t . C o m m u n . 7 1 , 2 7 3 ( 1 9 8 9 ) .
70. P. G a d e n n e , Y . Y a g i l a n d G. D e u t s c h e r , J . A p p l . P h y s . 6 6 , 3 0 1 9 ( 1 9 8 9 ) .
71. Y . Y a g i l , M . Y o s e f i n , D . J . B e r g m a n , G . D e u t s c h e r a n d P. G a d e n n e , to b e
published.
72. E . V a l k o n e n a n d C.-G. R i b b i n g , M a t e r . Lett. 3 , 2 9 ( 1 9 8 4 ) .
73. T. K a r l s s o n , C.-G. R i b b i n g , A . R o o s a n d E . V a l k o n e n , Int. J . E n e r g y R e s .
1 2 , 2 3 (1988).
74. P . O . J a r v i n e n , J. E n e r g y 2 , 9 5 ( 1 9 7 8 ) .
75. I. H a m b e r g , J . S . E . M . S v e n s s o n , T . S . E r i k s s o n , C . G . G r a n q v i s t , P. A r r e n i u s
and F. Norin, Appl. Opt. 2 6 , 2131 (1987).
76. Z.M. Jarzebski and J.P. Marton, J. Electrochem. Soc. 123, 199c, 299c, 333c
(1976).
77. G . H a a c k e , A n n . R e v . M a t e r . S c i . 7, 7 3 ( 1 9 7 7 ) .
78. Z . M . J a r z e b s k i , P h y s . Stat. S o l . Z L 13 ( 1 9 8 2 ) .
79. J.C. Manifacier, Thin Solid Films 9 0 , 297 (1982).
80. K . L . C h o p r a , S. M a j o r a n d K . P a n d y a , T h i n S o l i d F i l m s 1 0 2 , 1 ( 1 9 8 3 ) .
81. I. H a m b e r g a n d C . G . G r a n q v i s t , J . A p p l . P h y s . 6Q, R 1 2 3 ( 1 9 8 6 ) .
82. Z.-C. J i n , I. H a m b e r g a n d C . G . G r a n q v i s t , A p p l . P h y s . Lett. 5 L 1 4 9 ( 1 9 8 7 ) .
83. Z.-C. J i n , I. H a m b e r g a n d C . G . G r a n q v i s t , J . A p p l . P h y s . 6 4 , 5 1 1 7 (1988).
84. H . H a i t j e m a , J.J.P. E l i c h a n d C . J . H o o g e n d o o r n , S o l a r E n e r g y M a t e r . 1 8 ,
283 (1989).
85. B . Stjerna a n d C . G . G r a n q v i s t , A p p l . P h y s . Lett. 5 7 , 1 9 8 9 ( 1 9 9 0 ) .
86. M . Marezio, Acta Crystallogr. 20, 273 (1966).
87. S.-J. J i a n g a n d C . G . G r a n q v i s t , P r o c . S o c . P h o t o - O p t . I n s t r u m . E n g r .
5 6 2 , 1 2 9 (1985).
88. Y. S a w a d a and Y. Taga, Thin Solid Films 116, L55 (1984).
89. H . S c h a d e a n d Z . E . S m i t h , A p p l . Opt. 2 4 , 3 2 2 1 ( 1 9 8 5 ) .
90. J.G. O'Dowd, Proc. Soc. Photo-Opt. Instrum. Engr. 6 9 2 , 58 (1986).
91. I. H a m b e r g , C . G . G r a n q v i s t , K . - F . B e r g g r e n , B . E . S e r n e l i u s a n d L . E n g s t r ô m ,
Phys. Rev. Β 3 0 , 3240 (1984).
92. B . E . S e r n e l i u s , K . - F . B e r g g r e n , Z.-C. J i n , I. H a m b e r g a n d C . G . G r a n q v i s t ,
Phys. Rev. Β 3 7 , 1 0 2 4 4 (1988).
93. C . A . H o g a r t h a n d Z . T . A l - D h h a n , P h y s . Stat. S o l . 1 3 7 , K 1 5 7 ( 1 9 8 6 ) .
94. M.A. Sainz, A. Durân and J.M. Fernandez Navarro, J. Non-Cryst. Solids
1 2 1 , 3 1 5 (1990).
95. B . W . F a u g h n a n a n d R . S . C r a n d a l l , in Display Devices, e d i t e d b y J.I.
P a n k o v e , Topics in Applied Physics, V o l . 4 0 ( S p r i n g e r , B e r l i n , 1 9 8 0 ) , p. 1 8 1 .
96. G. Beni and J.L. Shay, Adv. I m a g e Pickup and Display 5, 83 (1982).
97. W . C . D a u t r e m o n t - S m i t h , D i s p l a y s , J a n u a r y 3, A p r i l 6 7 ( 1 9 8 2 ) .
98. S.A. A g n i h o t r y , K . K . S a i n i a n d S. C h a n d r a , I n d i a n J . P u r e A p p l . P h y s .
2 4 , 1 9 , 3 4 (1986).
99. S.K. D e b , P r o c . S o c . P h o t o - O p t . I n s t r u m E n g r . 6 9 2 , 1 9 ( 1 9 8 6 ) .
100. T. O i , A n n . R e v . M a t e r . S c i . 1 6 , 1 8 5 ( 1 9 8 6 ) .
101. A . D o n n a d i e u , M a t e r . S c i . E n g r . Β 3, 1 8 5 ( 1 9 8 9 ) .
102. A . M . A n d e r s s o n , C . G . G r a n q v i s t a n d J . R . S t e v e n s , A p p l . O p t . 2 8 , 3 2 9 5 (1989).
103. R . B . G o l d n e r , R . L . C h a p m a n , G . F o l e y , E . L . G o l d n e r , T. H a a s , P. N o r t o n ,
G. S e w a r d a n d K . K . W o n g , S o l a r E n e r g y M a t e r . 1 4 , 1 9 5 ( 1 9 8 6 ) .
104. R . B . G o l d n e r , G . S e w a r d , K . W o n g , G . B e r e r a , T. H a a s a n d P . N o r t o n , P r o c .
Soc. Photo-Opt. Instrum. Engr. 8 2 3 , 1 0 1 (1987).
105. G . S e w a r d , R . B . G o l d n e r , K . W o n g , T. H a a s , G . H . F o l e y , R . C h a p m a n a n d
S. S h u l t z , P r o c . S o c . P h o t o - O p t . I n s t r u m . E n g r . 8 2 3 , 9 0 ( 1 9 8 7 ) .
106. J . L . L a g z d o n s , G . E . Bajars a n d A . R . L u s i s , P h y s . Stat. S o l . A 8 4 , K 1 9 7 ( 1 9 8 4 ) .
107. C M . L a m p e r t , T . R . O m s t e a d a n d P . C . Y u , S o l a r E n e r g y M a t e r . 1 4 , 1 6 1 (1986).
108. J . S . E . M . S v e n s s o n a n d C . G . G r a n q v i s t , A p p l . P h y s . Lett. 4 9 , 1 5 6 6 ( 1 9 8 6 ) .
109. M.K. Carpenter, R.S. Conell and D.A. Corrigan, Solar Energy Mater. 16,
333 (1987).
110. M . Fantini and A. Gorenstein, Solar Energy Mater. 1 6 , 487 (1987).
111. J.S.E.M. Svensson and C.G. Granqvist, Solar Energy Mater. 16, 19 (1987).
112. J.S.E.M. Svensson and C.G. Granqvist, Appl. Opt. 2 6 , 1 5 5 4 (1987).
113. P.C. Y u , G. Nazri and C M . Lampert, Solar Energy Mater. 1 6 , 1 (1987).
114. K. Bange, F.G.K. Baucke and B . Metz, Proc. Soc. Photo-Opt. Instrum.
E n g r . 1 0 1 6 , 1 7 0 (1988).
115. P. D e l i c h e r e , S. J o i r e t , A . H u g o t - L e G o f f , K . B a n g e a n d B . M e t z , P r o c . S o c .
Photo-Opt. Instrum. Engr. 1 0 1 6 , 1 6 5 (1988).
116. W . Estrada, A.M. Andersson and C.G. Granqvist, J. Appl. Phys. 64, 3678
(1988).
117. N.R. L y n a m and H.R. Habibi, Proc. Soc. Photo-Opt. Instrum. Engr. 1 0 1 6 ,
63 (1988).
118. A. Pennisi and C M . Lampert, Proc. Soc. Photo-Opt. Instrum. Engr. 1016,
131 (1988).
119. S. Y a m a d a , T . Y o s h i o k a , M . M i y a s h i t a , K . U r a b e a n d M . K i t a o , P r o c . S o c .
Photo-Opt. Instrum. Engr. 1016, 34 (1988).
120. P C . Y u and C M . Lampert, Solar Energy Mater. 1 9 , 1 (1989).
121. S.F. Cogan, T.D. Plante, R.S. M c F a d d e n and R.D. Rauh, Proc. Soc. Photo-Opt.
I n s t r u m . E n g r . 8 2 3 , 1 0 6 (1987).
122. P.V. Ashrit, F.E. Girouard, V.-V. Truong and G. Bader, Proc. Soc. Photo-Opt.
Instrum. Engr. 5 6 2 , 53 (1985).
123. B.M. A r m a n d , Ann. Rev. Mater. Sci. 1 6 , 245 (1986).
124. J . R . S t e v e n s , J . S . E . M . S v e n s s o n , C . G . G r a n q v i s t a n d R . S p i n d l e r , A p p l . Opt.
2 6 , 3 4 8 9 (1987).
125. A . D e n e u v i l l e , P. G e r a r d a n d R. Billat, T h i n S o l i d F i l m s ZQ, 2 0 3 ( 1 9 8 0 ) .
126. T. Y o s h i m u r a , M . W a t a n a b e , Y. K o i k e , K. Kiyota and M . T a n a k a , Thin
S o l i d F i l m s ΠΗ, 141 ( 1 9 8 3 ) .
127. J . S . E . M . S v e n s s o n a n d C . G . G r a n q v i s t , A p p l . P h y s . Lett. 4 5 , 8 2 8 ( 1 9 8 4 ) .
128. D.K. Benson, C E . Tracy, J.S.E.M. Svensson and B.E. Liebert, Proc. Soc.
Photo-Opt. Instrum. Engr. 8 2 3 , 72 (1987).
129. Y . K a m i m o r i , J. N a g a i and M . Mizuhashi, Solar E n e r g y Mater. 1 6 , 27 (1987).
130. R. V i e n n e t , J . - P . R a n d i n a n d I.D. R a i s t r i c k , J . E l e c t r o c h e m . S o c . 1 2 9 , 2 4 5 1
(1982).
131. S. T a k a k i , K . M a t s u m o t o a n d K . S u z u k i , A p p l . S u r f a c e S c i . 3 3 / 3 4 , 9 1 9 ( 1 9 8 8 ) .
132. J . P . R a n d i n , in Proc. First European Display Research Conf., Eurodisplay
'81 ( V D E - V e r l a g , B e r l i n , 1 9 8 1 ) , p. 9 4 .
133. D . C r a i g e n , A . M a c k i n t o s h , J . H i c k m a n a n d K. C o l b o w , J . E l e c t r o c h e m . S o c .
1 3 3 , 1 5 2 9 (1986).
134. D. Davazoglou, A. Donnadieu, R. Fourcade, A. Hugot-LeGoff, P. Delichere

and A. Perez, Rev. Phys. Appl. 2 3 , 265 (1988).
135. H . U n u m a , K . T o n o o k a , Y . S u z u k i , T. F u r u s a k i , K . K o d a i r a a n d T.
M a t s u s h i t a , J . M a t e r . S c i . Lett. 5 , 1 2 4 8 ( 1 9 8 6 ) .
136. N.R. L y n a m , F.H. M o s e r and B.P. Hichwa, Proc. Soc. Photo-Opt. Instrum.
E n g r . 8 2 3 , 1 3 0 (1987).
137. K . S o n e a n d Y . F u k u d a , Inorganic Thermochromism, Springer Series on
I n o r g a n i c C h e m i s t r y C o n c e p t s , V o l . 10 ( S p r i n g e r , B e r l i n , 1 9 8 7 ) .
138. J.B. Goodenough, Progr. Solid State C h e m . 5 , 1 4 5 (1971).
139. C.B. Greenberg, Thin Solid Films 110, 73 (1983).
140. G.V. Jorgenson and J.C. Lee, Solar Energy Mater. 14, 205 (1986).
141. J.C. Lee, G.V. Jorgenson and R.J. Lin, Proc. Soc. Photo-Opt. Instrum.
E n g r . 6 9 2 , 2 (1986).
142. S . M . B a b u l a n a m , W . E s t r a d a , M . O . H a k i m , S. Y a t s u y a , A . M . A n d e r s s o n ,
J.R. Stevens, J.S.E.M. Svensson and C.G. Granqvist, Proc. Soc. Photo-Opt.
I n s t r u m . E n g r . 8 2 3 , 6 4 (1987).
143. K . A . K h a n , G . A . N i k l a s s o n a n d C . G . G r a n q v i s t , J . A p p l . P h y s . 6 4 , 3 3 2 7 (1988).
144. K . A . K h a n a n d C . G . G r a n q v i s t , A p p l . P h y s . Lett. 5 5 , 4 ( 1 9 8 9 ) .
145. G . M b i s e , G . B . S m i t h , G . A . N i k l a s s o n a n d C . G . G r a n q v i s t , A p p l . P h y s . Lett.
5 4 , 9 8 7 (1989).
146. S.M. Machaggah, R.T. Kivaisi and E.M. Lushiku, Solar Energy Mater.
19,315 (1989).
147. T. M o t o h i r o , H. Y a m a d e r a a n d Y . T a g a , R e v . S c i . I n s t r u m . 6Q, 2 6 5 7 (1989).
148. H . J . L e a m y , G . H . G i l m e r a n d A . G . D i r k s , in Current Topics in Materials
Science, e d i t e d b y E . K a l d i s ( N o r t h - H o l l a n d , A m s t e r d a m , 1 9 8 0 ) , V o l . 6 ,
p. 3 0 9 .
149. J . K r u g a n d P. M e a k i n , P h y s . R e v . A 4 0 , 2 0 6 4 ( 1 9 8 9 ) .
150. P. M e a k i n a n d J . K r u g , E u r o p h y s . Lett. 1L 7 ( 1 9 9 0 ) .
151. S.-J. J i a n g , Z.-C. Jin a n d C . G . G r a n q v i s t , A p p l . O p t . 2 7 , 2 8 4 7 (1988).
152. I. H a m b e r g a n d C . G . G r a n q v i s t , A p p l . Opt. 2 2 , 6 0 9 ( 1 9 8 3 ) .
153. C. A m r a , G . A l b r a n d a n d P. R o c h e , A p p l . O p t . 2 5 , 2 6 9 5 ( 1 9 8 6 ) .
154. F . H . N i c o l l , R C A R e v . 10, 4 4 0 ( 1 9 4 9 ) .
155. S.M. T h o m s e n , R C A Rev. 1 2 , 143 (1951).
156. K . J . C a t h r o , D . C . C o n s t a b l e a n d T. S o l a g a , S o l a r E n e r g y 2 7 , 4 9 1 ( 1 9 8 1 ) .
157. L . I g n b e r g , U p p s a l a U n i v e r s i t y T e c h n i c a l R e p o r t U P T E C 8 2 6 0 E (in S w e d i s h ;
unpublished, 1982).
158. H.J. G l â s e r , G l a s t e c h n . B e r . 5 0 , 2 4 8 (1977).
159. D . A r a s t e h , S. S e l k o w i t z a n d J . H a r t m a n n , in Proc. ASHRAE/DOE/BTECC
Conference on Thermal Performance of the Exterior Envelopes of
Buildings III, C l e a r w a t e r B e a c h , F l o r i d a , U S A , 2 - 5 D e c e m b e r 1 9 8 5 ; a l s o
Lawrence Berkeley Laboratory Report LBL-20348.
160. P. D e r n e r , G l a s t e c h n . B e r . 4 8 , 8 4 (1975).
161. T.S. Eriksson, C.G. Granqvist and J. Karlsson, Solar Energy Mater. 1 6 ,
2 4 3 (1987).
162. W.J. Platzer, Solar Energy Mater. 1 6 , 275 (1987).
163. A . P f l u g e r , P h . D . T h e s i s , F a k u l t à t fur P h y s i k d e r A l b e r t - L u d w i g s -
Universitàt, Freiburg, G e r m a n y (unpublished, 1988).
164. W . J . P l a t z e r , P h . D . T h e s i s , F a k u l t à t fur P h y s i k d e r A l b e r t - L u d w i g s -
Universitàt, Freiburg, Germany (unpublished, 1988).
165. W . J . P l a t z e r a n d V . W i t t w e r , in Proc. Workshop on Optical Measure-

ment Techniques, Ispra, Italy, 27-29 O c t o b e r (1987).
166. C . A . B i s h o p a n d R.P. H o w s o n , S o l a r E n e r g y M a t e r . 1 3 , 1 7 5 ( 1 9 8 6 ) .
167. K . C h i b a , S. S o b a j i m a a n d Y . Y a t a b e , S o l a r E n e r g y M a t e r . 8 , 3 7 1 ( 1 9 8 3 ) .
168. R.P. H o w s o n , M.I. Ridge and K. Suzuki, Proc. Soc. Photo-Opt. Instrum.
Engr. 4 2 8 , 1 4 (1983).
169. Z.-C. J i n a n d C . G . G r a n q v i s t , A p p l . O p t . 2 6 , 3 1 9 1 ( 1 9 8 7 ) .
170. T . M i n a m i , H . N a n t o a n d S. T a k a t a , J a p a n . J . A p p l . P h y s . 2 7 , L 2 8 7 ( 1 9 8 8 ) .
171. B . Stjerna a n d C . G . G r a n q v i s t , S o l a r E n e r g y M a t e r . 2 0 , 2 2 5 ( 1 9 9 0 ) ; A p p l . Opt.
2 9 , 4 4 7 (1990).
172. A . P f l û g e r , W . J . P l a t z e r a n d V . W i t t w e r , in Advances in Solar Energy
Technology, e d i t e d b y W . H . B l o s s a n d F . Pfisterer ( P e r g a m o n , O x f o r d , 1 9 8 8 ) ,
p. 636.
173. W . J . P l a t z e r a n d V . W i t t w e r , Transparente Wàrmedammaterialen fur den
Einsatz im Solarenergiebereich (1988).
174. V. Wittwer, private communication.
175. A . Pfluger, Solar Energy Mater. 16, 255 (1987).
176. J. Fricke, J. Non-Cryst. Solids 1 0 0 , 1 6 9 (1988).
177. J. Fricke, Sci. A m . 2 5 8 , (5), 9 2 (1988).
178. J . F r i c k e , e d i t o r , Aerogels, S p r i n g e r P r o c . in P h y s i c s , V o l . 6 ( S p r i n g e r , B e r l i n ,
1986).
179. S. H e n n i n g a n d L . S v e n s s o n , P h y s . S c r i p t a 2 3 , 6 9 7 ( 1 9 8 1 ) .
180. S. H e n n i n g , in Aerogels, e d i t e d b y J . F r i c k e ( S p r i n g e r , B e r l i n , 1 9 8 6 ) , p. 3 8 .
181. M . R u b i n a n d C M . L a m p e r t , S o l a r E n e r g y M a t e r . 7, 3 9 3 ( 1 9 8 3 ) .
182. W . J . P l a t z e r , V . W i t t w e r a n d M . M i e l k e , in Aerogels, edited b y J. Fricke
( S p r i n g e r , B e r l i n , 1 9 8 6 ) , p. 127.
183. P . H . T e w a r i , A . J . H u n t , J . G . L i e b e r a n d K . Lofftus, in Aerogels, e d i t e d b y
J. F r i c k e ( S p r i n g e r , B e r l i n , 1 9 8 6 ) , p. 1 4 2 .
184. J . Fricke, R. C a p s , D . Bûttner, U. H e i n e m a n n , E. H u m m e r and A. Kadur,
S o l a r E n e r g y M a t e r . 6, 2 6 7 (1987).
185. E. Boy, Bauphysik Π , 21 (1989).
186. D.K. Benson, C E . Tracy and G.J. Jorgensen, Proc. Soc. Photo-Opt. Instrum.
E n g r . 5 0 2 , 1 4 6 (1984).
187. S. R o b i n s o n a n d R . E . C o l l i n s , in Proc. ISES Solar Energy World Congress,
K o b e , J a p a n , 1 9 9 0 , to b e p u b l i s h e d .
188. D . K . B e n s o n , C E . T r a c y , T. P o t t e r , C. C h r i s t e n s e n a n d D . E . S o u l e , S o l a r
E n e r g y Research Institute Report SERI SP-255-3318 (1988).
189. N . Y . C C h u , Solar Energy Mater. U , 215 (1986).
190. T. N o v i n s o n , P r o c . S o c . P h o t o - O p t . I n s t r u m . E n g r . 8 2 3 , 1 3 8 ( 1 9 8 7 ) .
191. G . R e u s c h , G l a s w e l t 2 L ( 1 ) , 16 ( 1 9 6 8 ) .
192. J. Germer, Solar Age, October 1984, p. 20.
193. E . B o y a n d S. M e i n h a r d t , in Proc. Second International Workshop on
Transparent Insulation Materials in Solar Energy Conversion for Buildings
and Other Applications, Freiburg, Germany, 24-25 March (1988).
194. A.M. Andersson, G.A. Niklasson and C.G. Granqvist, Appl. Opt. 26, 2164
(1987).
195. Y . A n j a n e y u l u a n d D . W . Y o o n , S o l a r E n e r g y M a t e r . U, 2 2 3 ( 1 9 8 6 ) .
196. P. v a n K o n y n e n b u r g , S. M a r s l a n d a n d J . M c C o y , S o l a r E n e r g y M a t e r .
1 9 , 2 7 (1989).
Chapter 6
MATERIALS FOR RADIATIVE COOLING

TO LOW TEMPERATURES
C.G. Granqvist and T.S. Eriksson
Physics Department
ABSTRACT
R a d i a t i v e c o o l i n g u s e s t h e c l e a r s k y as a h e a t sink. T o a s s e s s t h e p o t e n t i a l o f this
free a n d a b u n d a n t s o u r c e o f c o o l i n g w e first p r e s e n t c o m p u t e d d a t a , b a s e d o n a
d e t a i l2
e d m o d e l o f t h e s k y r a d i a n c e , w h i c h s h o w that a c o o l i n g p o w e r o f ~ 1 0 0
W m " at a m b i e n t t e m p e r a t u r e a n d a m a x i m u m p r a c t i c a l t e m p e r a t u r e d i f f e r e n c e
of - 25°C can be accomplished. L o w temperature applications hinge on materials
development. W e review w o r k on selectively infrared-emitting surfaces with a
focus o n s i l i c o n - b a s e d c o a t i n g s b a c k e d b y m e t a l , m e t a l l i z e d p o l y m e r foils, g a s slabs
b a c k e d b y m e t a l , a n d c e r t a i n c e r a m i c o x i d e l a y e r s . W e a l s o treat i n f r a r e d - t r a n s -
parent polyethylene-based convection shields with a focus on cellular construc-
t i o n s , as w e l l as c o a t i n g s a n d p i g m e n t s for d i m i n i s h i n g t h e s o l a r t r a n s m i t t a n c e .
T h e r e s u l t s o f a f e w s e l e c t e d field tests a r e i n c l u d e d . U n d e r f a v o u r a b l e , b u t n o t
u n c o m m o n , meteorological conditions o n e can reach temperature differences of
1 5 - 2 0 ° C d u r i n g t h e n i g h t a n d ~ 1 0 ° C d u r i n g the d a y w i t h s i m p l e d e v i c e s .
I. INTRODUCTION
T h e c l e a r s k y c a n s e r v e as a h e a t s i n k a n d c a n t h u s b e u s e d to p r o d u c e t e m p e r a -
t u r e s b e l o w t h o s e o f t h e a m b i e n c e in a p u r e l y p a s s i v e w a y . T h i s p r o p e r t y o f t h e
clear s k y h a s b e e n k n o w n s i n c e a n c i e n t t i m e s , a n d scientific s t u d i e s o f a t t a i n a b l e
t e m p e r a t1 u r e differences d a t e b a c k at l e a s t as far as to t h e first p a r t o f t h e 19th
century. Cooling under clear weather conditions has n u m e r o u s important
p r a c t i c a l c o n s e q u e n c e s r e l a t e d to t e m p e r a t u r e c o n t r o l o f t h e E a r t h , m e t e o r o l o g y ,
n a t u r a l c l i m a t i z a t i o n , etc. T h e c o n s e q u e n c e s to M a n c a n b e b o t h g o o d a n d b a d : A s
an e x a m p l e w h e r e the cooling causes problems, w e can mention that growing
c r o p s c a n b e d a m a g e d b y frost e v e n if t h e air t e m p e r a t u r e is s e v e r a l d e g r e e s a b o v e
0 ° C , a s is w e l l k n o w n t o f a r m e r s a n d g a r d e n e r s . A n o t h e r e x a m p l e , w h e r e n a t u r a l
168
Materials for Radiative Cooling to Low Temperatures 169
c o o l i n g is u s e d to a d2
v a n t a g e , c a n b e f o u n d in t r a d i t i o n a l I r a n i a n i c e - m a k e r s a n d
desalination ponds.
E v e n i f p a s s i v e c o o l i n g u n d e r c l e a r s k i e s is a w i d e l y r e c o g n i z e d p h e n o m e n o n , t h e
d e v e l o p m e n t o f m a t e r i a l s a n d d e v i c e s for efficient u t i l 3 i z6
a t i o n o f this free a n d
a b u n d a n t s o u r c e o f c o o l i n g is a r e l a t i v e l y n e w s u b j e c t . " T h e k e y t o a c o n s c i o u s
m a t e r i a l s d e v e l o p m e n t lies in a n u n d e r s t a n d i n g o f t h e b a l a n c e b e t w e e n t h e
radiation w h i c h wells d o w n from the atmosphere, and the radiation emitted from
a surface exposed towards the atmosphere. Either type o f radiation m a y b e
c h a r a c t e r i z e d b y a s t r o n g s p e c t r a l d e p e n d e n c e . S e c t i o n II i n t r o d u c e s t h e s u b j e c t b y
p r e s e n t i n g c o m p u t e d r a d i a n c e s p e c t r a for 2 different m o d e l a t m o s p h e r e s a n d g i v i n g
e s t i m a t e s o f c o o l i n g p o w e r (~ 1 0 0 W m ' at a m b i e n t t e m p e r a t u r e ) a n d m a x i m u m
t e m p e r a t u r e d r o p ( < 2 5 ° C in a p r a c t i c a l d e v i c e ) . L o w - t e m p e r a t u r e a p p l i c a t i o n s o f
r a d i a t i v e c o o l i n g - a s w e h e n c e f o r t h call t h e p h e n o m e n o n o f p a s s i v e c o o l i n g
under clear skies - hinge on materials development. Specifically, two materials
issues are o f central importance. T h e y are surface treatments giving infrared
s e l e c t i v i t y w i t h h i g h e m i t t a n c e in t h e 8-13-μιτι w a v e l e n g t h i n t e r v a l a n d l o w
absorptance elsewhere, a n d convection shields with significant infrared
t r a n s m i t t a n c e . S e c t i o n III r e v i e w s w o r k o n i n f r a r e d - s e l e c t i v e s u r f a c e s , w i t h
d i s c u s s i o n o f s i l i c o n - b a s e d c o a t i n g s b a c k e d b y m e t a l , m e t a l l i z e d p o l y m e r foils, g a s
slabs backed b y metal, and certain ceramic oxide layers. Section IV summarizes
r e s u l t s o n i n f r a r e d - t r a n s p a r e n t c o n v e c t i o n s h i e l d s , for w h i c h p o l y e t h y l e n e - b a s e d
m a t e r i a l s h a v e b e e n u s e d w i t h o u t e x c e p t i o n . W e treat c e l l u l a r m a t e r i a l s as w e l l
as foils w i t h s i g n i f i c a n t solar r e f l e c t a n c e . S e c t i o n V is d e v o t e d to r e s u l t s from a
f e w s e l e c t e d field tests. W e i n c l u d e d a t a o b t a i n e d u s i n g s e l e c t i v e l y i n f r a r e d -
emitting surfaces placed under transparent convection shields, certain innovative
m u l t i s t a g e c o o l i n g d e v i c e s , a n d p o l y e t h y l e n e - b a s e d s o l a r r e f l e c t i n g foils.
B a s e d o n t h e w o r k c o n d u c t e d s o far, o n e c a n state that t h e r e is n o d o u b t r e g a r d i n g

the theoretical assessments o f the potential o f radiative cooling, or that such
c o o l i n g c a n b e a p p l i e d in p r a c t i c e . U n d e r f a v o u r a b l e - t h o u g h n o t u n c o m m o n -
meteorological conditions o n e can reach temperature differences o f 15-20°C
during the night and ~ 10°C during the day b y use of simple single-stage devices.
Multistage devices can reach even lower temperatures. T h e lowest temperatures
r e q u i r e s e l e c t i v e l y i n f r a r e d - e m i t t i n g s u r f a c e s , b u t if p r e m i u m is p u t o n a l a r g e
c o o l i n g p o w e r at a m o d e r a t e t e m p e r a t u r e d i f f e r e n c e , a b l a c k b o d y - l i k e r a d i a t o r is
often t h e b e s t o p t i o n . S o l a r - r e f l e c t i n g c o n v e c t i o n s h i e l d s a p p e a r t o offer a c h e a p
m e a n s for m o d e r a t e s p a c e c o o l i n g e v e n d u r i n g t h e d a y .
IL THE RESOURCE FOR RADIATIVE COOLING
T h i s s e c t i o n p r e s e n t s d a t a o n t h e s p e c t r a l r a d i a n c e f r o m different m o d e l
a t m o s p h e r e s r e p r e s e n t a t i v e o f v a r i o u s l a t i t u d e s ( S e c . I I A ) , as w e l l as o n t h e
r e l a t i o n s h i p b e t w e e n c o o l i n g p o w e r a n d t e m p e r a t u r e d i f f e r e n c e ( S e c . II B ) .
A. Atmospheric Radiance
78
T h e r a d i a n c e c o m i n g f r o m t h e a t m o s p h e r e is e x t r e m e l y c o m p l i c a t e d . ' T h e m a i n
g a s e s , n i t r o g e n a n d o x y g e n , c o n t r i b u t e v e r y little, w h e r e a s t h e v a r i a b l e constit-
u e n t s l i k e w a t e r v a p o u r , c a r b o n d i o x i d e , o z o n e , a n d - to a m u c h s m a l l e r e x t e n t -
n i t r o g e n o x i d e s a n d h y d r o c a r b o n s s h o w i m p o r t a n t a b s o r p t i o n b a n d s in t h e
t h e r m a l infrared r a n g e . T h i s is t a k e n to b e 3 < λ < 1 0 0 μ ι η , w h e r e λ d e n o t e s the
w a v e l e n g t h . W a t e r v a p o u r h a s a s t r o n g split v i b r a t i o n a l b a n d c e n t e r 9 ed around
6.3 μιη a n d a l s o s h o w s s i g n i f i c a n t r o t a t i o n a l a b s o r p t i o n at λ > 2 0 μ ι η . T h i s
a b s o r p t i o n c a n e x t e n d to s h o r t e r w a v e l e n g t h s if t h e h u m i d i t y is h 9 igh. Carbon
d i o x i d e h a s a b r o a d i n t e n s e v i b r a t i o n a l b a n d c e n t e r e d at ~ 15 μ ι η . O z o n e
a b s o r p t i o9n is n o t e q u a l l y i m p o r t a n t b u t s e v e r a l a b s o r p t i o n b a n d s lie in t h e
infrared. Most of these are m a s k e d b y water vapour and carbon dioxide, but a
n a r r o w a b s o r p t i o n b a n d at 9.6 μιη s h o w s u p distinctly. O n e c o n c l u d e s that t h e
a t m o s p h e r i c r a d i a t i o n d o w n w a r d s h o w s t w o i m p o r t a n t f e a t u r e s : F i r s t , the
s p e c t r a l r a d i a n c e h a s a m i n i m u m in a n i n t e r v a l w h i c h lies b e t w e e n t h e m a j o r
a b s o r p t i o n b a n d s o f w a t e r v a p o u r a n d c a r b o n d i o x i d e . S e c o n d , t h e o v e r a l l spectral
radiance depends strongly on climatic conditions - particularly on the a m o u n t of
w a t e r v a p o u r . T h e s e f e a t u r e s h a v e b e e n verified n u m e r o u s t i m e s b y d i r e c t
s p e c t r o r a d i o m e t r i c m e a s u r e m e n t s ( s e e , for e x a m p l e , Refs. 1 0 - 1 2 ) .
F o r q u a n t i t a t i v e a s s e s s m e n t s o f t h e c o o l i n g r e s o u r c e , it is useful to start f r o m
d e t a i l e d d a t a o n t h e s p e c t r a l s k y r a d i a n c e r e p r e s e n t a t i v e o f t y p i c a l c l i m a t e s at
different l a13 titudes. S u c h results can b e extracted from a c o m p u t e r p r o g r a m
known a s L O W T R A N 5 (or a m o r e r e c e n t v e r s i o n o f this). It u s e s a s i n g l e -
p a r a m e t e r b a n d m o d e l for t h e m o l e c u l a r a b s o r p t i o n a n d i n c l u d e s t h e effects o f
continuum absorption, molecular scattering, and aerosol extinction. Atmospheric
r e f r a c t i o n a n d e a r t h c u r v a t u r e are i n c l u d e d for slant a t m o s p h e r i c p a t h s . F o r
r a d i a t i v e c o o l i n g p u r p o s e s , t h e L O W T R A N 5 p r o g r a m n e e d s to b e u s e d e x c l u -
s i v e l y in t h e r a d i a n c e m o d e , in w h i c h a n u m e r i c a l e v a l u a t i o n o f t h e i n t e g r a l f o r m
o f t h e r a d i a t i v e transfer e q u a t i o n is e m p l o y e d . T h e e m i s s i o n f r o m a e r o s o l s a n d
t h e t r e a t m e n t o f a e r o s o l a n d m o l e c u l a r s c a t t e r i n g a r e c o n s i d e r e d o n l y to z e r o t h
o r d e r ; a d d i t i o n a l c o n t r i b u t i o n s to a t m o s p h e r i c e m i s s i o n f r o m s c a t t e r e d r a d i a t i o n
a r e n e g l e c t e d . L o c a l t h e r m o d y n a m i c e q u i l i b r i u m is a s s u m e d . T h e r a d i a n c e d a t a
obtained from L O W 13T R A N a r e k n o w n to b e in v e r y g o o d o v e r a l l a g r e e m e n t w i t h
measured results.
T h e L O W T R A N 5 p r o g r a m is p r o v i d e d w i t h d a t a for five s e a s o n a l a t m o s p h e r e s
t o g e t h e r w i t h t h e 1 9 6 2 U . S . s t a n d a r d a t m o s p h e r e . It is a l s o p o s s i b l e to r e p l a c e
these by user derived or measured values. The seasonal models are
representative of the following atmospheres: tropical (15° N ) , midlatitude
s u m m e r (45° N , July), midlatitude winter (45° N , January), subarctic s u m m e r
(60° N , J u l y ) a n d s u b a r c t i c w i n t e r ( 6 0 ° N , J a n u a r y ) . T h e a t m o s p h e r e s a r e specified
in t e r m s o f h e i g h t profiles for t e m p e r a t u r e , b a r o m e t r i c p r e s s u r e , a n d d e n s i t i e s o f
w a t e r v a p o u r , o z o n e , nitric a c i d , a n d o f the u n i f o r m l y m i x e d g a s e s ( C 0 , N 0 ,
2 2
C H 4 , C O , N and 0 ) . T h e L O W T R A N 5 program also contains several aerosol
2 2
m o d e l s . F i g u r e 1 s h o w s a t m o s p h e r i c z e n i t h r a d i a n c e for all s i x m o d e l a t m o s -
p h e r e s . W e d e n o t e this q u a n t i t y b y L (Θ = 0, λ, t ) , w i t h x b e i n g t h e t e m p e r a t u r e
a a a
o f t h e a t m o s p h e r i c b o u n d a r y layer. T h e d a t a a r e r e p r o d u c e d f r o m R e f . 1 4 . T h e s e
WAVELENGTH [ u m ]
5 6 7 β 9 10 15 20 30 S0100
Ί " 1 '—! ι I «I «I ' ' ι ι ι 1111 ] ι ι ι ι Γ Π
TROPICAL >^^^S^^^
τ;·3οοκ J I
0 1
Έ I
b
MIDLATITUDE SUMMER J / J \ 1
\ Ι Τς·294Κ j \ Ζ
10.5 - y^C y \ "
,5 I 0
g
c
MIDLATITUDE WINTER > ^ / \ I
g Γ V272.2K I \ ~
d
N
1 L
0 S U B A R C T I C SUMMER > ^ / ># >^ J
5 : t,«287k >^ / \ :
l ^ 05
J \
0 1
5S U B A R C T I C W I N T E R >^ I }/ \ J
- * T.«257.1K J \ -
10 : , * 1962 U.S. S T A N D A R D j / i X -
Γ Τ,«2ββ.1Κ / \ ~
°h •I , I . I •I T I . I .I . I •I •I . I . I . I •I I ,I ,I,
2000 1600 1200 800
1 400 0
FREQUENCY [ c n f ]
Fig. 1. Calculated spectral zenith radiance (lower curves in parts

a-f) a n d c o r r e s p o n d i n g b l a c k b o d y r a d i a n c e ( u p p e r c u r v e s
in p a r t s a-f) for s i x m o d e l a t m o s p h e r e s , a s c o m p u t e d f r o m
the L O W T R A N 5 model. T h e horizontal axis s h o w s
f r e q u e n c y as w e l l a s w a v e l e n g t h . ( F r o m R e f . 1 4 ) .
c u r v e s a r e s e e n to d r o p b e l o w , o r to a p p r o x i m a t e l y f o l l o w , b l a c k b o d y r-a d1i a n c e
s p e c t r a d e f i n e d b y τ , d e n o t e d L^b (λ, i ) , for f r e q u e n c i e s a b o v e 3 5 0 c m . A t l o w e r
3 a
f r e q u e n c i e s , w h e r e n o L O W T R A N d a t a a r e a v a i l a b l e , o n l y t h e b l a c k b o d y c u r v e is
p l o t t e d . W e find for all a t m o s p h e r e s t h a t t h e a c t u a l r a d i a n c e lies far b e l o w that o f
t h e b l a c k b o d y in t h e 8 - 1 3 - μ ι η r a n g e ( k n o w n as t h e " a t m o s p h e r i c w i n d o w " ) . A
s e c o n d a r y w i n d o w at 1 6 - 2 2 μιη is o f m u c h s m a l l e r s i g n i f i c a n c e .
T h e a n g u l a r d e p e n d e n c e o f t h e a t m o s p h e r i c r a d i a n c e is o f i m p o r t a n c e for
e v a l u a t i o n s o f t h e r a d i a t i v e c o o l i n g r e s o u r c e . F i g u r e 2 s h o w s this p r o p e r t y for
o n e p a r t1i4c u l a r m o d e l a t m o s p h e r e , t h e 1 9 6 2 U . S . s t a n d a r d , at f o u r different z e n i t h
angles. It is s e e n that t h e r a d i a n c e is e n h a n c e d w i t h i n t h e " a t m o s p h e r i c
w i n d o w s " w h e n t h e z e n i t h a n g l e θ is 5 increased (because the path length
c o n t r i b u t i n g to t h e r a d i a t i o n g o e s u p ) a n d that t h e v a r i o u s c u r v e s p r a c t i c a l l y
o v e r l a p in t h o s e s p e c t r a l r a n g e s w h e r e t h e e m i s s i o n f r o m w a t e r v a p o u r a n d
c a r b o n d i o x i d e a r e s t r o n g e s t . T h e s o l i d c u r v e refers t o θ = 4 5 ° a n d is h e n c e
representative o f the hemispherical radiance. By comparison with the b o t t o m
c u r v e i n F i g . 1, it is f o u n d that t h e r a d i a n c e at θ = 4 5 ° is o n l y s l i g h t l y h i g h e r t h a n
the radiance from the zenith direction. For larger zenith angles the "atmospheric
window" gradually b e c o m e s closed. T h e atmospheric hemispherical radiance,
w h i c h is p e r t i n e n t to a s s e s s m e n t s o f r a d i a t i v e c o o l i n g for s u r f a c e s freely e x p o s e d
to t h e s k i e s , c a n b e o b t a i n e d w i t h a c c u r a c y b y i n t e g r a t i n g o v e r Θ.
WAVELENGTH [μπί]
8 9 10 15 20 30 50100
41 Π j I ι ι ι « ι ' ι ι ι ι ι ni| ι I•IΊ Γ
'g · 7 1962 U.S. STANDARD ^...^ ~_

1
S -2j ZENITH ANGLE: "~
„ Γ 85° / ;f y \ "
2 1.0 - 75°
0 / /f Ç \ 3
y0.8- / /if \ -
< 1 BLACKBODY, / / .·" \ _I
§ - T =288.1K / / : \
DC 0.61- a y _ / : \
S ~ / ί ^ \ ~
I 0.2 j Vv j / ^ N ^ \ ~
0 — —^
I • I • I . I • l • I • I • I • I • I • I • I • I ι I • I ι l ι l ι I • l ι I ι
2000 1600 1200 1
800 400 0
FREQUENCY [cm" ]
Fig. 2. C a l c u l a t e d s p e c t r a l r a d i a n c e for t h e 1 9 6 2 U . S . s t a n d a r d
a t m o s p h e r e at four z e n i t h a n g l e s . A b l a c k b o d y c u r v e
c o r r e s p o n d i n g to 2 8 8 . 1 Κ a m b i e n t t e m p e r a t u r e is i n c l u d e d
for c o m p a r i s o n . T h e h o r i z o n t a l a x i s s h o w s f r e q u e n c y as
w e l l as w a v e l e n g t h . ( F r o m Ref. 1 4 ) .
T h e d a t a in F i g s . 1 a n d 2 r e p r e s e n t c l o u d - f r e e a t m o s p h e r e s . I f t h e a m o u n t o f
p r e c i p i t a b l e w a t e r is i n c r e a s e d s i g n i f i c a n t l y , t h e " a t m o s p h e r i c w i n d o w " is m u c h
l e s s a p p a r e n t ; d e t a i l e d r e s u l t s a r e g i v e n in R e f s . 5 a n d 1 1 . A t h i c k a n d l o w - l y i n g
cloud-cover eliminates radiative cooling entirely. T h i n a n d high-lying clouds are
l e s s significant; their i n f l u e n c e c a n b e e s t i m a t e d o n l y t h r o u g h c a l c u l a t i o n s b a s e d
o n a c t u a l h e i g h t profiles for w a t e r v a p o u r d e n s i t y a n d t e m p e r a t u r e .
It is c o n v e n i e n t to i n t r o d u c e a n a t m o s p h e r i c e m i t t a n c e e ( 9 , λ ) d e f i n e d b y
a
e ( 0 , λ) = L ( 0 , λ, τ ) / L
a a 3 bb(λ, τ 3) . (1)
C l e a r l y , e ( 0 , λ) is s i g n i f i c a n t l5
y different f r o m u n i t y o n l y in t h e 8-13 μ ι η r a n g e , a n d
a
o n e c a n d e f i n e a "box m o d e l " by
e ( 0 , λ) = 1, for 3 < λ < 8 μιη, (2)

a
1c o s e
eaœ,X) = l-[l-ë
a ( 02) ] / , for 8 < λ < 13 μ ι η , (3)
e ( 6 , λ) = 1, for λ > 13 μιη. (4)

a
H e r e ë 2 (0) denotes an average zenith emittance in the "atmospheric window",
a
w h i c h in p r i n c i p l e c a n b e o b t a i n e d f r o m L O W T R A N o r f r o m s p e c t r o r a d i o m e t r y
w i t h s u i t a b l e filters.
S o m e s i m p l i f i e d f o r m u l a s for h e m i s p h e r i c a l l y a v e r a g e d e m i t t a n c e v a l u e s a r e
k n o w n from the literature. T h e s e relate the integrated quantity, expressed
g e n e r a l l y as
π/2
χΗ= [ d(sin2 θ) χ(θ), (5)
to r e a d i l y a c c e s s i b l e p a r a m e t e r s 15
s u c h as w a t e r v a p o u r d e n s i t y o r d e w p o i n t
temperature τ^ . Recent w o r k h a s s h o w n t h a t h e m i s p h e r i c a l t h e r m a l (i.e.,
ρ
i n t e g r a t e d o v e r t h e full P l a n c k s p e c t r u m ) a t m o s p h e r i c e m i t t a n c e c a n b e o b t a i n e d
from
2
e H = 0.711 + 0.56 ( ^ ) + 0.73 ( ^ ) , (6)
a
w h e r e τ ^ is in ° C . T h i s f o r m u l a is useful for a s s e s s i n g r a d i a t i v e c o o l i n g o f b l a c k -
ρ
b o d y - l i k e s u r f a c e s . A r e l a t i o n for e ^ is g i v e n in R e f . 1 6 .
a
B. C o o l i n g P o w e r a n d T e m p e r a t u r e D i f f e r e n c e for I d e a l S u r f a c e s
T h e L O W T R A N d a t a o f L (θ, λ, τ ) c a n b e u s e d for q u a n t i t a t i v e p r e d i c t i o n s o f
a 3
c o o l i n g p o w e r a n d a c h i e v a b l e t e m p e r a t u r e difference. T o this e n d w e c o n s i d e r a
s u r f a c e w h i c h faces t h e s k y a n d d e r i v e t h e n e t t h e r m a l r a d i a t i v e flux a s5 t h e
difference b e t w e e n outgoing and incoming contributions according t o
π/2 oo
Prad = π J d(sin2 Θ) J dX [1 - R (θ, λ)] [ L
bb(λ, τ 5) - L a(θ, λ, t a) ] . (7)
H e r e t d e n o t e s t h e t e m p e r a t u r e o f the e x p o s e d ( n o n - t r a n s p a r e n t ) s u r f a c e a n d
s
1 - R is its a b s o r p t a n c e o r , e q u i v a l e n t l y , e m i t t a n c e . T h e o f f - n o r m a l r e f l e c t a n c e
m u s t b e r e g a r d e d as t h e a r i t h m e t i c m e a n o f t h e r e f l e c t a n c e d u e t o T E - a n d
T M - p o l a r i s e d r a d i a t i o n , i.e.,
R ( 9 , λ) = I [R
TE(θ, λ) + R
TM(θ, λ)]. (8)
R a d i a t i v e c o o l i n g c a u s e s a t e m p e r a t u r e d r o p Δ Τ w h i c h is g i v e n b y
ΔΤ = τ - τ . (9)
3 δ
A t Δ Τ > 0 it is n e c e s s a r y to r e g a r d t h e r o l e o f a n o n - r a d i a t i v e h e a t i n f l u x to the
e x p o s e d surface. T h i s limits the p r a c t i c a l l y useful c o o l i n g p o w e r P to
c
P
c = P r -aK AdT , (10)
w h e r e t h e l o s s is s p e c i f i e d in t e r m s o f a l i n e a r h e a t - t r a n s f e r coefficient κ.
It is e v i d e n t f r o m E q . (7) that t h e s p e c t r a l s u r f a c e r e f l e c t a n c e g o v e r n s t h e r a d i a t i v e
c o o l i n g . It is i l l u s t r a t i v e to c o n s i d e r t h r e e t y p e s o f i d e a l i z e d s u r f a c e s . T h e first o f
t h e s e is t h e fully reflecting s u r f a c e w i t h R ( 6 , λ) = 1. It s e r v e s as a n a p p r o x i m a t i o n
for g o o d m e t a l l i c s u r f a c e s ( c o a t e d w i t h « 0.1 μιη o f o x i d e , etc.) w h i c h c a n h a v e
R « 0 . 9 9 in t h e t h e r m a l infrared. S u c h s u r f a c e s e x p e1 rience no noticeable radiative
c o o l i n g , as o b s e r v e d a l r e a d y in t h e v e r y first s t u d i e s o n this subject. W e r e m a r k ,
in p a s s i n g , that t r a n s p a r e n t a n d infrared-reflecting S n 0 : F c o a t i n g s c a n p r e v e n t
2
r a d i a t i v e c o o l i n g o f g l a s s surfaces e x p o s e d to the clear s k y . S u c h ( e l e c t r i c a l l y
c o n d u c t i n g ) c o a t i n g s h a v e b e e n u s e d to e l i m i n a t e t h e f o r m a t i o n o f t h i c k frost
l a y e r s , w h i c h o t h e r w i s e o c c u r o n the w i n d s c r e e n s o f c a r s p a r k e d o u t d o o r s d u r i n g
c l e a r n i g h t s . T h o s e a s p e c t s o f r a d i a t i v e c o o l i n g a r e t r e a t e d further in R e f . 17.
S i m i l a r l y , s u r f a c e c o a t i n g s b a18
sed on non-conducting B e O can prevent radiative
c o o l i n g a n d frost f o r m a t i o n ; t h e y m a y b e o f i n t e r e s t for h i g h - v o l t a g e p o w e r
lines.
O u r s e c o n d s a m p l e r e g a r d s a b l a c k b o d y - r a d i a t i n g s u r f a c e defined b y R ( 0 , λ) = 0.
T h i s s u r f a c e y i e l d s t h e l a r g e s t c o o l i n g p o w e r at a m b i e n t t e m p e r a t u r e . A b l a c k b o d y
s e r v e s as a g o o d a p p r o x i m a t i o n for o r g a n i c m a t t e r , soils, r o c k s , w a t e r , i c e , m o s t
p a i n t l a y e r s , c o n c r e t e , a s p h a l t , o r d i n a r y u n c o a t e d g l a s s , etc.
T h e t h i r d , a n d for o u r p r e s e n t p u r p o s e s m o s t i n t e r e s t i n g , e x a m p l e is t h e
s e l e c t i v e l y i n f r a r e d - e m i t t i n g s u r f a c e d e s i g n e d for r e a c h i n g t h e l o w e s t p o s s i b l e
t e m p e r a t u r e . T h i s s u r f a c e s h o u l d h a v e h i g h e m i t t a n c e in t h e 8-13 μ ι η
" a t m o s p h e r i c w i n d o w " r a n g e , w h e r e t h e c o u n t e r r a d i a t i o n is w e a k , a n d l o w
a b s o r p t a n c e o u t s i d e this i n t e r v a l , s o that t h e m a i n p o r t i o n o f t h e r a d i a t i o n from
H 0 a n d C O 2 is n o t i n t e r a c t i n g w i t h t h e surface. H e n c e t h e i d e a l p r o p e r t y is
2
R(G, λ) = R
s l e(θ, λ) = 0, for 8 < λ < 1 3 μ ι η , (ID
= 1, e l s e w h e r e . (12)
In S e c . I l l b e l o w w e d i s c u s s p r a c t i c a l surfaces w h i c h a p p r o x i m a t e this i d e a l
property.
F i g u r e 3 s h o w s c a l c u l a t e d r e s u l t s o f P j as a function o f Δ Τ . T h e d a t a a p p l y to
r a c
s u r f a c e s w h i c h r a d i a t e freely t o w a r d m o d e l a t m o s p h e r e s o f t h e s i x t y p e s earlier
d i s c u s s e d . I n F i g . 3 a t h e r a d i a t i n g surface is t a k e n to b e a b l a c k b o d y ; in F i g . 3 b it
h a s a n i d e a l i n f r a r e d - s e l e c t i v e c h a r a c t e r i s t i c a c c o r d i n g to E q s . ( 1 1 ) a n d ( 1 2 ) . F o r
b o t h c a s e s , t h e i n c o m i n g p o w e r is g o v e r n e d b y t h e h e m i s p h e r i c a l r a d i a n c e . It is
f o u n d t h a t t h e2 r a d i a t i v e c o o l i n g p o w e r at a m b i e n t t e m p e r a t u r e l i e s b-2 e t w e e n 71
a n d 1 1 3 W m ~ for t h e b l a c k b o d y s u r f a c e a n d b e t w e e n 5 8 a n d 9 3 W m for t h e
i n f r a r e d - s e l e c t i v e s u r f a c e . T h e h i g h e s t c o o l i n g p o w e r s h o l d for t h e U . S . S T D
a t m o s p h e r e a n d t h e l o w e s t for the T R O P a t m o s p h e r e . T h e v a l u e s for t h e
i n f r a r e d - s e l e c t i v e s u r f a c e lie b e l o w t h o s e for the b l a c k b o d y s u r f a c e s i n c e o n l y t h e
latter t a k e s a d v a n t a g e o f t h e n o n z e r o m a g n i t u d e o f ( L - L ) o u t s i d e t h e 8-13 μιη
bb a
i n t e r v a l (cf. F i g . 1 ) .
T h e r a d i a t i v e c o o l i n g p o w e r is s e e n to d e c r e a s e m o n o t o n i c a l l y w i t h i n c r e a s i n g Δ Τ .
T h e d e c r e a s e is m u c h s l o w e r for the i n f r a r e d - s e l e c t i v e s u r f a c e t h a n for t h e
b l a c k b o d y s u r f a c e , s i n c e t h e f o r m e r e m p l o y s r a d i a t i o n b a l a n c e o n l y in t h e 8-13 μιη
r a n g e w h e r e t h e a t m o s p h e r i c r a d i a n c e is w e a k . It is s e e n that u l t i m a t e
t e m p e r a t u r e differences b e t w e e n 14 a n d 2 6 ° C for the b l a c k b o d y s u r f a c e a n d
b e t w e e n 2 7 a n d 6 2 ° C for t h e i n f r a r e d - s e l e c t i v e s u r f a c e a r e p r e d i c t e d . S u c h l a r g e
ATs c a n n o t b e o b t a i n e d in p r a c t i c e , t h o u g h , b u t t h e r o l e o f c o n d u c t i v e a n d
convective losses of cooling power must be included by use of a nonzero heat
transfer coefficient. A s a p r a c t i c a l l o w limit, o b t a i n a b l e b y 2u s_ e o1 f a n efficient
i n f r a r e d - t r a n s p a r e n t c o n v e c t i o n s h i e l d , w e set κ = 1 W m - K . W e r e t u r n to this
p o i n t in S e c . I V . T h i s r e q u i r e m e n t m a k e s the s h a d e d t r i a n g u l a r a r e a s in F i g . 3
i n a c c e s s i b l e for a c o o l i n g d e v i c e . It is s e e n f r o m t h e f i g u r e t h a t t e m p e r a t u r e
differences b e t w e e n 11 a n d 2 1 ° C for the b l a c k b o d y s u r f a c e a n d b2e t_w e1 e n 18 a n d 3 3 ° C
for t h e i n f r a r e d - s e l e c t i v e s u r f a c e are e x p e c t e d w i t h κ = 1 W m " K . A g a i n the
h i g h e r v a l u e s p e r t a i n to U . S . S T D a n d t h e l o w e r to T R O P . A n a l o g o u s
c o m p u t a t i o n s for e x c h a n g e o n l y w i t h t h e z e n i t h a t m o s p h e r i c r a d i a t i o n are f o u n d
in R e f . 1 3 . S o m e i m p r o v e m e n t o f the r a d i a t i v e c o o l i n g p e r f o r m a n c e c a n b e
obtained under such conditions.
[_l I M | I M I | I I I | | I I [ I | I I I I | I I I I | ι ι ι ι | ι ι
120 - HEMISPHERICAL RADIANCE:
100 - \ ^
^ \ MS Z
80 A \ -
t\\ ss I
eoAA\*\ blackbody sw z
-\^\ SURFACE -
oc H ι ι ι ι 11 h fi π ι ι 1
S Γ 10 20 30
2 1 0 0 Γ b
g N :
5 ^ \80 "
§ infrared-selective ~
α 6 0 ζτ'*·. ν SURFACE -
4 0 '-_ -
0 ι ι ι ι Iι ι ι ι Iι ι »ι I ι ι ι ι Iι ι ι ι I ι ι ι ι I • ι , , I, ,
10 20 30 40 50 60 70
TEMPERATURE DIFFERENCE, £ T f C ]
Fig. 3. Calculated relationship between radiative cooling power
a n d t e m p e r a t u r e d i f f e r e n c e for s i x m o d e l a t m o s p h e r e s
(cf. F i g . 1) a n d t w o ideal surfaces. ( F r o m R e f . 1 4 ) .
ΙΠ. SURFACES WITH INFRARED-SELECTIVE EMISSION
S u r f a c e s w h i c h a r e i n f r a r e d - s e l e c t i v e a c c o r d i n g t o E q s . (11) a n d (12) h a v e a
p o t e n t i a l for r e a c h i n g l o w e r t e m p e r a t u r e s t h a n n o n - s e l e c t i v e s u r f a c e s . S p e c t r a l
s e l e c t i v i t y c a n b e o b t a i n e d b y s e v e r a l m e a n s : b y thin s i l i c o n - b a s e d c o a t i n g s b a c k e d
b y m e t a l (Sec. I l l A ) , b y m e t a l l i z e d p o l y m e r foils (Sec. I l l B ) , b y g a s s l a b s b a c k e d b y
metal (Sec. Ill C ) , a n d b y certain ceramic oxide layers (Sec. Ill D ) .
It is e v i d e n t t h a t n o n e o f t h e m e n t i o n e d a p p r o a c h e s l e a d s t o a s u r f a c e w h i c h
c o m p l e t e l y m i m i c s t h e i d e a l r a d i a t i v e p r o p e r t y . I n o r d e r to b e a b l e t o o p t i m i z e a
p r a c t i c a l s u r f a c e for r a d i a t i v e c o o l i n g a p p l i c a t i o n s , it is t h e r e f o r e c o n v e n i e n t to
define t w o parameters which govern the essential features o f the radiative
c o o l i n g . T h e " b o x m o d e l " for t h e a t m o s p h e r i c e m i t t a n c e , g i v e n b y E 5q s . (2) - ( 4 ) ,
l e a d s n a t u r a l l y to i n t e g r a t e d s u r f a c e e m i t t a n c e v a l u e s a c c o r d i n g t o
oo oo
ëf =J dλL [1 - RH ( λ ) ] / J άλL
bb (λ, x a) bb (λ, τ ) ,
3 (13)
„ 13 μιη 13 μιη
e = J d\L a,T )[l-RH(x)]/ J dXL
s 28 μιη
b ba
8 μιη b f tb, x a) , (14)
n H
= Î
2/ f , (15)
H
where R is t h e h e m i s p h e r i c a l r e f l e c t a n c e d e f i n e d , in a n a l o g y w i t h E q . ( 5 ) , b y
H π/2 2
R ( X ) = ί d ( s i n 9 ) R (θ, λ). (16)
Η
E s s e n t i a l l y , e " g o v e r n s t h e c o o l i n g p o w e r at a m b i e n t t e m p e r a t u r e a n d η
s2
g o v e r n s t h e m a x i m u m a c h i e v a b l e t e m p e r a t u r e d r o p . Efficient c o o l i n g r e q u i r e s a
l a r g e v a l u e - i d e a l l y u n i t y - o f e *ί, aΗ n d if l o w t e m p e r a t u r e s a r e to b e r e a c h e d w e
also require a large m a g n i t u d e of η . T h e theoretical m a x i m u m o f the latter
q u a n t i t y is 3.39 at x = 0 ° C . S e v e r a l o f the p r a c t i c a l i n f r aΗ r e d - s e l e c t i v e surfaces
a
d i s c u s s e d b e l o w w i l l b e a n a l y z e d in t e r m s o f and η .
A. Silicon-Based Coatings Backed b y Metal
Thin coatings of Si-based materials, including Si-O and Si-N bonds, have been
s t u d i e d in c o n s i d e r a b l e detail for r a d i a t i v e c o o l i n g to l o w t e m p e r a t u r e s . T h e b a s i c
i d e a is to start w i t h a h i g h - r e f l e c t i n g m e t a l s u r f a c e , s u c h as a l u m i n i u m , a n d c o v e r
it w i t h a c o a t i n g w h i c h is s e l e c t i v e l y e m i t t i n g in t h e 8-13 μιη r a n g e . B y c h o o s i n g a
p r o p e r t h i c k n e s s o f t h e c o a t i n g , antireflection c a n b e u s e d to3m 5 a x i m i z e the emit-
t a n c e w i t h i n t h e " a t m o s p h e r i c w i n d o w " r a n g e . Initial w o r k ' u s e d S i O c o a t i n g s
p r o d u c e d b y r e s i s t i v e e v a p o r a t i o n . T h i s m a t e r i a l is c a p a b l e o f y i e l d i n g a h i g h
e m i t t a n c e o n l y in p a r t o f t h e 8-13 μιη i n t e r v a l , a n d S i O N is a s u p e r i o r c o a t i n g
x y
m a t e r i a l . S i l i c o n - o x y n i t r i d e c o a t i n g s h a v e b e e n p1
r9e p a r e d for r a d i a t i v e c o o l i n g
2 0
applications both by reactive e-beam e v a p o r a t i o n and reactive radio frequency
magnetron sputtering.
F i g u r e 4 a - c i l l u s t r a t e s t h e i n f r a r e d n e a r - n o r m a l r e f l e c t a n c e in t h e 5 < λ < 5 0 μ ι η
i n t e r v a l for a p u r e s i l i c o n d i o x i d e c o a t i n g ( S i 0 ; p a r t a ) , an e s s e n t i a l l y p u r e silicon
2
n i t r i d e c o a t i n g ( S i O Q . ^ N j ; p a r t b ) , a n d a s i l i c o n - o x y n i t r i d e c o a t i n g ( S i O } .47N0.54;
5 2
p a r t c ) . A l l c o a t i n g s a r e a b o u t 1 μιη thick a n d b a c k e d b y h i g h l y reflecting
aluminium. The compositions were determined by Rutherford Backscattering
Spectrometry. T h e pronounced reflectance m i n i m a stem from p h o n o n absorp-

tion. It a p p e a r s t h a t p u r e s i l i c o n d i o x i d e y i e l d s a b s o r p t i o n in t h e s h o r t - w a v e -
l e n g t h p a r t o f t h e " a t m o s p h e r i c w i n d o w " , a n d that s i l i c o n n i t r i d e y i e l d s a b s o r p -
t i o n p r e d o m i n a n t l y in t h e l o n g - w a v e l e n g t h p a r t o f t h e " a t m o s p h e r i c w i n d o w " .
N o t surprisingly, a silicon-oxynitride coating, with substantial amounts of both
oxygen and nitrogen, gives a g o o d coverage of the entire "atmospheric window"
r a n g e , as e v i d e n t from F i g . 4 c . T h e r a d i a t i v e p r o p e r t i e s o f s i l i c o n - o x y n i t r i d e s c a n
b e u n d e r s t o o d in detail b y first a s s u m i n g their m i c r o s t r u c t u r e to b e d e s c r i b e d b y
five f u n d a m e n t a l S i - b a s e d t e t r a h e d r a , w h o s e r e l a t i v e o c c u r r e n c e is g i v e n b y the
s t o i c h i o m e t r y , a n d t h2e n20
1u s i n g Effective M e d i u m T h e o r y to a v e r a g e o v e r t h e
different t e t r a h e d r a . ' T h e p e r t i n e n t t h e o r i e s w e r e i n t r o d u c e d in t h e c h a p t e r
o n O p t i c a l P r o p e r t i e s o f T w2 o23
- C2o m p o n e n t M a t e r i a l s . Superimposed
Si-oxide/Si-nitride layers ' d o n o t p r o d u c e as f a v o u r a b l e r a d i a t i v e p r o p e r t i e s as
t h o s e f o u n d in t h e s i l i c o n - o x y n i t r i d e s .
WAVELENGTH (μιη)
SO 20 10 7 5
ρ ι ι r~i—ι—ι 1 1 1
ioo U-— — ! 1
!
R
£ _ TM V ~
9i 6 0 _
Λ R -
- - \ ΧΛ™ -
S i 0
Ο - I\ 2 I V Μί.Οβμιη
40
- Α
.' HHP
20 - /
0 —
J—» ι ι ι I ι ι ι t 1 ι ι ι ι I ι ι ι ι I
0 500 1000 1500 1 2000
WAVENUMBER (cm' )
Fig. 4 . M e a s u r e d s p e c t r a l infrared r e f l e c t a n c e at 2 5 ° a n g l e o f i n c i d e n c e
for r e a c t i v e l y R F - s p u t t e r e d S i O N films o n a l u m i n i u m c o a t e d
x y
glass. T h e d a t a refer to T M p o l a r i s a t i o n , b u t t h e s m a l l n e s s o f
t h e a n g l e o f i n c i d e n c e g u a r a n t e e s that t h e r e f l e c t a n c e o f T E
p o l a r i s e d light is p r a c t i c a l l y t h e s a m e . P a r t s a-c refer to diffe-
r e n t c o m p o s i t i o n s r a n g i n g from p u r e s i l i c o n d i o x i d e to a l m o s t
pure silicon nitride. T h e insets indicate the experimental
c o n f i g u r a t i o n s a n d s t a t e v a l u e s o f film t h i c k n e s s e s a n d
c o m p o s i t i o n s . P a r t a is s h o w n a b o v e ; p a r t s b - c f o l l o w o n t h e
n e x t p a g e . ( R e d r a w n from Ref. 2 0 ) .
WAVELENGTH (μπι)
50 20 10 7 5
Γ——γη ι Ι [-Τ—ι ι Ι | Ι
100 —
80- V/ \ R
g - T M \
LU ~ I
ϋ 60 - \ N R_ S J O
S40 Γ Ι i.47 o.54 Âi.20um-
û! ~ I / glass WWM
LU I /
oc _ \ I
20- \ /
0
l I I I I I I I I I I I I I I I I ί I I I
0 500 1000 1500 1 2000
WAVENUMBER(cm~ )
Fig. 4 b .
WAVELENGTH (urn)
50 1 20 10 7 5
ί Π" —I ' I ' 1 I
100
1(b) Χ ^ 1
80 - \ /
5
—
~
-
R
" t m \
/
/
~
I " 60
\ / \ /™ ~ R
ξ : \ J Si00.25N152
yAl1.17Mm -
in \ / A'
i
WÊÊÊÊÊÊ "
j 40- I / glass W W% ~
til \ /
AC - I / —
20 - 1/ -
Oh
1 I I I ;I I I I I I
,
I I 1 1 1
,
I I I I I
1I 2000
;
0 500 1000 1500
WAVENUMBER (cm" )
Fig. 4 c .
F i g u r e 5 s h o w s s p e c t r a l infrared r e f l e c t a n c e , a n a l o g o u s w i t h F i g . 4 , for a SIOq^Nq

2
c o a t i n g p r o d u c e d b y e v a p o r a t i o n o f S13N4 in t h e p r e s e n c e o f s o m e o x y g e n . T h e
c u r v e s refer to T E a n d T M p o l a r i s a t i o n a n d 4 5 ° a n g l e o f i n c i d e n c e . T h e t w o sets o f
d a t a a r e q u i t e s i m i l a r a n d s h o w l o w r e f l e c t a n c e s e l e c t i v e l y in t h e 8 - 1 3 μ ι η r a n g e
( i n d i c a t e d b y d o t t e d lines).
WAVELENGTH (μηπ)
50 20 10 7 5
ι Γ Γ Ί — j — ι 1 ι—ι—j 1 1 1
w " iΛ \ f "
< '_ ιi I -
4 0 R
S r V I 45^1 -
N
S Γ _ R t e
\R β 1 . 3 4 Mr r ^ a f ^ ^ "
20- — " ™ I fj\/ : glass -
Ideal \ ^ / '
_J I I I I I I I I ι I ιΤ ι I I ι ι ι ι I
0 500 1000 1500 - 1 2000
WAVENUMBER ( c m )
Fig. 5. M e a s u r e d s p e c t r a l infrared r e f l e c t a n c e at 4 5 ° a n g l e o f
i n c i d e n c e for a n e - b e a m e v a p o r a t e d S i O N film o n
XY
a l u m i n i u m c o a t e d g l a s s . T h e c u r v e s refer t o T E a n d T M
p o l a r i s a t i o n . D o t t e d lines s h o w t h e i d e a l s p e c t r a l p r o f i l e for
r a d i a t i v e c o o l i n g to l o w t e m p e r a t u r e s .
S p e c t r o p h o t o m e t r i c d a t a o n t r a n s m i t t a n c e a n d r e f l e c t a n c e w e r e u s e d to e v a l5u1a t2
e9
0
t h e c o m p l e x d i e l e c t r i c f u n c t i o n s o f v a r i o u s s i l i c o n - b a s eΗ
d coating m a t e r i a l s , ' '
from which the integrated emittance values e and η were derived.
s2
F i g u r e 6 s h o w s r e s u l t s for S i 0 a n d four different s i l i c o n - o x y n i t r i d e s m a d e b y
2
r e a c t i v e R F - s p u t t e r i n g . C o a t i n g s w i t h s u b s t a n t i a l a m o u n tΗ
s o f o x y g e n a s w e l l as
n i t r o g e n a r e s e e n to y i e l d l a r g e m a g n i t u d e s o f a n d η w h e n t h e t h i c k n e s s is
a b o u t 1 μιη o r s o m e w h a t h i g h e r . F i g u r e 7 r e p o r t s c o r r e s p o n d i n g d a t a for
SiOo Nq 2 a n d S i O m a d e b y evaporation. T h e oxynitride has values that are
6
c o n s i s t e n t w i t h t h o s e for t h e c o r r e s p o n d i n g s p u t t e r - d e p o s i t e d cΗoatings. The SiO
c o a t i n g h a s a n inferior m a g n i t u d e o f e ^ . V a l u e s o f e ^ a n d η for Α 1 θ 3 c o a t i n g s
2
a r e g i v e n in R e f . 2 4 .
Ί 1 I I I I Ij
0.8 -
Iy
0.4- -J/
0.2 - A , ' /
/J'// Si02
Si0
1— ^^0^
1 N50.N444 -
1
||0 0.25*1.52
0 !° 1.47 0.54
Si0 0 N 81 190
y
s ••' i w.^
- y .··· x yr\v
1.0- ^ -
_J I ι ι I ι ι ι ιI I ι ι I ι ι ιι
0.1 0.2 0.5 1 2 5
Thickness (μηι )
Η
Fig. 6. B a s i c c o o l i n g p a r a m e t e r s , e a n d η , v e r s u s t h i c k n e s s for
g2
Si-based coatings m a d e by reactive RF-magnetron sputtering.
B. Metallized Polymer Foils

4
A s l o n g as t w o d e c a d e s a g o it w a s p r o p o s e d b y T r o m b e that c e r t a i n m e t a l l i z e d
p o l y m e r foils c o u l d b e u s e d for r a d i a t i v e c o o l i n g . S o m e o f t h e s e foils e x h i b i t a fair
d e g r e e o f s p e c t r a l selectivity. F i g u r e 8 r e p o r t s t r a n s m i t t a n c e d a t a for t h r e e diffe-
r e n t t y p e s o f p o l y m e r foils. T h e s h o w n r e s u l t s c o r r e s p o n d to t h e e x p e c t e d reflec-
t a n c e s p e c t r u m for a foil h a v i n g h a l f t h e t h i c k n e s s s t a t e d for t h e t r a n s m i t t a n c e
c u r v e s , p r o v i d e d t h a t t h e u n e x p o s e d s i d e o f t h e p o l y m e r is c o v e r e d w i t h a n
o p a q u e and highly reflecting metal layer (normally a l u m i n i u m ) . T h e u p p e r
1 1111 1
Τ 1— I 1
- 0.8 / N ^ ^ ^ ^ l -
H
§ / * /
-0.6 //
- 0.4 /
-0.2 / SiOo.6No.2-
1 — S i 0
_
—0 JL
r2 . 2 T a= 0°C
:
-1.8 y s
\ \\
-
- \\ -
\ -
-1.0 -'
U I Ι Ι I Ι Ι NI I » • Ι Μ , , Ι I
0.1 0.2 0.5 1 2 5 10
THICKNESS (μιη) Η
Fig. 7. B a s i c c o o l i n g p a r a m e t e r s , e a n d η , v e r s u s t h i c k n e s s for
s2
Si-based coatings m a d e by evaporation.
c u r v e in F i g . 8 p e r t a i n s to 1 0 0 μιη o f p o l y v i n y l c h l o r i d e ( P V C ) . T h e s p e c t r a l
s e l e c t i v i t y is q u i t e w e a k . T h e o t h e r t w o c u r v e s a p p l y to 1 2 . 5 μιη o f p o l y v i n y l f l u -
o r i d e ( T e d l a r ; d a t a f r o m Ref. 2 5 ) a n d 3 4 0 μιη o f p o l y - 4 - m e t h y l p e n t e n e ( T P X ; d a t a
f r o m Ref. 2 6 ) . T h e s e latter foils a r e s p e c t r a l l y s e l e c t i v e , a l t h o u g h t h e i r far-infrared 5
a b s o r p t i o n is u n d e s i r a b l y l a r g e . I n t e g r a t e d e m i t t a n c e v a l u e s w e r e e s t i m a t e d from
t hΗe s p e c t r a l t r a n s m i t t a n c e c u r v e s . It w a sΗf o u n d tht P V C y i e l d e d e = 0.78 a n d
Η s2
η = 1.2, T e d l a r y i e l d e d e " = 0.84 a n d η = 1.6, a n d T P X y i e l d e d e " = 0.89 and
g s
η = 1.6. It s h o u l d b e n o t e d that T P X a p p e a r s b l a c k w h e r e a s t h e o t h e r foils a r e
t r a n s p a r e n t . N o n e o f t h e m e t a l l i z e d p o l y m e r foils is as s e l e c t i v e as t h e b e s t m e t a l -
backed silicon-oxynitride coatings.
KX)I ι ι l r π ι ι ι ι n j ι ι ι ι ι ι ι ι ι ι ι ι
1001 —
S :\ΓΛ ,
ί '-\
χ k \
S _ " Tedlar
IoL 11 l/v 125um _

Κ1 0 0 Γ — —
\ ί τρχ
J Wavelength
/ν / [υm] 340um
Fig. 8. Ql SΙp eΙ c tIr aΙl Ν
t r aΙ n sΙm iI t t Ιa nΙc eΙ for
Ι I t hΙ r eΙ e Ιp oΙ l yI mΙe rΙ foils
ι ι Io fι iιn t e r e s t
for r a5d i a t i v e c o10 o l i n g . ( F r15 o m Ref. 5 )20 . 25
C Gas Slabs Backed b y Metal
A s an a l t e r n a t i v e to m e t a l - b a c k e d s i l i c o n - b a s e d c o a t i n g s or p o l y m e r foils, o n e m a y
u s e s l a b s o f c e r t a i n s e l e c t i v e l y i n f r a r e d - e m i t t i n g g a s e s c o n f i n e d b y a n infrared-
t r a n s p a r e n t foil a n d b a c k e d b y a h i g h l y reflecting m e t a l . A t h o r o u g h s u r v e y 27 o f
~ 2 0 0 a v a i l a b l e o r g a n i c a n d i n o r g a n i c g a s e s l e d to t h e c o n c l u s i o n that t h o s e o f
m a j o r i n t e r e s t w e r e a m m o n i a ( N H 3) , e t h y l e n e ( C 2H 4) , e t h y l e n e o x i d e (C2H4O),
a n d m i x t u r e s o f t h e latter t w o . T h e r a d i a t i v e p r o p e r t i e s c a n b e r e l a t e d to t h e i r
m o l e c u l a r c o n f i g u r a t i o n s . 9' 28 G a s e s h a v e the a d v a n t a g e o f b e i n g c h e a p , a n d
allowing easy transport and heat-exchange of the coolant. T h e y also permit
a p p l i c a t i o n s w h i c h r e q u i r e t h e m i x i n g o f t w o or m o r e c o m p o n e n t s .
F i g u r e 9 s h o w s infrared t r a n s m i s s i o n s p e c t r a for N H 3 w i t h t h r e e different p a t h

l e n g t h s a n d at n o r m a l p r e s s u r e . T h e g a s cells w e r e t u b e s w i t h t w o 1 2 μιη thick
p o l y e t h y l e n e w i n d o w s . T h e u p p e r g r a p h s in F i g s . 9 a - c i n d i c a t e t h e t r a n s m i t t a n c e
t h r o u g h air-filled cells a n d t h e l o w e r g r a p h s w e r e r e c o r d e d w i t h gas-filled cells.
T h e differences a m o n g t h e pairs o f c u r v e s ( s h a d e d a r e a s ) s h o w that N H 3 d i s p l a y s a
WAVELENGTH [μm]
,5 6 7 8 9 10 15 20 30 50
1 |0 l0 • ι ι ι τ | ι ι ι ι | ι ι ii|—ι | ι Ml
~ 8 ^ ^ ^ ^ ^
100_^
100Γ
2000 1600 1200 800 400

FREQUENCY [cm"l
Fig. 9. S p e c t r a l t r a n s m i t t a n c e for a m m o n i a g a s at n o r m a l p r e s s u r e
as m e a s u r e d w i t h cells h a v i n g t h e s h o w n l e n g t h s , L .
( F r o m Ref. 2 7 ) .
b r o a d a b s o r p t i o n b a n d c o v e r i n g the d e s i r e d 8-13 μ ι η i n t e r v a l for p a t h l e n g t h s

e x c e e d i n g ~ 1 c m . T h e i n t e r e s t i n g a b s o r p t i o n is c e n t e r e d a r o u n d a n i n f r a r e d -
a c t i v e f u n d a m e n t a l at t h e f r e q u e n c y 9 5 0 c m - . 1T h e c o r r e s p o n d i n g v i b r a t i o n c a n b e
v i s u a l i z e d as t h e Ν a t o m m o v i n g p e r p e n d i c u l a r t o t h e H 3 p l a n e o f t h e a m m o n i a
m o l e c u l e w h i l e its p y r a m i d a l c o n f i g u r a t i o n is r e t a i n e d . 9 T h i s f u n d a m e n t a l
undergoes b r o a d e n i n g as a result o f several m e c h a n i s m s including inversion

d o u b l i n g , r o t a t i o n (i.e., q u a n t i z a t i o n o f t h e a n g u l a r m o m e n t u m ) , c e n t r i f u g a l
d e f o r m a t i o n a n d p r e s s u r e effects. It is s e e n f r o m F i g . 9 that t h e a b s o r p t i o n
b e c o m e s t o o h i g h at t h e l a r g e s t p a t h l e n g t h s a n d , in p a r t i c u l a r , a s t r o n g a b s o r p t i o n
d u e t o a t h e r m a l p o p u l a t i o n o f free r o t a t i o n a l l e v e l s s e t s in at t h e far-infrared e n d
o f t h e s p e c t r u m . T r a n s m i t t a n c e s p e c t r a for C 2 H 4 a n d C 2 H 4 O d i s p l a y a s t r o n g
a b s o r p t i o n in t h e 8-13 μ ι η b a n d , s i m i l a r to t h e c a s e o f NH3, a n d h e n c e t h e t w o
h y d r o c a r b o n g a s e s a r e useful for r a d i a t i v e c o o l i n g . T h e h y d r o c a r b o n s d o n o t s h o w
a n y free r o t a t i o n a l a b s9o r p t i o n in t h e far-infrared, w h i c h c a n b e r e l a t e d t o their
molelcular structure.
T h e t r a n s m i t t a n c e d a t a for t h e t h r e e g a s e s w e r e u s e d to d e r i v e s p e c t r a l a b s o r p t i o n
coefficients, f r o m w h i c h i n t e g r a t e d e m i t t a n c e v a l u e s w e r e o b t a i n e d in p r i n c i p a l lΗ y
t h e s a m e m a n n e r as for t h e solid c o a t i n g s a n d foils. F i g u r e 1 0 s h o w s e a n d η
g2
1 ι 1 I 11M| -τ- T ~ T
1.0
0.8
0.6
0.4
ΠΠ3
C2H4
0.2| C 2H 40
3.0
2.6
2.2
1.8
1.4
1.0U I ι ι l ι ι ι il I ι ι l ι ι ni I ι ι I
0.1 0.2 0.5 1 2 5 10 20 50
THICKNESS, t (cm) Η
Fig. 1 0 . B a s i c c o o l i n g p a r a m e t e r s , e^l a n d η , for N H 3 , C 2 H 4 a n d
C 2 H 4 O g a s l a y e r s h a v i n g different t h i c k n e s s e s . ( F r o m R e f . 2 7 ) .
for g a s s l a b s o f t h i c k n e s s e s b e t w e e n 0.1 a n d 5 0 c m . T h e s l a b s a r e t h o u g h t to b e
b a c k e d b y a l u m i n i u m . It is s e e n that for g a s l a y e r s t h i c k e r t h a n ~ 1 c m , t h e c o o l i n g
p o w e r at a m Η b i e n t t e m p e r a t u r e is l a r g e r for N H 3 t h a n for t h e h y d r o c a r b o n g a s e s .
H o w e v e r , η is l a r g e r for C 2 H 4 a n d C 2 H 4 O t h a n for N H 3 , i m p l y i n g t h a t t h e
h y d r o c a r b o n s d i s p l a y a h i g h e r d e g r e e o f s p e c t r a l selectivity.
A s a l r e a d y m e n t iΗ o n e d , it is o f p a r t i c u l a r i n t e r e s t to r e g a r d g a s m i x t u r e s . F i g u r e 11
s h o w s e ^ a n d η for C 2 H 4 + C H 0 c o m b i n a t i o n s w i t h t h r e e l a y e r t h i c k n e s s e s .
2 4
It is a p p a r e n t t h a t t h e m i x t u r e s c a n h a v e a h i g h e r c o o l i n g p o w e r t h a n e i t h e r o f the
Η
c o n s t i t u e n t g a s e s , w h i c h is an i m p o r t a n t r e s u l t for p r a c t i c a l a p p l i c a t i o n s . T h e
p a r a m e t e r η , o n t h e o t h e r h a n d , is n o t s t r o n g l y i n f l u e n c e d b y t h e m i x i n g . T h e
s u p e r i o r c o o l i n g p o w e r o f t h e m i x t u r e s is r e a d i l y u n d e r s t o o d f r o m t h e s p e c t r a l
t r a n s m i t t a n c e data, w h i c h s h o w that a m o r e c o m p l e t e c o v e r a g e o f t h e 8-13 μ ι η
i n t e r v a l is p o s s i b l e w i t h a c o m b i n a t i o n o f g a s e s t h a n b y a n y o n e o f t h e p u r e g a s e s
a l o n e . F o r c o m p l e t e n e s s w e m e n t i o n that g a s m i x t u r e s c a n a l s o b e u29 s e d to p r o v i d e
r a t h e r h i g h a b s o r p t i o n a c r o s s t h e full t h e r m a l r a d i a t i o n s p e c t r u m .
•f—Z™zzz:r<~j
• Y-s
(/ --"-Ή"
8
s e
2
\M
\y
_Γ t(cm) Ά
7\N.
η
" "
Ο 20 40 60 80 100
PERCENT C 2H 40 IN C 2H 4
Η
Fig. 1 1 . Basic cooling parameters, a n d η , for m i x t u r e s o f C H
2 4
a n d C 2 H 4 O h a v i n g t h r e e l a y e r t h i c k n e s s e s , t. ( F r o m R e f . 2 7 ) .
D. Ceramic Oxide Layers
T h e e a r l i e r d i s c u s s e d a p p r o a c h e s to s e l e c t i v e i n f r a r e d e m i s s i o n r e l y o n h i g h l y
reflecting s u r f a c e s c o v e r e d w i t h a s o l i d o r g a s e o u s s u b s t a n c e w h i c h d e c r e a s e s the
r e f l e c t a n c e p r e d o m i n a n t l y in t h e 8-13 μιη i n t e r v a l . A n o t h e r p o s s i b i l i t y is to u s e a
m a t e r i a l w h i c h y i e l d s a h i g h r e f l e c t a n c e at λ > 13 μιη b y t h e R e s t s t r a h l e n effect.
C e r t a i n c e r a m i c l a y4 e3
rs3 ,0
1a p p r o x i m a t e l y 1 m m in t h i c k n e s s , c a n h a v e t h e d e s i r e d
optical p r o p e r t i e s . ' ' S o m e further i m p r o v e m e n t m a y b e a c c o m p l i s h e d b y
b a c k i n g t h e c e r a m i c l a y e r w i t h a reflecting s u r f a c e .
F i g u r e 1 2 , b a s e d o n Ref. 3 0 , s h o w s s p e c u l a r r e f l e c t a n c e in t h e t h e r m a l infrared for

a 1.1 m m t h i c k l a y e r o f M g O c e r a m i c . T h e m a t e r i a l is o f h i g h d e n s i t y a n d p o l i s h e d
t o a g o o d s u r f a c e finish. T h e h i g h r e f l e c t a n c e at 13 < λ < 2 5 μιη is s t r i k i n g . T h i s is
t h e r a n g e w i t h i n w h i c h m o s t o f t h e a t m o s p h e r i c r a d i a n c e is i m p i n g i n g (cf. F i g . 1).
T h e Reststrahlen band agrees with com 31p u t a t i o n s b a s e d o n o p t i c a l d a t a for s i n g l e
crystals o f M g O . Calculations p r e d i c t that ~ 0.5 m m thick L i F l a y e r s s h o u l d h a v e
r a d i a t i v e p r o p e r t i e s s i m i l a r to t h o s e for M g O .
1 1
1001 —Ι Ι ' — R
? 80- / \
UJ
Ο 60-
I \\
/
< / \ -
Ο
ω
-j
40-
/
/ /
\Χ -
u. ι
α 20- /
01 ^ ^ - / I Ι Ι Ι
5 8 13 20 30 40
W A V E L E N G T H (μητι)
Fig. 1 2 . N e a r - n o r m a l s p e c t r a l r e f l e c t a n c e for a 1.1 m m t h i c k c e r a m i c
M g O l a y e r b a c k e d b y a reflecting surface. ( R e d r a w n f r o m
Ref. 3 1 ) .
IV. INFRARED-TRANSPARENT CONVECTION SHIELDS
R a d i a t i v e c o o l i n g is g o v e r n e d b y t h e d i f f e r e n c e in o u t g o i n g a n d i n c o m i n g
r a d i a t i v e p o w e r , as w e l l as b y t h e n o n - r a d i a t i v e h e a t influx, as d i s c u s s e d in
S e c . I I A . T h e n o n - r a d i a t i v e c o m p o n e n t c a n b e s p e c i f i e d in t e r m s o f a l i n e a r h e a32
t-
transfer coefficient κ, w h i c h for free e x p o s u r e to t h e a t m o s p h e r e c a n b e w r i t t e n
κ = 5.7 + 3.8 ν (17)

2 _ 1 1
in u n i t s o f W m - K , w h e r e ν is t h e w i n d v e l o c i t y in m s " . A l a r g e t e m p e r a t u r e
difference, o r a l a r g e c o o l i n g p o w e r at a m o d e r a t e t e m p e r a1t u r e d i f f e r e n c e , r e q u i r e s
t h a t κ b e d i m i n i s h e d to a v a l u e o n t h e o r d e r o f 1 W m ^ K ' , w h i c h c a n b e a c c o m p -
lished o n l y b y placing the infrared-emitting surface b e l o w a convection shield
w h i c h is t r a n s p a r e n t in t h e 8-13 μιη r a n g e .
A practical infrared-transparent convection shield can b e constructed from high-

d e n s i t y p o l y e t h y l e n e foil. F i g u r e 1 3 i l l u s t r a t e s t h e n o r m a l t r a n s m i t t a n c e t h r o u g h
3 0 μιη o f this m a t e r i a l in the 5 - 5 0 μ ι η i n t e r v a l . S i m i l a r d a t a w e r e s h o w n in F i g . 9
a b o v e . T h e t r a n s m i t t a n c e is ~ 8 5 % in t h e 8-13 μιη r a n g e . N a r r o w m i n i m a at 6.8
a n d 1 3 . 8 μιη - i.e., o u t s i d e t h e " a t m o s p h e r i c w i n d o w " - signify m o l e c u l a r a b s o r p -
tion in t h e m a t e r i a l . O s c i l l a t i o n s at t h e far-infrared e n d o f t h e s p e c t r u m a r e
c a u s e d b y o p t i c a l i n t e r f e r e n c e b e t w e e n the parallel s u r f a c e s o f t h e foil. C o n v e c -
tion s h i e l d s o f p o l y e t h y l e n e h a v e b e e n u s e d in e a r l i e r field tests o f r a d i a t i v e
c o o l i n g . 4,5,12,25-27,31,33-35 j p r i n c i p l e , a p l a t e o f a n i n f r a r e d - t r a n s p a r e n t m a t e r i a l
n
s u c h a s a n t i r e f l e c t i o n - c o a t e d Si o r G e c o u l d b e e m p l o y e d as c o n v e c t i o n s h i e l d , b u t
the cost would b e prohibitive.
WAVELENGTH (pm)
5 7 10 20 50
: 1^ τ
ω _ sijsljijljij Π!;!·
ζ 60- -
|40- I f -
oc ~_ WÊ& 'mi J
20- riis -
I WSè ATM.
_ I :fil : WINDOW :§|jg;

::::::: _
0 · *# # :::::::
I ι
2000 ι ι ι I ι ι I 1000
1500 I I I I I I1500 I I I I I 0I
WAVENUMBER (cm" )
Fig. 1 3 . N o r m a l s p e c t r a l t r a n s m i t t a n c e o f a 3 0 μ ι η t h i c k foil o f h i g h -
d e n s i t y p o l y e t h y l e n e . T h e 8-13 μ ι η " a t m o s p h e r i c w i n d o w "
is i n d i c a t e d . ( F r o m R e f . 3 6 ) .
H i g h - d e n s i t y p o l y e t h y l e n e foil h a s s e v e r a l a t t r a c t i v e f e a t u r e s w h i c h m a k e s it
useful for r a d i a t i v e c o o l i n g a p p l i c a t i o n s . H o w e v e r , t h e r e a r e a l s o p r o b l e m s w h i c h
call for m a t e r i a l s d e v e l o p m e n t . First, a flexible foil is e a s i l y m o v e d e v e n b y w e a k
w i n d s s o t h a t f o r c e d c o n v e c t i o n t a k e s p l a c e , w h i c h l e a d s to a n u n d e s i r e d h e a t
transfer to t h e r a d i a t i v e l y c o o l e d surface. T h e s i t u a t i o n c a n b e i m p r o v e d b y u s e o f
a p o l y e t h y l e n e - b a s e d c e l l u l a r m a t e r i a l , as d i s c u s s e d i n S e c . I V A b e l o w . S e c o n d , i f
r a d i a t i v e c o o l i n g is to b e u t i l i z e d d u r i n g t h e d a y o n e s h o u l d t r y to l i m i t t h e i n f l o w
o f s o l a r e n e r g y to t h e r a d i a t i n g surface. O n e w a y o f d o i n g this is b y d e c r e a s i n g t h e
s o l a r t r a n s m i t t a n c e o f t h e foil, as w e r e t u r n to in S e c . I V B . F i n a l l y , it w o u l d b e
useful to h a v e a c c e s s to a p o l y e t h y l e n e foil o r p l a t e w i t h a l o w e r r e s i d u a l a b s o r p -
t a n c e in t h e 8-13 μιη b a n d t h a n for t h e s t a n d a r d q u a l i t i e s .
A. Polyethylene-Based Cellular Material
H i g h d e n s i t y p o l y e t h y l e n e w i t h infrared t r a n s m i t t a n c e a c c o r d i n g to F i g . 1 3 , w a s
u s e d for t h e c o n s t r u c t i o n o f m e c h a n3i6c a l l y r a t h e r r i g i d m a t e r i a l s c o m p r i s i n g
several layers of V-corrugated f o i l s . Figure 14 shows a sketch of a typical sample:
t h e c o r r u g a t e d l a y e r s , w i t h h e i g h t h a n d a p e x a n g l e Θ, a r e o r i e n t e d at r i g h t a n g l e s .
T h e s a m p l e s s t u d i e d b e l o w h a v e h e q u a l to 0 . 5 , 1 o r 1.5 c m , a n d θ e q u a l to 9 0 ° o r
45°. T h e individual layers were m a d e by hot-forming.
Fig. 1 4 . T h e m a i n figure s h o w s a material with high infrared trans-

mittance and l o w non-radiative heat exchange. It consists
o f t h r e e c r o s s e d c o r r u g a t e d foils o f p o l y e t h y l e n e . T h e l o w e r
figure indicates the pertinent parameters: the height h and
t h e a p e x a n g l e Θ. ( F r o m R e f . 3 6 ) .
T h e infrared transmittance through the material was determined b y use of the

e x p e r i m e n t a l a r r a n g e m e n t s h o w n in t h e i n s e t o f F i g . 1 5 . T h e s a m p l e w a s p l a c e d
c l o s e l y in front o f a b l a c k b o d y - l i k e r a d i a t o r a n d w a s v i e w e d b y i n f r a r e d - i m a g i n g
e q u i p m e n t . T h i s t y p e o f m e a s u r e m e n t m a d e it p o s s i b l e to e v a l u a t e t h e t r a n s -
m i t t a n c e as a f u n c t i o n o f t h e n u m b e r o f i n d i v i d u a l foils. F i l l e d c i r c l e s a n d o p e n
t r i a n g l e s in F i g . 15 p e r t a i n to c o r r u g a t e d foils w i t h different a p e x a n g l e s . T h e
t r a n s m i t t a n c e g o e s m o n o t o n i c a l l y f r o m ~ 9 0 % for a s i n g l e foil to ~ 6 0 % for five
foils, w h i c h is t h e e x p e c t e d b e h a v i o u r . D a t a for flat foils, i n d i c a t e d b y o p e n

s q u a r e s , w e r e in a c c e p t a b l e a g r e e m e n t w i t h s p e c t r o p h o t o m e t r i c r e c o r d i n g s . It is
f o u n d f r o m F i g . 1 5 t h a t t h e t r a n s m i t t a n c e is h i g h e r for 3 c7o r r u g a t e d foils t h a n for
flat o n e s ; this is c o r r o b o r a t e d b y r e c e n t literature d a t a .
1001 i 1
HEATED
BLACKBODY
\. m •
LU
DETECTOR J
Ο 90|
<
5
(/> 80h \ \ SAMPLE
Ζ •
<
CE
Π-
Α 70h
LU
<
CC • 0=90° ^0\.
- 60h a 0=45° \ \ ?
• FLAT FOIL
50 JL
1 2 3 4 5
NUMBER OF FOILS
Fig. 1 5 . T r a n s m i t t a n c e in the 8-13 μ η \ r a n g e v s . n u m b e r o f p o l y -
e t h y l e n e foils for different s a m p l e g e o m e t r i e s . ( F r o m Ref. 3 6 ) .
The non-radiative thermal resistance was measured b y a modifiction of the well

k n o w n g u a r d e d h o t - p l a t e t e c h n i q u e . T h e i n s e t o f F i g . 16 s h o w s t h e e s s e n t i a l
f e a t u r e s o f this t e c h n i q u e . H i g h l y r e f l e c t i n g a l u m i n i u m foil w a s a t t a c h e d to t h e
p l a t e s in o r d e r to m i n i m i z e d i r e c t r a d i a t i v e c o u p l i n g b e t w e e n t h e m . F i g u r e 16
s h o w s n o n - r a d i a t i v e t h e r m a l r e s i s t a n c e as a f u n c t i o n o f s a m p l e t h i c k n e s s . T h e
d a t a for c o r r u g a t e d foils y i e l d a c o n s i s t e n t p a t t e r n w i t h a m o n o t o n i c a l l y v a r y i n g
t h e r m a l r e s i s t a n c e l y i n g b e l o w that o f t h e v a l u e s for e m p t y air g a p s . H e a t flow
t h r o u g h p a r t i a l l y t r a n s p a r e n t m a t e r i a l s is c o m p l i c a t e d , a n d t h e s h o w n d a t a a r e n o t
r e a d i l y a m e n a b l e to t h e o r e t i c a l m o d e l l i n g .
L o o k i n g at F i g s . 15 a n d 1 6 , it is e v i d e n t that a n i n c r e a s e o f t h e t h e r m a l r e s i s t a n c e is
a c c o m p a n i e d b y a d e c r e a s e o f t h e infrared t r a n s m i t t a n c e . W i t h r e g a r d t o r a d i a t i v e
c o o l i n g a p p l i c a t i o n s , t h e r e is t h u s a trade-off b e t w e e n t h e t w o p r o p e r t i e s . A s a
c h a r a c t e r i s t i c r e s u l t it is f o u n d that at a t h i c k n e s s o f 4 . 5 c m - c o r r e s p2o n d i_n1g to
t h r e e 1.5 c m - t h i c k c o r r u g a t e d foils - t h e t h e r m a l r e s i s t a n c e is 1.1 m K W a n d the
i n f r a r e d t r a n s m i t t a n c e is 7 3 %. F u r t h e r i n f o r m a t i o n o n h e a t t r a n s f e r t h r o u g h
c e l l u l a r m a t e r i a l s is g i v e n in t h e c h a p t e r o n T r a n s p a r e n t I n s u l a t i o n M a t e r i a l s .
1
^2.5F ι • ι — — ι — • — r
HOT PLATE
CM Al FOIL
ε , SAMPLE
ο POLYSTYRENE FOAM FRAME
ζ
< Al FOIL -°
Η COLD PLATE
£2 ι
LU
OC
<
ce 1.0
LU
o^^^YMBOL h (cm) 0(DEG.)
D · 0.5 90
ρ 0.5h ^ δ 1.0 90
<
Ο • 1.5 45
< AIR GAP
CC
ι
Z .L _L
ο 1 2 3 4 5 6
z
THICKNESS (cm)
Fig. 16. N o n - r a d i a t i v e t h e r m a l r e s i s t a n c e v e r s u s t h i c k n e s s for
different s a m p l e g e o m e t r i e s . ( F r o m R e f . 3 6 ) .
Β. Polyethylene-Based Solar Reflecting Foils
It is p o s s i b l e to l i m i t t h e s o l a r t r a n s m i t t a n c e o f p o l y e t h y l e n e foils, w h i l e t h e i r
t r a n s m i t t a n c e in t h e 8-13 μιη r a n g e is c o n s e r v e d , b y a p p l y i n g a c o a t i n g o r b y
p i g m e n t a t i o n o f t h e m a t e r i a l . W i t h r e g a r d to c o a t i n g s , it is p o s s i b l e t o u s e a s e m i -
c o n d u c t o r w i t h a cut-off w a v e l e n g t h l a r g e r t h a n t h e i n f r a r e d e n d o f t h e s o l a r
s p e c t r u m ( ~ 2.5 μιη). A m o n g t h e i n t e r e s t i n g m a t e r i a l s a r e t e l l u r i u m a n d P b T e (cf.
R e f s . 2 6 a n d 3 8 ) . I f t h e t h i c k n e s s is > 0.05 μιη, t h e s o l a r t r a n s m i t t a n c e w i l l b e l o w
( < 0.01 at λ = 0.5 μιη). T h e refractive i n d i c e s o f t h e s e c o a t i n g s a r e h i g h , t h o u g h ,
w h i c h t e n d s to l i m i t t h e t r a n s m i t t a n c e in t h e 8-13 μιη b a n d . T h r e e d e s i g n p o s s i b i -
lities exist: T h e first o f t h e s e is to u s e a v e r y thin l a y e r . C u r v e 1 in F i g . 1 7 ,
r e f e r r i n g to 0.05 μιη o f t e l l u r i u m , s h o w s that t h e t r a n s m i t t a n c e is ~ 8 7 % w i t h i n
t h e " a t m o s p h e r i c w i n d o w " . T h e s e c o n d p o s s i b i l i t y is to h a v e a t h i c k n e s s s u c h
t h a t t h e film s e r v e s as a λ / 2 - l a y e r for λ « 11 μιη. A t e l l u r i u m film m e e t i n g this
c o n d i t i o n s h o u l d b e 1.1 μιη t h i c k ; its c a l c u l a t e d t r a n s m i t t a n c e is s h o w n b y c u r v e 2
in F i g . 1 7 . It is f o u n d that t h e t r a n s m i t t a n c e is h i g h o n l y in p a r t o f t h e
" a t m o s p h e r i c w i n d o w " . T h e t h i r d a n d p r i n c i p a l l y b e s t d e s i g n is t o e m b e d t h e
t e l l u r i u m film b e t w e e n t w o l a y e r s w h i c h antireflect in t h e 8 - 1 3 μ ι η r a n g e . C u r v e
3 in F i g . 17 p e r t a i n s to t h e c a l c u l a t e d t r a n s m i t t a n c e for 0.7 μιη o f t e l l u r i u m
b e t w e e n 0 . 8 8 μιη o f C d T e a n d 1.0 μιη o f Z n S . T h e t r a n s m i t t a n c e is s e e n to b e h i g h
within the whole "atmospheric window".
3 100
tu
O
s
</)
z
<
oc
8 10 20
W A V E L E N G T H (μιη)
Fig. 17. Calculated infrared transmittance through tellurium b a s e d
films. T h e c u r v e s 1, 2 a n d 3 refer to 0 . 0 5 μ ι η t e l l u r i u m , 1.1 μ ι η
t e l l u r i u m , a n d 0 . 8 8 μ ι η C d T e / 0 . 7 μιη T e / 1 . 0 μ ι η Z n S , r e s p e c -
tively. T h e effect o f a n u n d e r l y i n g p o l y e t h y l e n e s u b s t r a t e is
n o t i n c l u d e d in t h e c o m p u t a t i o n . ( R e d r a w n f r o m R e f . 2 6 ) .
P i g m e n t a t i o n o r d y e i n g o f t h e p o l y e t h y l e n e foils offers a n o t h e3 r p4
92o s s i b i l i t y t o
c o m b i n e s o l a r r e j e c t i o n w42 ith thermal infrared t r a n s m i t t a n c e . " Figures 18 and
19 s h o w s o m e m e a s u r e d r e f l e c t a n c e a n d t r a n s m i t t a n c e d a t a for 1 0 0 - μ ι η - t h i c k
p o l y e t h y l e n e foils p i g m e n t e d w i t h 0 . 2 3 ^ m - d i a m e t e r T1O2 (rutile) p a r t i c l e s to t h e
s h o w n v o l u m e fractions (f). It is s e e n that a r a t h e r h i g h r e f l e c t a n c e o f s o l a r e n e r g y
(cf. F i g . 18) c a n b e c o m b i n e d w i t h s o m e t r a n s m i t t a n c e in t h e 8 - 1 3 μιη r a n g e (cf. Fig.
19). T h e p r o p e r t i e s a r e n o t i d e a l for r a d i a t i v e c o o l i n g a p p l i c a t i o n s , t h o u g h , a n d a
p i g m e n t w h o s e p h o n o n a b s o r p t i o n lies at l o n g e r w a v e l e n g t h s t h a n t h a t for4T1O2 42
3
w o u l d b e b e t t e r . T h e o p t i c a l p r o p e r t i e s o f p i g m e n t e d foils c a n b e m o d e l e d , ' at
l e a s t s e m i q u a n t i t a t i v e l y , b y t h e t h e o r y for r a d i a t i o n s c a t t e r i n g that w a s i n t r o d u c e d
in t h e c h a p t e r o n O p t i c a l P r o p e r t i e s o f I n h o m o g e n e o u s T w o - C o m p o n e n t
M a t e r i a l s . I n o r d e r to d i m i n i s h t h e s o l a r t r a n s m i t t a n c e it m a y b e f a v o u r a b l e to
c o m b i n e a w h i t e T i 0 2 - c o n t a i n i n g foil w i t h a d o w n w a r d s - f a c i n g s o l a r a b s o r b i n g
foil, w h i c h c a n c o n s i s t o f p o l y e t h y l e n e c o n t a i n4i1n g c a r b o n b l a c k . F i g u r e 2 0 s h o w s
s p e c t r a l t r a n s m i t t a n c e for s u c h a t a n d e m f o i l . It a p p e a r s that a s o l a r t r a n s m i t -
t a n c e o f - 0 . 1 c a n b e c o m b i n e d w i t h a t r a n s m i t t a n c e o f ~ 0.7 for t h e 8 - 1 3 μ ι η r a n g e .
V. RESULTS O F S O M E FIELD T E S T S
S e v e r a l field tests h a v e b e e n c o n d u c t e d w i t h r a d i a t i v e l y c o o l e d d e v i c e s . T h e y
h a v e s h o w n u n a m b i g u o u s l y that r a d i a t i v e e x c h a n g e w i t h t h e c l e a r s k y is a v i a b l e
m e a n s for r e a c h i n g l o w t e m p e r a t u r e s . It is fair to s a y , t h o u g h , t h a t o n l y a f e w o f
t h e d e v i c e s h a v e t a k e n full a d v a n t a g e o f t h e c o o l i n g p o t e n t i a l . A s e r i e s o f e x p e r i -
m e n t s h a v e b e e n p e r f o r m e d to e l u c i d a t e the c o o l i n g p o w e r a n d a t t a i n a b l e
temperature difference using selectively infrared-emitting surfaces m o u n t e d
under simple transparent convection shields of polyethylene. S o m e examples of
test r e s u l t s a r e r e p o r t e d in S e c . V A . In o r d e r to r e a c h v e r y l o w t e m p e r a t u r e s , o n e
1.01 ' rÛ^J. J ' ' I ' ' f' ' I ' ' ' • ! · - • >
J ^ C ^ ^ ^ ' C j - = 0.39 L
N
% f » 0.065 >^ \ .
5 0.4- V
0.2 f
/ T i 0 2- Polyethylene
Ol
1 0
[
S0.8-
c
.5 0.6 - y
" * Λ ~ f =0.065 ^^λ/
c 0.4 - ν -
0 39 f
n ~ C*~~*"**~'\ = · I I
0.5
Ο I 1*+^· \ ι ι ι 1.0
I ι ι ι ι 1.5
I ι ι ι ι 2.0
I ι ι ι l I
Wavelength (μιη)
Fig. 1 8 . T o t a l r e f l e c t a n c e a n d total t r a n s m i t t a n c e for T i 0 - p o l y -
2
e t h y l e n e foils w i t h p i g m e n t v o l u m e f r a c t i o n , f, a s g i v e n
in t h e figure. ( F r o m R e f . 4 2 ) .
1
1.0 ' I I ι ι I
T i 0 2- P o l y e t h y l e n e -|
ο
σ> bo
f = 0.13
tance
f=0.26
ο
F f = 0.39
g 0.4 - I
^0.2
0 ι - I ι J_
4 8 12 16 20
Wavelength (μηι)
Fig. 19. T o t a l t r a n s m i t t a n c e in t h e t h e r m a l - i n f r a r e d w a v e l e n g t h
r e g i o n for T i C ^ - p o l y e t h y l e n e foils w i t h p i g m e n t v o l u m e
fraction, f, as g i v e n in t h e figure. ( F r o m R e f . 4 2 ) .
100
80
60
40
20
0
0 5 10 15
W A V E L E N G T H (μπι)
Fig. 2 0 . T r a n s m i t t a n c e o f a d o u b l e - f a c e b l a c k - a n d - w h i t e foil o f
pigmented polyethylene. (Redrawn from Ref. 41).
c a n w o r k w i t h m u l t i s t a g e c o o l i n g d e v i c e s , as i l l u s t r a t e d in S e c . V B . S o l a r ref-
l e c t i n g c o n v e c t i o n s h i e l d s offer a v e r y s i m p l e a p p r o a c h to r a d i a t i v e c o o l i n g .
S o m e initial r e s u l t s b a s e d o n this i d e a a r e g i v e n in S e c . V C.
A. Selectively Infrared-Emitting Surfaces Placed under Transparent

Convection Shields: S o m e Examples
A n u m b e r o f s e l e c t i v e l y i n f r a r e d - e m i t t i n g s u r f a c e s w e r e d i s c u s s e d in S e c . I l l , a n d
s i l i c o n - o x y n i t r i d e c o a t i n g s , b a c k e d b y h i g h l y r e f l e c t i n g a l u m i n i u m , w e r e f o u n d to
h a v e v e r y g o o d s p e c t r a l p r o p e r t i e s w i t h l o w r e f l e c t a n c e in t h e 8-13 μ ι η b a n d a n d
h i g h r e f l e c t a n c e 4for 4 o t h e r w a v e l e n g t h s . S u c h s u r f a c e s h a v e b e e n i n t e g r a t e d in
c o o l i n g2 d e v i c e s w h o s e g e n e r a l d e s i g n is i l l u s t r a t e d i n F i g . 2 1 . T h e c o o l i n g plate,
0.25 m in s i z e , is o f a l u m i n i u m a n d h a s a 1.2 μιη t h i c k c o a t i n g o f SiO1.47N0.54
produced b y reactive radio frequency magnetron sputtering. T h e near-normal
s p e c t r a l r e f l e c t a n c e o f t h e s u r f a c e w a s s h o w n in Fig. 4 c . T h e c o o l i n g p l a t e w a s
m o u n t e d u n d e r a s i n g l e h i g h - d e n s i t y p o l y e t h y l e n e foil w i t h t r a n s m i t t a n c e
a c c o r d i n g to F i g . 1 3 . A n a r r a n g e m e n t w i t h s t r e t c h i n g ribs h e l d t h e foil in tension.
T h e r m a l emission from the walls surrounding the cooling plate w a s m i n i m i z e d
b y t h e u s e o f a l u m i n i z e d M y l a r foil. T h e r m a l i n s u l a t i o n o f t h e c o o l i n g p l a t e w a s
accomplished b y polyurethane foam. T h e underside o f the cooling plate was
equipped with thermometers and electrical heating elements.
C o o l i n g tests w e r e c o n d u c t e d u n d e r a v a r i e t y o f c l i m a t i c c o n d i t i o n s . F i g u r e 2 2
s h o w s t h e t e m p e r a t u r e w h i c h w a s r e c o r d e d for free e x p o s u r e to t h e c l e a r s k y
d u r i n g a w i n t e r n i g h t in G o t h e n b u r g , S w e d e n . T h e d e w - p o i n t t e m p e r a t u r e is
, STRETCHING RIBS
/ ΑΙ-COATED MYLAR
EH F
LD 0P ,
/ / / CABLE FOR
,__// y ^COOLING PLATE ^ THERMOMETER
R
/ ^ /
Fig. 2 1 . S k e t c h o f a d e v i c e for testing r a d i a t i v e c o o l i n g o f s i l i c o n -

o x y - n i t r i d e c o a t e d surfaces.
1
p — . — ι — ι — ι — < — ι — "i 1
-10- \
gC -20— \ \ dew
< - \ \
Œ _ \ \
HI \ \
S -30h \ \
' NX^BIackbody Ts
Selective^ , „ ζ
-40U ι I ι I ι I ι I ι L
14 16 18 20 22 24
TIME (hours)
Fig. 2 2 . C o o l i n g p e r f o r m a n c e v s . t i m e for a m b i e n t t e m p e r a t u r e x ,
a
d e w p o i n t t e m p e r a t u r e x ^ , a n d for t h e s u r f a c e t e m p e r a t u r e
e w
τ o f materials with an infrared selective silicon-oxy-nitride
5
coating and with a blackbody-like paint layer. T h e data w e r e
t a k e n w i t h d e v i c e s o f the k i n d i l l u s t r a t e d in F i g . 2 1 .
~ - 1 8 ° C, a n d h e n c e t h e test s i m u l a t e s to s o m e e x t e n t t h e c o o l i n g p e r f o r m a n c e
p e r t i n e n t to a v e r y d r y c l i m a t e . T h e c u r v e s d e n o t e d "selective" a n d " b l a c k b o d y "
i n d i c a t e t h e t e m p e r a t u r e v s . t i m e for t w o c o o l i n g d e v i c e s i n c o r p o r a t i n g a n
i n f r a r e d - s e l e c t i v e s i l i c o n - o x y n i t r i d e s u r f a c e a n d , for r e f e r e n c e , a b l a c k b o d y - l i k e
p a i n t e d surface. It is s e e n that t h e i n f r a r e d - s e l e c t i v e s u r f a c e r e a c h e d Δ Τ « 2 0 ° C
w h e r e a s the b l a c k b o d y - l i k e s u r f a c e r e a c h e d Δ Τ ~ 1 8 . 5 ° C . T h e o b s e r v e d t e m p e r a -
t u r e difference, 44 a n d its d e p e n d e n c e o n the n e t c o o l i n g p o w e r , is c o n s i s t e n t w i t h
c a l c u l a t i o n s based on the L O W T R A N computer c o d e and a m o d e l atmosphere
of the Subarctic W i n t e r type. M u c h larger temperature drops, a n d larger
differences b e t w e e n t h e s e l e c t i v e a n d n o n - s e l e c t i v e s u r f a c e s , a r e e x p e c t e d in
d e v i c e s w i t h l o w e r n o n - r a d i a t i v e h e a t influx.
G a s s l a b s b a c k e d b y m e t a l offer a n o t h e r p o s s i b i l i t y to e x27 p l o i t r a d i a t i v e c o o l i n g , as
d i s c u s s e d in S e c . I l l C. P r a c t i c a l t e s t i n g w a s p e r f o r m e d w i t h c o o l i n g p a n e l s o f the
t y p e s h o w n in F i g . 2 3 . T h e y c o m p r i s e a p o l y s t y r e n e b o x w i t h a n infrared-trans-
p a r e n t w i n d o w c o n s i s t i n g o f t h r e e p o l y e t h y l e n e foils. T h e i n t e r i o r o f t h e b o x w a s
c l a d w i t h a l u m i n i u m foil. D e p r e s s u r i z e d g a s at a m b i e n t t e m p e r a t u r e w a s r u n via
a f l o w m e t e r t h r o u g h a 10 c m t h i c k r e g i2 on under the infrared-transparent window.
T h e a r e a e x p o s e d to t h e s k y w a s 0.38 m . T h e r m o m e t e r s w e r e a r r a n g e d to m e a -
s u r e t h e g a s t e m p e r a t u r e at t h e inlet a n d outlet.
F i g u r e 2 4 s h o w s a n e x a m p l e o f r e s u l t s from a c o o l i n g test w i t h C2H4 g a s . T h e

e x p e r i m e n t w a s c a r r i e d o u t in full d a y l i g h t w i t h a s m a l l s c r e e n set t o b l o c k t h e
d i r e c t s o l a r r a d i a t i o n . T- h e2 e n s u i n g l o a d d u e to diffuse r a d i a t i o n is e x p e c t e d to b e
o n t h e o r d e r o f 1 0 W m . T h e air t e m p e r a t u r e w a s ~ 5 ° C a n d t h e r e l a t i v e h u m i -
dity was 3 ~ 430 %. 1 A t p o i n t A in t h e figure the g a s w a s i n t r o d u c e d a t a r a t e o f
0.6 χ 1 0 ~ m s" . A t e m p e r a t u r e difference o f 7 ° C w a s e s t a b l i s h e d w i t h i n a f e w
m i n u t e s . A t p o i n t Β t h e g a s f l o w w a s s t o p p e d at w h i c h p o i n t Δ Τ b e c a m e a s l a r g e
as 1 0 ° C . R e s u m e d g a s f l o w at p o i n t C a g a i n l e d to Δ Τ ~457 ° C . D e v i c e s u s i n g self-
circulation of radiatively cooled gas have been t e s t e d .
Gas outlet
Test panel for / O ^ ^
radiative cooling / / 3 polyethylene
of C 2H 4 gas / ~-éf\
" ~^^Ι κ — Thermometer

asF l o w i n
/ / r J W / 9 9
y / χ ~ Aluminium foil
^- — ' / .— Polystyrene box
Thermometer
Gas inlet
Fig. 2 3 . C u t a w a y d i a g r a m o f p a n e l for t e s t i n g r a d i a t i v e g a s c o o l i n g .
The large arrows indicate laminar gas flow. ( F r o m Ref. 2 7 ) .
C e r t a i n c e r a m i c s c a n d i s p l a y infrared s e l e c t i v i t y as a c o n s e q u e n c e o f t h e i r
R e s t s t r a h l e n b a n d . M g O is s u c h a m a t e r i a l , as p o i n t e d o u t in S2 ec. Ill D. Test
r e s u l t s for311.1 m m t h i c k p o l i s h e d M g O c e r a m i c p l a t e s , ~ 0.5 m in s i z e , h a v e b e e n
reported. T h e plates were well insulated on the underside and m o u n t e d b e l o w
—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι—ι ι ι ι ι ι ι ι—ι—I I
ο 5
τΓ ^^~~~\
ο _ ^
φ - \
3 ~ \
2±0 \_ v
ε - ν
Ê - t \ ^
-5- I _
I I I I I I I I I I I I I I I I I I I I I I I I I
0 5 10 15 20
Time [minutes]
Fig. 2 4 . E x c e r p t f r o m a n e x p e r i m e n t for t e s t i n g r a d i a t i v e c o o l i n g
with a 10-cm-thick slab of C H . x and x
2 4 in o t due n o t e t h e
t e m p e r a t u r e s at t h e g a s i n l e t a n d o u t l e t , r e s p e c t i v e l y , i n t h e
p a n e l s h o w n in F i g . 2 3 . x is t h e a m b i e n t t e m p e r a t u r e . A t
a
A , B , a n d C , t h e g a s f l o w w a s a d j u s t e d to t h e s h o w n rates.
( F r o m Ref. 2 7 ) .
a 5 0 μιτι t h i c k p o l y e t h y l e n e foil. T h e y c o u l d b e h e a t e d e l e c t r i c a l l y . F i g u r e 2 5
s h o w s m e a s u r e d t e m p e r a t u r e v s . t i m e for c o o l i n g d e v i c e s i n c o r p o r a t i n g a M g O
p l a t e a n d , for r e f e r e n c e , a b l a c k b o d y - l i k e p a i n t e d s u r f a c e . A t e m p e r a t u r e m o r e
than 20°C lower than x was measured on the M g O plate. T h e blackbody-like
a
s u r f a c e c o u l d r e a c h a t e m p e r a t u r e difference w h i c h w a s ~ 3 ° C s m a l l e r . T h e
d i f f e r e n c e b e t w e e n t h e t w o t y p e s o f surfaces i n c r e a s e d to - 5 ° C w h e n t h e d i s t a n c e
between the cooling surface and the convection shield w a s increased from the
o r i g i n a l 2 . 5 c m u p to 5 c m . T h e d i f f e r e n c e in p e r f o r m a n c e b e t w e e n t h e t w o t y p e s
o f s u r f a c e s b e c a m e s m a l l e r as p o w e r w a s fed i n t o t h e h e a t e r , w h i c h is t h e e x p e c t e d
result.
B. Multistage Cooling Devices
C a r e f u l l y c o n s t r u c t e d m u l t i s t a g e d e v i c e s c a n b e u s e d to c r e a t e v e r y l o w
t e m p e r a t u r e s o n s m a l l s u r f a c e s e x p o s e d to a t m o s p h e r e s w i t h l o w h u m i d i t y . A
n u m b e r o f i m p o r t a n t e x p e r i m e n t s44 w6i t h s u c h d e v i c e s w e r e c o n d u c t e d at 47h i g h
a l t i t u d e in t h e F r e n c h P y r e n n é e s ' a n d in t h e A t a c a m a d e s e r t i n C h i l e d u r i n g
the 1960's and 1970's.
20 π 1 1 1 1 j 1 Γ
g 10
-
LU
CC
D
H Blackbodv^
<
CC \ paint
LU
α
S
LU
90 ce cC
S e l e c t i v e MgO
•10
H60 s
Ί
30 α
0 ce
_i L LU
18 20 22 24 02 <
LU
TIME (hours) X
Fig. 2 5 . C o o l i n g p e r f o r m a n c e vs. t i m e for a m b i e n t t e m p e r a t u r e

x a n d for t h e s u r f a c e t e m p e r a t u r e x o f i n f r a r e d - s e l e c t i v e
a s
M g O c e r a m i c a n d o f b l a c k - b o d y - l i k e paint. T h e r e s u l t o f a n
i n p u t o f e l e c t r i c p o w e r to t h e s u r f a c e s is s h o w n . ( R e d r a w n
from Ref. 31).
46
F i g u r e 2 6 illustrates a five-stage d e v i c e w i t h 1.2 m b a s e s i d e . N u m b e r s 1-5
denote infrared-radiating surfaces of oxidized a l u m i n i u m or T i 0 paint.
2
N u m b e r s 6 - 1 0 d e n o t e 3 0 μιη t h i c2k p o l y e t h y l e n e foils. T h e i n n e r m o s t c o o l i n g
surface, h a v i n g a n a r e a o f 2 5 c m , c o u l d r e a c h Δ Τ ~ 3 7 ° C u n d e r f a v o u r a b l e
m e t e o r o l o g i c a l c o n d i t i o n s d e s p i t e t h e fact that t h e r a d i a t i n g s u r f a c e s m u s t h a v e
b e e n r a t h e r b l a c k b o d y - l i k e . I f t h e interior o f t h e c o o l i n g d e v i c e w a s filled w i t h
C 0 g a s , a t e m p e r a t u r e difference e x c e e d i n g 4 0 ° C w a s o b s e r v e d .
2
F i g u r e 2 7 i l l u s t r a t e s t h e t h e r m a l p e r f o r m a n c e o f a f o u r - s t a g e d e v i c e a n a l o g o u s to
t h e o n e s h o w n in F i g . 2 6 . T h e different c u r v e s d e n o t e x a n d t h e t e m p e r a t u r e s x
a s
o f t h e c o o l i n g s u r f a c e s . T h e r e l a t i v e h u m i d i t y w a s a b o u t 5 0 %. A n a r r o w m a r k s
the introduction o f C 0 gas. A m a x i m u m temperature difference o f ~ 3 3 ° C w a s
2
o b s e r v e d in this e x p e r i m e n t .
^^^^
Fig. 2 6 . S k e t c h o f a five-stage c o o l i n g d e v i c e . ( F r o m R e f . 4 6 ) .
— ι — ι — ι — ι — ι — ι — ι — ι — ι — ι — ι ι ι
o-
10- · -
LU
CC
20-
<
CC
ω - 3 0 P
: : : :
40-^ ^ -
ι ι ι I » I ι I ι I ι I ι
20 22 24 2 4
TIME (hours)
Fig. 2 7 . C o o l i n g p e r f o r m a n c e vs. t i m e for a m b i e n t t e m p e r a t u r e x

a
a n d for t h e t e m p e r a t u r e x o f four s u c c e s s i v e l y s m a l l e r a n d
s
c o l d e r s u r f a c e s a r r a n g e d in a f o u r - s t a g e c o o l i n g d e v i c e s i m i l a r
to t h e o n e in F i g . 2 6 . A n d a r r o w m a r k s t h e i n t r o d u c t i o n o f C 0
2
gas. ( R e d r a w n f r o m Ref. 4 6 ) .
G Cooling with Polyethylene-Based Solar Reflecting Foils
C o o l i n g c a n b e a c c o m p l i s h e d e v e n d u r i n g t h e d a y b y p l a c i n g a foil w i t h h i g h s o l a r
r e f l e c t a n c e a n d s i g n i f i c a n t t r a n s m i t t a n c e in t h e 8-13 μιη r a n g e o v e r t h e s p a c e to b e
c o o l e d . S u c h foil m a t e r i a l s h a v e b e e n d i s c u s s e d in t h e l i t e r a t u r e , a n d t h e r e s u l t s
of som 3 e 9d 4e8v-e l4o p m1e n t w o r k w e r e m e n t i o n e d in S e c . I V B . T h e foils w e r e
used ' for s p a c e c o o l i n g . F i g u r e 2 8 s h o w s t h e t e m p e r a t u r e i n s i d e a n d o u t s i d e
a g r e e n h o u s e c o n s t r u c t e d w i t h foils a c c o r d i n g t o F i g . 2 0 . A t e m p e r a t u r e difference
o f 3 - 4 ° C , w i t h t h e i n t e r i o r b e i n g t h e c o l d e r , is o b s e r v e d b o t h in t h e d a y a n d t h e
night. H e n c e t h e r e is n o d o u b t as to t h e feasibility o f s p a c e c o o l i n g b y u s e o f solar
r e f l e c t i n g a n d infrared t r a n s m i t t i n g foils. T h e s t u d i e d foil m a t e r i a l d o e s n o t
e x h i b i t o p t i m i z e d p r o p e r t i e s , t h o u g h , a n d it is e x p e c t e d t h a t a s i g n i f i c a n t
i m p r o v e m e n t c o u l d b e a c c o m p l i s h e d if t h e foils h a d a h i g h e r s o l a r r e f l e c t a n c e .
1 1 1
' I I —I—'—ι—'—ι— —I—r—
ω
cc
<
CC
LU
α
S
LU
101 ι I ι I ι I ι I ι I ι I ι
12 24 12
12 24 12 24
TIME (hours)
Fig. 2 8 . C o o l i n g p e r f o r m a n c e v s . t i m e for a m b i e n t t e m p e r a t u r e
x a n d for t h e t e m p e r a t u r e T j i n s i d e a g r e e n h o u s e
a nt
constructed with solar reflecting and infrared transmitting
foil. ( R e d r a w n f r o m Ref. 4 8 ) .
VI. CONCLUDING REMARKS
R a d i a t i v e c o o l i n g is a n u b i q u i t o u s 2
p h e n o m e n o n under a clear sky. T h e power
a v a i l a b l e for c o o l i n g is ~ 1 0 0 W m ~ at a m b i e n t t e m p e r a t u r e . T o p u t this n u m b e r
in p e r s p e c t i v e , w e p o i n t o u t that t h e m a x i m u m s o l a r e n e r g y a v a i l a b l e for h e a t i n g
is ~ 1 0 0 0 W m - 2 , i.e., o n l y o n e o r d e r o f m a g n i t u d e l a r g e r .
T h e relation between cooling p o w e r and temperature difference can b e under-

s t o o d q u a n t i t a t i v e l y if t h e f o l l o w i n g t h r e e p r o p e r t i e s a r e s p e c i f i e d :
(i) T h e atmospheric d o w n w a r d s radiance should be known. Often one can use

d a t a for m o d e l a t m o s p h e r e s to s i m u l a t e r e s u l t s for c l o u d - f r e e s k i e s . A n
a l t e r n a t i v e is to r e l y o n r a d i o s o u n d i n g s , w h i c h a r e d o n e o n a r e g u l a r b a s i s
at m o s t a i r p o r t s .
(ii) T h e spectral emittance of the radiating surface should b e known. Spectro-

p h o t o m e t r i c d a t a for t h e r e f l e c t a n c e at a 4 5 ° a n g l e o f i n c i d e n c e y i e l d useful
information.
(iii) T h e n o n - r a d i a t i v e h e a t influx to t h e c o o l i n g s u r f a c e s h o u l d b e k n o w n .
P r a c t i c a l e x p e r i e n c e tells t h a t this l i m i t i n g factor is difficult to c o m e to
g r i p s w i t h , a n d it a p p e a r s that m o s t p r a c t i c a l d e v i c e s a r e c h a r a c t e r i z e d
b y l a r g e r h e a t transfer coefficients t h a n p r e d i c t e d f r o m s i m p l e t h e o r i e s
of thermal insulation involving stationary non-convecting gases.
A n i n f r a r e d - s e l e c t i v e s u r f a c e w i t h l a r g e e m i t t a n c e in t h e 8-13 μιτι r a n g e a n d l o w
a b s o r p t a n c e e l s e w h e r e is c a p a b l e o f y i e l d i n g t h e l o w e s t t e m p e r a t u r e in a w e l l -
insulated device. S u c h surfaces have been produced and optimized as discussed
in this c h a p t e r . A t a m b i e n t t e m p e r a t u r e t h e h i g h e s t c o o l i n g p o w e r is o b t a i n e d
w i t h a b l a c k b o d y - l i k e s u r f a c e , a n d w h e t h e r a n i n f r a r e d - s e l e c t i v e s u r f a c e offers a n y
a d v a n t a g e in a d e v i c e c a n o n l y b e j u d g e d w h e n t h e r e q u i r e d c o o l i n g p e r f o r m a n c e
a n d t h e n o n - r a d i a t i v e h e a t i n f l u x a r e specified. I n m a n y p r a c t i c a l c a s e s it t u r n s
o u t that a c h e a p b l a c k b o d y - l i k e s u r f a c e is, in fact, t h e b e s t o p t i o n . O n t h e o t h e r
h a n d it s h o u l d b e r e m e m b e r e d that a n i n f r a r e d - s e l e c t i v e g a s h a s a d v a n t a g e s w i t h
r e g a r d to t r a n s p o r t a n d h e a t e x c h a n g e o f the c o o l a n t . T h i s g a s m u s t b e safely
e n c a s e d in a tight b u t infrared t r a n s p a r e n t c o n t a i n e r , w h i c h m a y b e difficult to
achieve under practical conditions.
A b e t t e r i n f r a r e d - t r a n s p a r e n t c o n v e c t i o n s h i e l d is n e e d e d if r a d i a t i v e c o o l i n g to
l o w t e m p e r a t u r e s is g o i n g to b e g e n e r a l l y a p p l i c a b l e . It a p p e a r s t h a t p o l y e t h y l e n e
is t h e o n l y v i a b l e a l t e r n a t i v e a n d efforts s h o u l d b e f o c u s s e d o n t r y i n g to m a k e
m o r e mechanically stable materials without sacrificing too m u c h infrared
t r a n s m i t t a n c e . F o i l s w i t h a s u p p o r t i n g m e t a l g r i d as w e l l as e x t r e m e l y h i g h -
d e n s i t y foils w i t h m i n i m i z e d a b s o r p t i o n in t h e 8-13 μηι b a n d a r e o f i n t e r e s t .
A n o t h e r i m p o r t a n t i s s u e is to p r o d u c e p i g m e n t e d foils w i t h a h i g h e r s o l a r
r e f l e c t a n c e t h a n t h e o n e m e a s u r e d for p r e v i o u s l y p r o d u c e d m a t e r i a l s .
In a g l o b a l p e r s p e c t i v e t h e n e e d for c o o l i n g is as i m p o r t a n t a s t h e n e e d for
heating. Radiative cooling has almost innumerable potential applications. Cold
s t o r a g e o f f o o d is o f o b v i o u s i m p o r t a n c e a n d c a n b e a c c o m p l i s h e d w i t h s i m p l e
r a d i a t i v e l y c o o l e d d e v i c e s . D e e p freezing, o n t h e o t h e r h a n d , is 3f e3 a3s3
i4
b l4
8e 4o1
8n l y
u n d e r s p e c i a l c l i m a t i c c o n d i t i o n s . 2C l i m a t i z a t i o n o f b u i l d i n g s , ' ' " '
d e s a l i n a t i o n o f w a t e r b y f r e e z i n g , a n d c o n d e n s a t i o n o f a t m o s p h e r i c h u m i d i t y 4are59
0
o t h e r i m p o r t a n t a p p l i c a t i o n s . In fact, c o n d e n s a t i o n i r r i g a t i o n h a s b e e n t e s t e d '
with r2 a d i a t i v e l y c o o l e d s u r f a c e s , a n d a b o u t 0.4 litres o f w a t e r h a s b e e n e x t r a c t e d
p e r m o f r a d i a t i n g s u r f a c e a n d p e r n i g h t in different c l i m a t e s . T h e list o f p o s s i b l e
applications can be continued.
A s a final p o i n t w e r e m a r k that it is s u r p r i s i n g t h a t t h e d e v e l o p m e n t o f m a t e r i a l s
a n d d e v i c e s for e x p l o i t i n g r a d i a t i v e c o o l i n g is still in its i n f a n c y . It is o u r o p i n i o n
t h a t r a d i a t i v e c o o l i n g offers m a n y i n t e r e s t i n g a n d i m p o r t a n t o p p o r t u n i t i e s for
fundamental and applied research.
REFERENCES
1. F . A r a g o , A n n u a i r e d u B u r e a u d e s L o n g i t u d e s p o u r l ' A n 1 8 2 8 , p. 1 4 9 ;
r e p r i n t e d in Oeuvres Completes de François Arago, V o l . 8 ( G i d e & W e i g e l ,
P a r i s a n d L e i p z i g , 1 8 5 8 ) , p. 8 7 .
2. M . N . B a h a d o r i , S c i . A m . 2 3 8 , 1 4 4 ( 1 9 7 8 ) ; in Solar Energy Conversion: An
Introductory Course, e d i t e d b y A . E . D i x o n a n d J . D . L e s l i e ( P e r g a m o n , N e w
Y o r k , 1 9 7 9 ) , p. 4 6 1 .
3. A.K. Head, Australian Patent N o . 239364 (1959); U.S. Patent N o . 3043112
(1962).
4. F. T r o m b e , Rev. Gen. Therm. 6, 1285 (1967).
5. C.G. Granqvist and A. Hjortsberg, J. Appl. Phys. 52, 4205 (1981).
6. M . M a r t i n , in Passive Cooling, e d i t e d b y . J . C o o k ( M I T P r e s s , C a m b r i d g e ,
1 9 8 9 ) , p. 1 3 8 .
7. K . Y a . K o n d r a t y e v , Radiation in the Atmosphere (Academic, N e w York,
1969).
8. V . E . Z u e v , Propagation of Visible and Infrared Radiation in the Atmos-
phere ( W i l e y , N e w Y o r k , 1 9 7 4 ) .
9. G . H e r z b e r g , Molecular Spectra and Molecular Structure II. Infrared and
Raman Spectra of Polyatomic Molecules (Van Nostrand, Princeton, 1945).
10. E . E . Bell, L . E i s n e r , J . Y o u n g a n d R . A . Oetjen, J . O p t . S o c . A m . 5 0 , 1 3 1 3 ( 1 9 6 0 ) .
11. P. B e r d a h l a n d R. F r o m b e r g , S o l a r E n e r g y 2 9 , 2 9 9 ( 1 9 8 2 ) .
12. S. B r u n o l d , U n t e r s u c h u n g e n z u m P o t e n t i a l d e r S t r a h l u n g s k u h l u n g in
A r i d e n K l i m a t z o n e n , T h e s i s , F r a u n h o f e r I n s t i t u t fur S o l a r e
Energiesysteme, Freiburg, Germany, 1989 (unpublished).
13. F.X. Kneizys, E.P. Shettle, W . O . Gallery, J.H. C h e t w y n d , Jr., L.W. Abreu,
J.E.A. Selby, R.W. Fenn, and R.A. McClatchey, Atmospheric T r a n s m i t t a n c e /
Radiance C o m p u t e r C o d e L O W T R A N 5, Air Force Geophysics Laboratory,
Technical Report AFGL-TR-80-0067 (February 1980).
14. T.S. Eriksson and C.G. Granqvist, Appl. Opt. 2 L 4381 (1982).
15. M . M a r t i n a n d P. B e r d a h l , S o l a r E n e r g y 3 3 , 3 2 1 ( 1 9 8 4 ) .
16. S . B . I d s o , W a t e r R e s o u r c e s R e s . 1 7 , 2 9 5 (1981).
17. I. H a m b e r g , J . S . E . M . S v e n s s o n , T . S . E r i k s s o n , C . G . G r a n q v i s t , P. A r r e n i u s
a n d F . N o r i n , A p p l . O p t . 2 6 , 2 1 3 1 (1987).
18. C . G . R i b b i n g , Opt. Lett. 1 5 , 8 8 2 (1990).
19. T.S. Eriksson and C.G. Granqvist, Appl. Opt. 2 2 , 3204 (1983).
20. T.S. Eriksson and C.G. Granqvist, J. Appl. Phys. 6 0 , 2081 (1986).
21. D.E. Aspnes and J.B. Theeten, J. Appl. Phys. 5 0 , 4928 (1979).
22. T . S . E r i k s s o n , S.-J. J i a n g a n d C . G . G r a n q v i s t , S o l a r E n e r g y M a t e r . 1 2 , 3 1 9
(1985).
23. M . D . D i a t e z u a , A . D e r e u x , A . R o n d a , J.P. V i g n e r o n , P. L a m b i n a n d R .
Caudano, Proc. Soc. Photo-Opt. Instrum. Engr. 1149, 8 0 (1989).
24. T.S. Eriksson, A. Hjortsberg and C.G. Granqvist, Solar Energy Mater. 6,
191 (1982).
25. S. C a t a l a n o t t i , V . C u o m o , G . P i r o , D . R u g g i , V . S i l v e s t r i n i a n d G . T r o i s e ,
Solar Energy 1 7 , 8 3 (1975).
26. Ph. Grenier, Rev. Phys. Appl. 14, 87 (1979).
27. E.M. Lushiku and C.G. Granqvist, Appl. Opt. 2 3 , 1 8 3 5 (1984).
28. L . J . B e l l a m y , The Infra-Red Spectra of Complex Molecules (Chapman &
Hall, London, 1975).
29. T.S. Eriksson, C.G. Granqvist and J. Karlsson, Solar Energy Mater. 1 6 , 2 4 3
(1987).
30. B . P i r i o u , R e v . Int. H a u t e s T e m p . Refract. 1 0 , 2 8 3 ( 1 9 7 3 ) .
31. P. B e r d a h l , A p p l . O p t . 2 3 , 3 7 0 (1984).
32. J . A . D u f f i e a n d W . A . B e c k m a n , Solar Energy Thermal Processes (Wiley,
N e w York, 1974), p.83.
33. D . M i c h e l l a n d K . L . B i g g s , A p p l . E n e r g y 5, 2 6 3 ( 1 9 7 9 ) .
34. B . L a n d r o a n d P . G . M c C o r m i c k , Int. J . H e a t M a s s T r a n s f e r 2 3 , 6 1 3 (1980).
35. P. B e r d a h l , M . M a r t i n a n d F . S a k k a l , Int. J . H e a t M a s s T r a n s f e r 2 6 , 8 7 1 ( 1 9 8 3 ) .
36. N.A. Nilsson, T.S. Eriksson and C.G. Granqvist, Solar Energy Mater. 1 2 , 3 2 7
(1985).
37. T. I s h i b a s h i a n d M . I s h i d a , in Solar World Forum, e d i t e d b y D . O . H a l l a n d
J. M o r t o n ( P e r g a m o n , O x f o r d , 1 9 8 2 ) V o l . 1, p. 1 9 8 .
38. S. El G o l l i a n d Ph. G r e n i e r , J . P h y s . (Paris) 4 2 , C l - 4 3 1 ( 1 9 8 1 ) .
39. A. Addeo, E. M o n z a , M. Peraldo, B . Bartoli, B . Coluzzi, V. Silvestrini and G.
Troise, N u o v o C i m e n t o 1Ç, 419 (1978).
40. A. Addeo, L. Nicolais, G. R o m e o , B . Bartoli, B. Coluzzi and V . Silvestrini,
S o l a r E n e r g y 2 4 , 9 3 (1980).
41. A. Andretta, B . Bartoli, B . Coluzzi and V. C u o m o , J. Phys. (Paris) 4 2 , C l - 4 2 3
(1981).
42. G.A. Niklasson and T.S. Eriksson, Proc. Soc. Photo-Opt. Instrum. Engr.
1 0 1 6 . 8 9 (1988).
43. T.M.J. Nilsson and G.A. Niklasson, Gothenburg Institute of Physics Report
GIPR-299, 1991 (unpublished).
44. T.S. Eriksson, Ph. D. Thesis, Dept. of Physics, Chalmers University of
Technology, Gothenburg, Sweden, 1985 (unpublished).
45. E . M . L u s h i k u , P h . D . T h e s i s , D e p t . o f P h y s i c s , U n i v e r s i t y o f D a r es S a l a a m ,
D a r es S a l a a m , T a n z a n i a , 1 9 8 6 ( u n p u b l i s h e d ) .
46. F. Trombe, A. L e Phat Vinh and M. L e Phat Vinh, J. Rech. C N R S 6 5 , 563
(1964).
47. G.S. Castellanos and J. Fournier, Chauffage, Ventilation, Conditionnement
3 , 3 1 (1975).
48. Β . Bartoli and V. Silvestrini, L e Scienze 1 3 9 , 70 (1980).
49. J. Rademaekers, T.S. Eriksson and E.M. Lushiku, unpublished.
50. E.M. Lushiku and R.T. Kivaisi, Proc. Soc. Photo-Opt. Instrum. Engr. 1 1 4 9 ,
111 (1989).

Materials Science for Solar Energy Conversion Systems - C. G. Granqvist 1991

Uploaded by

Copyright:

Available Formats

You might also like

Materials Science for Solar Energy Conversion Systems - C. G. Granqvist 1991

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Materials Science for Solar Energy Conversion Systems - C. G. Granqvist 1991

Uploaded by

Copyright:

Available Formats

RENEWABLE ENERGY SERIES

Pergamon Titles of Related Interest

SAYIGH & MCVEIGH

STECCO & MORAN

Pergamon Related Journals (free specimen copy gladly sent on

Copyright © 1991 Pergamon Press pic

British Library Cataloguing in Publication Data

Printed in Great Britain by BPCC Wheatons Ltd, Exeter

R a p i d advances in materials science n o w m a k e possible n e w vistas in solar

INTRODUCTION T O MATERIALS SCIENCE FOR SOLAR

I. RENEWABLE ENERGY CONVERSION PATHWAYS

T h e importance o f renewable energy sources are currently attracting widespread

Geosphere | | Biosphere | | Technosphere

Fig. 1. Renewable energy conversion pathways. ( F r o m Ref. 2).

III. S O M E GOALS OF MATERIALS SCIENCE FOR SOLAR

(2) H i g h absorption of solar radiation can be c o m b i n e d with l o w emittance o f

(3) H i g h transmittance of solar radiation can b e c o m b i n e d w i t h l o w emittance

(5) C o a t i n g s w i t h r a d i a t i v e p r o p e r t i e s that can b e c h a n g e d to m a t c h differing

I t e m s (1) - (6) a r e c o v e r e d in s e v e r a l topical c h a p t e r s b e l o w . T h e y a r e p r e c e d e d b y a

OPTICAL PROPERTIES OF INHOMOGENEOUS

For radiative cooling applications solar reflecting and infrared-transmitting

IL THIN FILM OPTICS AND THE DIELECTRIC PERMEABILITY.

Fig. 1. Definitions of symbols entering Fresnel's relations.

a n d a n a l o g o u s l y for nj. F r e s n e l ' s r e l a t i o n s c a n b e u s e d to d i s c u s s t h e o p t i c a l

T 2 (sε 3μ=1) ΐ2/ 2 α ) 8θ 3 s, t 2

m u l t i p l y reflected b e a m s . T h e final e x p r e s s i o n s for t h e r e f l e c t a n c e a n d t h e

ε(ω) = ει (ω) + ίε2(ω). (14)

W e n e x t d i s c u s s t h e g e n e r a l f o r m o f ε ( ω ) for different homogeneous materials. In

F i g u r e 3 g i v e s a s c h e m a t i c r e p r e s e n t a t i o n o f t h e χ^. T h e νΕ r e a l a n d Ρi mΗ aginary parts

T h e dielectric permeability o f m a n y metals, semiconductors and insulators have

ΙΠ. R I G O R O U S B O U N D S AND EFFECTIVE M E D I U M THEORIES

W e first c o n s i d e r t h e s i t u a t i o n w h e n o n l y the d i e l e c t r i c p e r m e a b i l i t i e s o f the t w o

E q u a t i o n (18) c o r r e s p o n d s to n o s c r e e n i n g o f the field w h i l e E q . (19) c o r r e s p o n d s to

I » Material "A"; filling factor fA

RANDOM UNIT CELLS

^ Ratio of volumes -Probability fAof being "A"

T h e b a s i c definition o f a n effective m e d i u m is that t h e R U C , w h e n e m b e d d e d in

"optical t h e o r e m " for a b s o r b i n g m e d i a ; it r e l a t e s t h e e x t i n c t i o n o f t h e s p h e r i c a l cell

For the opposite situation w e obtain

RANDOM UNIT CELLS

Effective m e d i u m t h e o r i e s w h i c h a r e d e r i v e d from e l l i p s o i d a l u n i t cells c o r r e s -

T h e effective m e d i u m t h e o r i e s d e s c r i b e d in this s e c t i o n a r e often in fairly g o o d

Fig. 8. B e r g m a n - M i l t o n b o u n d s for the e f f e c t i v e d i e l e c t r i c p e r m e a -

Another type of composite consists of a mixture of metal and crystalline insulator

IV. EFFECTS OF PAIR AND THREE-POINT CORRELATION

' (ξ/rp-D 2α<τ<ξ

where L 77* is a m e a s u r e o f t h e "holes" in t h e s t r u c t u r e a n d r e l a t e d to t h e l a c u -

W e first c o n s i d e r t h e i n t e g r a l o v e r the p a i r c o r r e l a t i o n f u n c t i o n , x . Inserting

Recently the information available on χ has increased substantially and accurate

x = (1 - fA> Ρ + fA (1 " P> / W6)

First w e consider gas evaporated metal particle coatings. T h e y are p r o d u c e d b y

b e t w e e n c o r e a n d c o a t i n g . W h e n t h e sizes o f the m e t a l p a r t i c l e s a r e l e s s t h a n the

200 300 400 500 600

o f t h e d i e l e c t r i c p e r m e a b i l i t y for C0-AI2O3 c o a t i n g s w i t h different filling factors. It

V. MATERIALS WITH LARGE INHOMOGENEITIES

O u r definition o f an effective m e d i u m required that the R a n d o m U n i t Cell, w h e n

S (0) = S (π) = 0 , (49)

W h e n t h e p a r t i c l e s i z e is s o l a r g e that E q . (49) is n o l o n g e r v a l i19 d o n e h a s to r e s o r t

filling factors r e m a i n s a n o b j e c t for future r e s e a r c h . A l s o E q s . ( 5 0 ) a n d (51) w e r e