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Microelectronics Processing
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Dennis W. Hess and Klavs F. Jensen

1 2

Department of Chemical Engineering, University of California, Berkeley, CA

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94720-9989
Department of Chemical Engineering and Materials Science, University of
2

Minnesota, Minneapolis, M N 55455

This chapter gives an overview of issues related to electronic materials

processing, with particular emphasis on the fabrication of silicon-
-basedintegrated circuits. Selected aspects of solid-state physics are
reviewed as a background for processing issues. Unit operations in
integrated-circuit manufacturing are summarized, and an example
of a process sequence for the fabrication of a metal-
-oxide-semiconductoris given to provide a perspective of the specific
processes described in subsequent chapters.

SINCE 1980, F I R M S S P E C I A L I Z I N G IN T H E P R O C E S S I N G of electronic materials

have e m p l o y e d 1 5 - 3 0 % of c h e m i c a l e n g i n e e r i n g graduates at a l l degree
levels. L i k e other specialized areas for c h e m i c a l engineers (e.g., b i o t e c h -
nology, waste treatment, food processing, a n d pharmaceuticals), the elec-
tronic materials field makes use of the b r o a d m u l t i d i s c i p l i n a r y scientific a n d
e n g i n e e r i n g b a c k g r o u n d of c h e m i c a l engineers. I n particular, the processing
of materials a n d the fabrication of electronic, magnetic, a n d optical devices
r e q u i r e a k n o w l e d g e of c h e m i s t r y , solid-state physics, materials science,
c h e m i c a l k i n e t i c s , reactor d e s i g n , heat transfer, fluid flow, a n d mass trans-
port. N u m e r o u s examples of these topics w i l l be e v i d e n t i n s u c c e e d i n g
chapters. T h e o v e r a l l goal of this book is to demonstrate that the manufacture
of solid-state materials a n d devices is s i m p l y c h e m i c a l processing.
T h e m i c r o e l e c t r o n i c (or semiconductor) i n d u s t r y is not the o n l y s o l i d -
state-processing i n d u s t r y that extensively uses chemists a n d c h e m i c a l e n -
gineers, although this p a r t i c u l a r i n d u s t r y often gets the most attention b e -
cause of the extraordinary a n d r a p i d success it has a c h i e v e d . Industries

0065-2393/89/0221-0001$09.25/0
© 1989 American Chemical Society

Hess and Jensen; Microelectronics Processing

Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
2 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

i n v o l v e d i n optical coatings; solar-energy conversion; wear-resistant layers;

solid-state batteries; e l e c t r o c h e m i s t r y ; a n d magnetic, o p t i c a l , a n d p h o t o n i c
devices are i n t e n s e l y i n t e r e s t e d i n chemists a n d a n d c h e m i c a l engineers for
process research a n d d e v e l o p m e n t a n d p r o d u c t manufacture. T h e scientific
b a c k g r o u n d a n d process technology n e e d e d for m i c r o e l e c t r o n i c - d e v i c e fab­
rication is used i n essentially a l l of the industries j u s t m e n t i o n e d .
T h i s book w i l l concentrate o n the c h e m i s t r y a n d f u n d a m e n t a l c h e m i c a l
e n g i n e e r i n g p r i n c i p l e s n e e d e d for integrated-circuit (IC) manufacture. I n ­
tegrated circuits are c u r r e n t l y u s e d i n c o n s u m e r items, s u c h as h a n d - h e l d
calculators, digital watches, m i c r o w a v e ovens, a n d automobiles, a n d i n
microprocessors for c o m m u n i c a t i o n , defense, education, m e d i c i n e , a n d
space exploration. N a t u r a l l y , n e w application areas are c o n t i n u a l l y b e i n g
developed.
T o appreciate the r a p i d d e v e l o p m e n t of process technology, the p r o ­
gression of the I C i n d u s t r y m u s t be c o n s i d e r e d first. ( F o r s u m m a r i e s of the
historical d e v e l o p m e n t of this field, see references 1 a n d 2.) A c e n t r a l t h e m e
i n the I C i n d u s t r y is the simultaneous fabrication of h u n d r e d s of m o n o l i t h i c
I C s (or chips) o n a wafer (or slice) of silicon (or other m a t e r i a l such as g a l l i u m
arsenide), w h i c h is t y p i c a l l y 1 0 0 - 1 5 0 m m i n d i a m e t e r a n d 0.75 m m t h i c k .
I n s i l i c o n technology, c h i p areas generally range from a few square m i l l i ­
meters to over 100 m m . A large n u m b e r (often m o r e than 100) of i n d i v i d u a l
2

process steps, w h i c h are p r e c i s e l y c o n t r o l l e d a n d carefully s e q u e n c e d , are

r e q u i r e d for the fabrication.
A s an example of S i technology, F i g u r e 1 illustrates a packaged 1-megabit
dynamic-random-access-memory ( D R A M ) chip on a 150-mm-diameter Si
substrate c o n t a i n i n g fabricated chips. E a c h of the chips w i l l b e cut f r o m the
wafer, tested, a n d packaged l i k e the c h i p s h o w n o n top of the wafer. T h e
c h i p is based o n a l-μΐΉ m i n i m u m feature size a n d contains 2,178,784 active
devices. It can store 1,048,516 bits of i n f o r m a t i o n , w h i c h corresponds to
approximately 100 t y p e w r i t t e n pages.
I C s are b u i l t - u p f r o m layers of t h i n (usually b e t w e e n 1 n m a n d 2 μιτι)
c o n d u c t i n g , i n s u l a t i n g , a n d s e m i c o n d u c t i n g films. E a c h film has a p a t t e r n
e t c h e d i n t o i t , so that an exactly registered array of these layers forms
i n d i v i d u a l components s u c h as transistors, resistors, diodes, a n d capaci­
tors. T h e s e components are i n t e r c o n n e c t e d b y p a t t e r n e d c o n d u c t i n g films
("wires") to y i e l d circuits. F i g u r e 2 illustrates a t y p i c a l process sequence
starting from the S i raw m a t e r i a l , t h r o u g h S i wafer p r o d u c t i o n , device m a n ­
ufacture, wafer section, a n d , finally, to packaging o f the final c h i p (3).
T h e application areas for I C s have e x p a n d e d c o n t i n u o u s l y , because
greater c i r c u i t c o m p l e x i t y can b e r e a l i z e d as the n u m b e r of components o n
a single c h i p increases ( F i g u r e 3) (4). F r o m the i n c e p t i o n o f the s e m i c o n ­
d u c t o r i n d u s t r y i n 1959 u n t i l the early 1970s ( F i g u r e 3, segment A ) , the
n u m b e r of components on a s i l i c o n c h i p d o u b l e d e v e r y year. T h e pace s l o w e d
a b i t from 1972 to 1984, w h e n the n u m b e r of components o n a c h i p d o u b l e d

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
1. HESS & JENSEN Microelectronics Processing 3

Figure 1, A packaged 1-megabit dynamic-random-access-memory (DRAM) sil­

icon chip on a processed 150-mm-diameter Si wafer. (Used by courtesy of G.
B. Larrabee, Texas Instruments.)

e v e r y L 5 years. Projections to the year 2015 ( F i g u r e 3, segments C E F a n d

C D G ) d e p e n d u p o n the m i n i m u m feature (pattern) size assumed for the
circuits. T h a t is, i f the p a t t e r n e d - f i l m dimensions decrease, t h e n c o m p o n e n t
sizes also decrease, a n d m o r e components can be fabricated o n a s i l i c o n c h i p
of fixed area. T h e m i n i m u m feature size of mass-produced (production) c i r ­
cuits has steadily d r o p p e d over the past 25 years ( F i g u r e 4). M a r k e r s p l a c e d
along or near the l i n e i n F i g u r e 4 serve as indicators of relative p a t t e r n sizes.
T h e different l e n g t h scales a n d small feature sizes i n v o l v e d i n m i c r o ­
electronic devices are d e m o n s t r a t e d graphically i n F i g u r e 5 b y c o m p a r i s o n
of the size of device features to that of a l a d y b u g . T h e magnification increases
for each p i c t u r e i n clockwise d i r e c t i o n starting at the u p p e r left p i c t u r e ,
w h i c h shows a l a d y b u g o n a 7 5 - m m - d i a m e t e r wafer, a n d e n d i n g at the l o w e r
left p i c t u r e , w h i c h shows 2-μ m m e t a l lines of an i n d i v i d u a l e l e c t r i c a l device.
To appreciate the fabrication sequences a n d , thus, the future directions
a n d needs of I C process technology, the operation of s i m p l e solid-state
devices m u s t be u n d e r s t o o d . T h e f o l l o w i n g section gives a short i n t r o d u c t i o n

Hess and Jensen; Microelectronics Processing

Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
 Hess and Jensen; Microelectronics Processing
Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
2. Schematic of process sequence showing the fabrication of a Si-based integrated circuit. (Reproduced
with permission from reference 3. Copyright 1985 McGraw-Hill.)
1. HESS & JENSEN Microelectronics Processing 5

10 ,
7
Ύ

)
\J- I I I LxJ I I I l_
1960 1970 1980 1990 2000 2010

Year

Figure 3. Components per silicon chip versus calendar year. Segments A and
Β are history; segments COG and CEF are projections based upon 0.5- and
0.25-μm minimum feature sizes, respectively. (Reproduced with permission
from reference 4. Copyright 1984 IEEE.)

to solid-state physics. A d d i t i o n a l d e t a i l m a y be f o u n d i n solid-state a n d d e v i c e

physics textbooks b y , for instance, W a r n e r a n d G r u n g (2), Ashcroft a n d
M e r m i n (5), K i t t e l (6), Sze (7, 8), a n d G r o v e (9).

Overview of Solid-State Physics

Crystal Structure. Solids can be classified into t h r e e groups a c c o r d ­
i n g t h e i r c o n d u c t i v i t y . Insulators s u c h as S i 0 2 t y p i c a l l y have c o n d u c t i v i t i e s
less t h a n 1 0 " ( Ω - c m ) " , whereas conductors (e.g., metals) have c o n d u c t i v i t i e s
8 1

greater than 1 0 ( Ω - c m ) " . Solids w i t h i n t e r m e d i a t e c o n d u c t i v i t i e s are c a l l e d

3 1

semiconductors. T h e s e i n c l u d e e l e m e n t a l semiconductors (e.g., Si) or c o m ­

p o u n d semiconductors m a d e u p of atoms from groups II to V I of the p e r i o d i c
table, s u c h as Z n S e (group I I - V I c o m p o u n d semiconductor), G a A s (group
I I I - V c o m p o u n d semiconductor), S i C (group I V - I V c o m p o u n d semicon­
ductor), a n d P b T e (group I V - V I c o m p o u n d semiconductor).
A s o l i d can have an a m o r p h o u s , p o l y c r y s t a l l i n e , or s i n g l e - c r y s t a l l i n e
p h y s i c a l structure. I n single crystals, the atoms are arranged i n t h r e e - d i ­
m e n s i o n a l p e r i o d i c arrays. T h e crystal structure of S i is the d i a m o n d lattice,
i n w h i c h each S i a t o m is t e t r a h e d r a l l y c o o r d i n a t e d w i t h four other S i atoms.
T h i s structure can b e v i e w e d as two i n t e r p e n e t r a t i n g face-centered-cubic
(fee) lattices d i s p l a c e d f r o m each o t h e r b y one-quarter of the distance a l o n g
the c u b e diagonal ( F i g u r e 6a). C o m p o u n d semiconductors of the type A B
(e.g., G a A s ) t y p i c a l l y have a z i n c b l e n d e lattice ( F i g u r e 6b), w h i c h is s i m p l y
the d i a m o n d structure w i t h one fee lattice c o m p o s e d o f A atoms (e.g., Ga)

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
6 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

Smallest Bacteria Ô

0.11
I960 1970 1980 1990
YEAR

Figure 4. Trend in minimum feature size on silicon integrated circuits versus

year of circuit introduction. Markers (o) give an indication of relative feature
size.

a n d the o t h e r fee lattice c o m p o s e d o f Β atoms (e.g., As). T h e long-range

o r d e r persists i n p o l y c r y s t a l l i n e solids b u t is r e s t r i c t e d to small crystallites
separated b y imperfections o r defects c a l l e d grain boundaries. A m o r p h o u s
materials have no long-range lattice s t r u c t u r e , b u t the nearest n e i g h b o r (i.e.,
short-range) b o n d i n g is regular. F o r instance, insulators s u c h as S i 0 a n d 2

S i N are d e p o s i t e d as a m o r p h o u s films.
3 4

T h e specific a p p l i c a t i o n o f a material generally d e t e r m i n e s the particular

structure d e s i r e d . F o r e x a m p l e , h y d r o g e n a t e d amorphous silicon is u s e d for
solar cells a n d some s p e c i a l i z e d e l e c t r o n i c devices (10). Because o f t h e i r
h i g h e r c a r r i e r m o b i l i t y (see C a r r i e r T r a n s p o r t , G e n e r a t i o n , a n d R e c o m b i ­
nation), single-crystalline e l e m e n t a l o r c o m p o u n d semiconductors are u s e d
i n the majority o f e l e c t r o n i c devices. P o l y c r y s t a l l i n e m e t a l films a n d h i g h l y
d o p e d p o l y c r y s t a l l i n e films o f silicon are used for conductors a n d resistors
i n device applications.

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
 Hess and Jensen; Microelectronics Processing
Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
Figure 5. Characteristic chip length scales illustrated by comparison to a ladybug. The magnification increases
for each picture in the clockwise direction starting with the upper left corner, which shows a ladybug on 62-
kilobit random-access-memory chips on a 75-mm-diameter silicon wafer. The final magnification in the lower
left corner shows the metal lines (2 μπι) at the device level. (Reproduced with permission from reference 3.
Copyright 1985 McGraw-Hill.)
8 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

Zinc blende

Figure 6. Top, diamond lattice (Si); bottom, zinc blende lattice (GaAs). (Re-
produced with permission from reference 8. Copyright 1985 Wiley.)

Energy Bands. E l e c t r o n s make u p the c h e m i c a l b o n d s b e t w e e n at-

oms i n a solid. I n s i l i c o n , this b o n d i n g is p r i m a r i l y covalent, whereas i n
c o m p o u n d semiconductors (group I I - V I c o m p o u n d s i n particular), the b o n d s
also have substantial i o n i c character. T h e electrons p a r t i c i p a t i n g i n these
bonds are t e r m e d valence electrons. F r e e electrons created b y b r e a k i n g
bonds o r doping (see C h a p t e r 6) are available for c u r r e n t flow a n d are k n o w n
as conduction electrons.
W h e n a b o n d is b r o k e n a n d a free e l e c t r o n is r e m o v e d , a hole o r e l e c t r o n
vacancy is created. W h e n this vacancy is filled b y an e l e c t r o n f r o m a n e i g h -
b o r i n g b o n d , the result is a hole m o v i n g i n a d i r e c t i o n opposite to that of
the electron. T h u s the hole may be c o n s i d e r e d as a (fictitious) particle w i t h

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
1. HESS & JENSEN Microelectronics Processing 9

a positive charge. T h e s e free electrons a n d holes are responsible for the

operation of e l e c t r o n i c devices.
E l e c t r o n s associated w i t h gas molecules have discrete energy l e v e l s ,
because t h e y are essentially u n p e r t u r b e d b y o t h e r molecules. W h e n atoms
are b r o u g h t together to f o r m a s o l i d , t h e i r e l e c t r o n wave functions interact,
a n d the r e s u l t i n g discrete e n e r g y states f o r m n e a r l y continuous bands o f
a l l o w e d e l e c t r o n energies. T h e e n e r g y levels w i t h i n each b a n d are filled b y
p a i r i n g electrons a c c o r d i n g to the P a u l i exclusion p r i n c i p l e . T h e highest
e n e r g y filled or partially filled b a n d is c a l l e d the valence band, a n d the next
highest (often empty) b a n d is c a l l e d the conduction band. B e t w e e n these
bands of a l l o w e d e n e r g y levels are gaps of f o r b i d d e n e n e r g y levels. T h e
e n e r g y difference b e t w e e n the valence b a n d m a x i m u m a n d the c o n d u c t i o n
b a n d m i n i m u m is the band gap, E . g

A t 0 Κ the valence b a n d is c o m p l e t e l y filled a n d the c o n d u c t i o n b a n d

is e m p t y for insulators a n d semiconductors. I n insulators s u c h as S i 0 , a 2

large a m o u n t of e n e r g y is r e q u i r e d to break a b o n d a n d p r o m o t e an e l e c t r o n
to the c o n d u c t i o n b a n d , that is, the b a n d gap is large ( £ > 5 eV). T h u s ,
g

t h e r m a l vibrations w i t h energy of the o r d e r kT (in w h i c h k is the B o l t z m a n n

constant a n d Τ is t e m p e r a t u r e ; kT = 0.026 e V at 300 K ) cannot generate
c o n d u c t i o n electrons (or holes), a n d the material cannot conduct c u r r e n t .
S e m i c o n d u c t o r s have smaller b a n d gaps (E < g 2 - 3 e V ) , so there w i l l b e a
finite p r o b a b i l i t y of p r o m o t i n g an e l e c t r o n f r o m the valence b a n d to the
c o n d u c t i o n b a n d a n d c r e a t i n g a hole i n the valence b a n d ; thus the material
can transport electrons a n d conduct c u r r e n t .
E n e r g y b a n d gaps for selected semiconductors are s u m m a r i z e d i n T a b l e
I. O n the basis o f the nature of the transition f r o m the valence b a n d to the
c o n d u c t i o n b a n d , semiconductors are classified as direct or indirect. I n a
direct s e m i c o n d u c t o r , the transition does not r e q u i r e a change i n e l e c t r o n
m o m e n t u m , whereas i n an i n d i r e c t semiconductor, a change i n m o m e n t u m
is r e q u i r e d for the transition to occur. T h i s difference is i m p o r t a n t for o p t i c a l
devices s u c h as lasers, w h i c h r e q u i r e direct-band-gap materials for efficient
radiation e m i s s i o n (7, 8). A s i n d i c a t e d i n F i g u r e 7, S i is an i n d i r e c t s e m i ­
c o n d u c t o r , whereas G a A s is a d i r e c t semiconductor.
C o n d u c t o r s (e.g., metals) have partially filled c o n d u c t i o n bands or o v e r ­
l a p p i n g c o n d u c t i o n a n d valence bands. Because of the easily accessible e n ­
ergy levels (i.e., no b a n d gap), electrons can r e a d i l y m o v e to h i g h e r e n e r g y
levels a n d conduct c u r r e n t .

Carrier Concentrations. Intrinsic Carriers. T h e n u m b e r of a v a i l ­

able carriers d e p e n d s o n t h e r m a l l y generated c o n d u c t i o n b a n d electrons a n d
valence b a n d holes, as w e l l as carriers p r o d u c e d f r o m the i n c o r p o r a t i o n
(intentional or unintentional) of i m p u r i t i e s . I n an i n t r i n s i c s e m i c o n d u c t o r ,
the t h e r m a l l y generated carriers d o m i n a t e . T h e n u m b e r of electrons (n) i n
the c o n d u c t i o n b a n d can t h e n be calculated f r o m the integral o v e r the d e n s i t y

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
 Table I. Energy Band Gaps and Transport Properties for Semiconductors
Effective Mass
Band Gap Mobility at 300 Κ 2ÎÎL
2 0
(eV) (cm /V-s) Band* Electrons Holes*
Semiconductor 300 Κ OK Electrons Holes Type m„ || m„ 1 mi,i m/,/,
Group IV
C 5.47 5.48 2000 2100 I 1.4 0.36 0.3 1.1
Si 1.12 1.17 1450 300 I 0.92 0.19 0.15 0.54
Ge 0.66 0.74 3900 1800 I 16 0.08 0.04 0.28
iroup IV-IV
e e
a-SiC 2.50 3.03 900 25 I 0.7 0.25
Group III-V
AlN 6.2 6.28 10 D

Hess and Jensen; Microelectronics Processing

A1P 2.5 50 450 I 3.67 0.21 0.21 0.51'
AlAs 2.16 2.22 300 200 I 1.1 0.19 0.15 0.41/
AlSb 1.62 1.69 200 400 I 1.8 0.26 0.12 0.34'
GaN 3.36 3.50 380 D
GaP 2.27 2.35 160 135 I 1.12 0.22 0.12 0.45

Advances in Chemistry; American Chemical Society: Washington, DC, 1989.

GaAs 1.42 1.52 9200 400 D 0.067 0.076 0.50
GaSb 0.75 0.82 3750 700 D 0.042 0.05 0.28
InP 1.34 1.42 5900 150 D 0.077 0.12 0.60
InAs 0.36 0.42 33,000 450 D 0.024 0.026 0.35
InSb 0.17 0.23 77,000 850 D 0.014 0.016 0.45
 Group I I - V I
g
ZnO 3.35 3.42 200 180 D 0.28 (0.59)
ZnS 3.68 3.84 165 10 D 0.38 0.2 1.7
ZnSe 2.7 2.82 540 30 D 0.15 0.15 1.47
ZnTe 2.26 2.39 340 100 D 0.12 0.15 0.63
CdS 2.42 2.56 400 50 D 0.21 (0.65) «
fi
CdSe 1.75 1.83 800 D 0.13 (0.45)
CdTe 1.49 1.61 1000 D 0.095 0.13 0.72
Group I V - V I
h
PbS 0.42 0.29 600 700 1 (0.25) (0.25)
h
PbTe 0.31 0.19 6000 4000 I (0A7) (0.20)
Group 1-VII
7-CuCl 3.17 3.39 D
7-CuBr 0.91 3.08 D
AgCl 2.99 3.25 I
AgBr 2.44 2.68 1
NOTE: The table is based on data from references 7 and 23. Blank entries mean no or insufficient data.
"The abbreviations I and D stand for indirect and direct, respectively.
0
''Effective mass is given in terms of the free electron mass, m .
c
n n n
The abbreviations m || and m _L denote the longitudinal and transverse effective electron masses, respectively. m is the effective
mass for isotropic conduction band minimum.
h hh
''The abbreviations m i and m denote the light and heavy effective hole masses, respectively.
^Values are not reported because of the nonparabolic nature of the valence band.

Hess and Jensen; Microelectronics Processing

r
|| <100>; see reference 23 for other directions.
e
Value in parentheses is the overall value for the effective hole mass.
''Value in parentheses is the overall value for the effective electron mass.

Advances in Chemistry; American Chemical Society: Washington, DC, 1989.

12 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

CRYSTAL MOMENTUM ρ
(α) (b)
Figure 7. Energy band structures of Si (a) and GaAs (h). Open circles denote
holes in the valence bands, and closed circles denote electrons in the conduction
bands. Crystal direction is indicated by the bracketed Miller indices. (Repro­
duced with permission from reference 8. Copyright 1985 Wiley.)

of states, N (E), t i m e s the p r o b a b i l i t y that an e l e c t r o n i c state is o c c u p i e d b y

e

an e l e c t r o n , F ( £ ) , that is,

η = Ρ* N (E)F(E)dE
e (1)
JEch

in which £ c b and E c t are the energies at the b o t t o m a n d top o f the c o n d u c t i o n

band, respectively.
T h e p r o b a b i l i t y d i s t r i b u t i o n , F ( E ) , is the F e r m i - D i r a c distribution
function

F ( £ )
1 + exp[(E - E )/kT]
F
( 2 )

i n w h i c h Γ is t e m p e r a t u r e , k is the B o l t z m a n n constant, a n d Ε is e l e c t r o n
energy. E is the F e r m i l e v e l , w h i c h is the energy at w h i c h the p r o b a b i l i t y
F

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1. HESS & JENSEN Microelectronics Processing 13

of e l e c t r o n occupancy is exactly 0.5. I n an i n t r i n s i c s e m i c o n d u c t o r at r e a ­

sonable t e m p e r a t u r e s , t h e f e w available electrons are c o n f i n e d near t h e
c o n d u c t i o n b a n d m i n i m u m , a n d e q u i v a l e n t l y , the holes are f o u n d p r i m a r i l y
i n levels near t h e valence b a n d m a x i m u m . T h e r e f o r e , a s i m p l e quadratic
a p p r o x i m a t i o n m a y b e u s e d to express the density o f states for t h e electrons
(5, 7):

N (E)
e = V2|£ - £ |g (3)
IT

I n e q u a t i o n 3, m is t h e effective mass of the e l e c t r o n , h is t h e P l a n c k constant

n

d i v i d e d b y 2 i r , a n d E is t h e b a n d gap. U n l i k e t h e free electron mass, t h e

g

effective mass takes into account the interaction of electrons w i t h the p e r i o d i c

potential o f the crystal lattice; thus, t h e effective mass reflects t h e c u r v a t u r e
of t h e c o n d u c t i o n b a n d (5). T h i s c u r v a t u r e of t h e c o n d u c t i o n b a n d w i t h
m o m e n t u m is apparent i n F i g u r e 7. Values o f effective masses for selected
semiconductors are l i s t e d i n T a b l e I. T h e different values for t h e l o n g i t u d i n a l
a n d transverse effective masses for t h e electrons reflect t h e variation i n t h e
c u r v a t u r e of the c o n d u c t i o n b a n d m i n i m u m w i t h crystal d i r e c t i o n . S i m i l a r l y ,
the l i g h t - a n d heavy-hole m o b i l i t i e s are d u e to t h e different curvatures o f
the valence b a n d m a x i m u m (5, 7).
Insertion o f equation 3 into equation 1, a p p r o x i m a t i o n o f t h e F e r m i
d i s t r i b u t i o n b y a classical M a x w e l l - B o l t z m a n n d i s t r i b u t i o n , a n d integration
of e q u a t i o n 1 y i e l d t h e expression for the total n u m b e r o f electrons i n t h e
conduction band:

η = 2(^¥ë *-W E kT
(4)

i n w h i c h E is t h e energy o f t h e c o n d u c t i o n b a n d m i n i m u m .
c

S i m i l a r l y , t h e concentration o f holes (p) i n the valence b a n d c a n b e

expressed as

i n w h i c h m is t h e effective mass o f t h e hole a n d E is t h e energy o f t h e

p v

valence b a n d m a x i m u m .
F o r a n i n t r i n s i c (undoped) semiconductor, t h e n u m b e r o f holes i n the
valence b a n d equals t h e n u m b e r of electrons i n the c o n d u c t i o n b a n d , because
the o n l y free carriers available arise from t h e p r o m o t i o n o f electrons from

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14 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

the valence b a n d (a process that creates holes) to the c o n d u c t i o n b a n d .

T h e r e f o r e , the f o l l o w i n g relationship exists

n = η = ρ
{ (6)

i n w h i c h n is the i n t r i n s i c c a r r i e r concentration. C o m b i n a t i o n of equation

{

6 w i t h equations 4 a n d 5 gives the i n t r i n s i c F e r m i l e v e l £ as a f u n c t i o n of

F i

temperature:

£ , = ±E
F g + |fcrln^ (7)
2 4 m n

Because kT is s m a l l at r o o m t e m p e r a t u r e (0.026 eV) a n d because the effective

masses usually d o not differ substantially, the F e r m i l e v e l is p o s i t i o n e d near
the m i d d l e o f the b a n d gap. F r o m the l a w of mass action,

np = n* (8)

the i n t r i n s i c c a r r i e r concentration may b e d e r i v e d as a function of m a t e r i a l

properties:

(m m f e-^
n p
A /2kT
(9)

A t r o o m t e m p e r a t u r e the value of n for S i is approximately 1.45

x Χ 10 1 0

electrons p e r c m . 3

Extrinsic Carriers. W h e n sufficient dopant is a d d e d to a s e m i c o n d u c t o r

so that the r e s u l t i n g c a r r i e r concentration exceeds the i n t r i n s i c l e v e l , the
s e m i c o n d u c t o r is c a l l e d extrinsic. D o p a n t s that donate free electrons to the
c o n d u c t i o n b a n d are c a l l e d donors, a n d dopants that accept electrons a n d
release holes to the valence b a n d are c a l l e d acceptors. D e s i r e d dopants
i n t r o d u c e energy levels w i t h i n the f o r b i d d e n gap that are slightly b e l o w the
c o n d u c t i o n b a n d edge or slightly above the valence b a n d edge; these are
k n o w n as shallow dopants. Ρ a n d A s are shallow donors i n S i , whereas Β is
a shallow acceptor i n S i . D o p a n t s that i n t r o d u c e energy states i n the m i d d l e
of the b a n d gap, the so-called d e e p levels, are t y p i c a l l y not useful for d e v i c e
purposes, because they do not ionize significantly at r o o m t e m p e r a t u r e .
E x a m p l e s of i m p u r i t i e s that create d e e p levels i n S i are C , A u , a n d P t .
T o calculate the n u m b e r o f carriers r e s u l t i n g f r o m the d o p i n g of a s e m i ­
conductor, the degree of i o n i z a t i o n of the donors m u s t be k n o w n . M o s t

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1. HESS & JENSEN Microelectronics Processing 15

shallow donors i n S i are c o m p l e t e l y i o n i z e d at r o o m t e m p e r a t u r e , a n d the

n u m b e r of electrons equals the n u m b e r of donors ( n ) : D

η = ηΌ
(10)

A t e q u i l i b r i u m the n u m b e r of holes may t h e n be c o m p u t e d f r o m the l a w of

mass action (equation 8), because b o t h electrons a n d holes are always present
i n a semiconductor. T h e F e r m i l e v e l can b e d e t e r m i n e d from equation 4.

Carrier Transport, Generation, and Recombination. W h e n an

electric field is a p p l i e d to a semiconductor, electrons are accelerated i n the
d i r e c t i o n opposite to the field w i t h a drift velocity, v , n p r o p o r t i o n a l to the
field, E:

(H)

T h e p r o p o r t i o n a l i t y factor is the electron mobility, μ , w h i c h has units of

η

square centimeters p e r volt p e r second. T h e m o b i l i t y is d e t e r m i n e d b y

electron-scattering mechanisms i n the crystal. T h e two p r e d o m i n a n t m e c h ­
anisms are lattice scattering a n d i m p u r i t y scattering. Because the a m p l i t u d e
of lattice vibrations increases w i t h t e m p e r a t u r e , lattice scattering b e c o m e s
the d o m i n a n t m e c h a n i s m at h i g h temperatures, and therefore, the m o b i l i t y
decreases w i t h i n c r e a s i n g t e m p e r a t u r e .
T h e o r y predicts that the m o b i l i t y decreases as T ~ because of lattice
3 / 2

scattering (8). B u t because electrons have h i g h e r velocities at h i g h t e m p e r ­

atures, they are less effectively scattered b y i m p u r i t i e s at h i g h temperatures.
C o n s e q u e n t l y , i m p u r i t y scattering becomes less i m p o r t a n t w i t h i n c r e a s i n g
t e m p e r a t u r e . T h e o r e t i c a l models p r e d i c t that the m o b i l i t y increases as
r / n j , i n w h i c h η is the total i m p u r i t y concentration (8). T h e m o b i l i t y is
3 / 2
λ

related to the electron diffusivity, D , t h r o u g h the E i n s t e i n relation

n

(12)

i n w h i c h q is the electronic charge.

B y analogy to e q u a t i o n 11, the drift v e l o c i t y for holes (t? ) i n the valence
p

b a n d may be expressed as

(13)

i n w h i c h μ is the hole m o b i l i t y a n d the m i n u s sign is m i s s i n g because holes

ρ

drift i n the same d i r e c t i o n as the electric field. T h e hole m o b i l i t y has the

same characteristics as the e l e c t r o n m o b i l i t y a n d is r e l a t e d to the hole dif-

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fusivity b y the appropriate E i n s t e i n relation. Because of the larger effective

mass o f holes, the h o l e m o b i l i t y is less t h a n the electron m o b i l i t y .
I n a semiconductor, the total c u r r e n t flowing due to an a p p l i e d field is
the s u m of the c o n t r i b u t i o n s of electrons ( i ) a n d holes ( i ) , as g i v e n b y
n p

equation 14

/ = I n + Z = (ηημ
p η + ηρμ )Ε ρ (14)

i n w h i c h the enclosed q u a n t i t y is the c o n d u c t i v i t y , σ , w h i c h is the r e c i p r o c a l

of the s e m i c o n d u c t o r resistivity. M o b i l i t i e s are weak functions of t e m p e r a ­
ture c o m p a r e d w i t h the exponential d e p e n d e n c e of the c a r r i e r c o n c e n t r a ­
tions, η a n d ρ (equations 4 a n d 5). T h e r e f o r e , an estimate of the b a n d gap
energy, E , may be o b t a i n e d b y p l o t t i n g In σ against 1/Γ for an i n t r i n s i c
g

semiconductor. T h e slope is t h e n -E /2k. g

L i k e the performance of c h e m i c a l reactors, i n w h i c h the transport a n d

reactions of c h e m i c a l species govern t h e o u t c o m e , the performance of elec­
tronic devices is d e t e r m i n e d b y the transport, generation, a n d r e c o m b i n a t i o n
of carriers. T h e m a i n difference is that electronic devices i n v o l v e charged
species a n d e l e c t r i c fields, w h i c h are present o n l y i n specialized c h e m i c a l
reactors s u c h as p l a s m a reactors a n d e l e c t r o c h e m i c a l systems. F u r t h e r m o r e ,
electronic devices i n v o l v e o n l y two species, electrons a n d holes, whereas
1 0 - 1 0 0 species are e n c o u n t e r e d c o m m o n l y i n c h e m i c a l reactors. I n the same
m a n n e r that species c o n t i n u i t y balances are u s e d to p r e d i c t the performance
of c h e m i c a l reactors, c o n t i n u i t y balances for electrons a n d holes m a y b e u s e d
to simulate e l e c t r o n i c devices. T h e basic c o n t i n u i t y e q u a t i o n for electrons
has the form

^ = -V-I a + G -R B B (15)
dt q

i n w h i c h t is t i m e , G n is the rate of generation of electrons, R n is the rate

of r e c o m b i n a t i o n of electrons, a n d I n is the e l e c t r o n c u r r e n t d e n s i t y (i.e.,
flux). T h e e l e c t r o n c u r r e n t d e n s i t y is d e f i n e d as

i n = qp nEn 4- qD Vn n (16)

w h i c h is the s u m o f drift components d u e to an electric field a n d diffusion

components d u e to concentration gradients. E q u a t i o n 15 is v e r y similar to
the c o n t i n u i t y balance for n e u t r a l species for a b i n a r y system (10)

^ = - V - N A + R A (15a)
dt

in which c A is the concentration of species A , R A represents the reaction

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1. HESS & JENSEN Microelectronics Processing 17

t e r m s , a n d N is t h e m o l a r flux o f species A . T h e flux is d e f i n e d b y e q u a t i o n

A

16a

dx
N A = x (N A A + N ) - B cD A B -^ (16a)
dz

i n w h i c h x is t h e m o l e fraction o f species A , N is t h e m o l a r flux o f species

A B

B , c is t h e total m o l a r c o n c e n t r a t i o n , D is t h e b i n a r y m o l a r difiusivity, a n d
A B

ζ is t h e spatial coordinate. I n e q u a t i o n 16a t h e first t e r m is t h e flux d u e to

molar flow (drift), a n d t h e second t e r m represents diffusion.
G e n e r a t i o n typically occurs b y carrier i n j e c t i o n across a j u n c t i o n or b y
optical excitation. Photoexcitation is a c c o m p l i s h e d b y s h i n i n g a l i g h t source
o n t h e semiconductor. I f the e n e r g y hv is greater than t h e b a n d gap energy
of the s e m i c o n d u c t o r , t h e p h o t o n can b e absorbed a n d an e l e c t r o n - h o l e p a i r
is generated. D i r e c t r e c o m b i n a t i o n of electrons a n d holes d o m i n a t e i n d i r e c t -
band-gap semiconductors such as G a A s , b u t this process r a r e l y occurs i n
i n d i r e c t - b a n d - g a p semiconductors because conservation o f m o m e n t u m c a n ­
not b e satisfied. I n i n d i r e c t - b a n d - g a p semiconductors, i n d i r e c t r e c o m b i n a ­
tion i n v o l v i n g l o c a l i z e d states i n the gap p r e d o m i n a t e (7, 8). R e c o m b i n a t i o n
is often d e s c r i b e d i n terms o f c a r r i e r lifetimes, τ, w h i c h c o r r e s p o n d to the
t i m e constant i n an exponential decay o f c a r r i e r concentration (8).
A c o n t i n u i t y equation s i m i l a r to equation 15 can b e d e r i v e d for holes:

| U - I v . I ( + G , - R F
(17
>

I n equation 17, J is t h e hole c u r r e n t density, G

p p is the rate of generation
of holes, a n d R p is the rate o f r e c o m b i n a t i o n of holes. T h e hole c u r r e n t
density is d e f i n e d b y e q u a t i o n 18

I p = ημ Ε ρΡ - qD Vp
p (18)

i n w h i c h D is t h e hole diffusivity.
p

I n a d d i t i o n to the e l e c t r o n a n d hole c o n t i n u i t y equations, Poissons

equation must b e satisfied.

eVE = q( ρ — η + ^ concentrations o f i o n i z e d i m p u r i t i e s ) (19)

In e q u a t i o n 19, € is t h e d i e l e c t r i c p e r m i t t i v i t y o f the semiconductor.

W i t h t h e appropriate b o u n d a r y conditions, equations 1 7 - 1 9 f o r m a c o m ­
plete d e s c r i p t i o n o f c a r r i e r generation, r e c o m b i n a t i o n , a n d transport that
can b e u s e d to simulate d e v i c e performance. M a n y examples are g i v e n i n
the books b y W a r n e r a n d G r u n g (2), Sze (7, 8), a n d S h u r (12), w i t h p a r t i c u l a r
emphasis o n device applications. A c o m p l e t e treatment of electronic a n d

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18 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

optical devices is outside the scope of this chapter. H o w e v e r , to gain some

insight into the i m p o r t a n t issues i n device fabrication, a b r i e f r e v i e w of the
basic features of p - n j u n c t i o n s a n d transistors is useful.

ρ—η Junctions. T h e p - n j u n c t i o n is the basic e l e m e n t of most elec­

tronic devices, i n c l u d i n g m e t a l - o x i d e - s e m i c o n d u c t o r field effect transistors
( M O S F E T s ) , b i p o l a r transistors, a n d solar cells. A s illustrated i n F i g u r e 8,
the j u n c t i o n is the r e g i o n b e t w e e n p - a n d n - t y p e - d o p e d s e m i c o n d u c t o r m a ­
terials. T h i s j u n c t i o n can be f o r m e d b y i o n i m p l a n t a t i o n f o l l o w e d b y a n ­
n e a l i n g , dopant diffusion, or epitaxial g r o w t h of a layer of one d o p i n g type
(e.g., ρ type) o n the substrate (e.g., η type). T h e s e i n d i v i d u a l processing
steps are discussed i n subsequent chapters. E l e c t r i c a l l y acceptable j u n c t i o n
properties cannot be r e a l i z e d b y p h y s i c a l l y p r e s s i n g n - a n d p-type s e m i c o n ­
ductors together because o f the n u m e r o u s defects at the interface. N e v e r ­
theless, from the standpoint o f d e s c r i b i n g the operation of a p - n j u n c t i o n ,
the j o i n i n g of u n i f o r m l y d o p e d p - a n d η-type semiconductors ( F i g u r e s 8a
a n d 8b) can b e c o n s i d e r e d .
W h e n p - a n d η-type semiconductors are b r o u g h t together, holes from
the ρ side diffuse into the η side, a n d electrons from the η side diffuse to
the ρ side. T h i s process continues u n t i l a steady state is r e a c h e d i n w h i c h
electric-field-generated drift a n d c a r r i e r diffusion are balanced a n d no net
c u r r e n t flow occurs. A t this e l e c t r o c h e m i c a l e q u i l i b r i u m c o n d i t i o n , the F e r m i
l e v e l is constant (8). A s electrons leave the η-type material, they leave b e h i n d
u n c o m p e n s a t e d positive d o n o r atoms that create a positive space charge.
S i m i l a r l y , u n c o m p e n s a t e d negative acceptor atoms that r e m a i n i n the p - t y p e
material create a r e g i o n o f negative space charge. T h e result is an e l e c t r i c
field d i r e c t e d from the p o s i t i v e l y c h a r g e d donors t o w a r d the negatively
charged acceptors.
The built-in potential V b is given b y equation 20

(20)

i n w h i c h n , n , a n d n are the concentrations of i o n i z e d acceptors, i o n i z e d

A D x

donors, a n d i n t r i n s i c carriers, respectively. A voltage a p p l i e d to the j u n c t i o n

changes the balance b e t w e e n diffusion a n d drift currents. I f a positive (V >
0) bias is a p p l i e d to the ρ side, the energy b a r r i e r for e l e c t r o n m o v e m e n t
across the j u n c t i o n is r e d u c e d a n d electrons are i n j e c t e d f r o m the η side
into the ρ side. T h e net c u r r e n t across the j u n c t i o n is g i v e n by:

I = h(e" vlkT
- 1) (21)

I n e q u a t i o n 2 1 , I is a constant c u r r e n t i n d e p e n d e n t of the a p p l i e d bias.

R

T h u s , the c u r r e n t increases exponentially w i t h the a p p l i e d voltage. T h i s

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1. HESS & JENSEN Microelectronics Processing 19

a) E
F

V.

Drift

m
\ > « Diffusion
b)
1 P /Ç/j η

mm.
y/M
Diffusion

Drift

d)

Figure 8. Schematic representations of p-n junctions and corresponding en­

ergy band diagrams under various conditions: (a) uniformly doped p-type and
η-type semiconductors before junction is formed, (b) thermal equilibrium, (c)
forward bias, and (d) reverse bias. Abbreviations are defined as follows: E , c

electron energy at conduction band minimum; E , electron energy at valence

c

band minimum; I , forward current; V , forward voltage; V , reverse voltage;

F F fl

and ε, electric field.

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20 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

situation ( F i g u r e 8c) is r e f e r r e d to as forward bias, because this bias d i r e c t i o n

is for e n h a n c e d c u r r e n t flow.
I n the case o f reverse bias, ( F i g u r e 8d), the η side is positive a n d the
a p p l i e d voltage is negative ( V < 0). T h i s configuration increases the b a r r i e r
h e i g h t for the f o r w a r d e l e c t r o n c u r r e n t (from η side to ρ side) w h i l e the
reverse c u r r e n t r e m a i n s t h e same. T h e j u n c t i o n e q u a t i o n (equation 21) also
applies to this case. Because V < 0, the e x p o n e n t i a l t e r m is s m a l l ; i f qV >
4kT, the c u r r e n t is essentially constant (-IR). T h e c u r r e n t - v o l t a g e (I-V)
characteristics of the j u n c t i o n are i l l u s t r a t e d i n F i g u r e 9. T h e r e c t i f y i n g
b e h a v i o r of a p - n j u n c t i o n (large f o r w a r d c u r r e n t a n d m i n i m a l reverse c u r ­
rent) is basic to its use i n diodes, transistors, a n d o p t i c a l devices (e.g., l i g h t -
e m i t t i n g diodes, p h o t o d i o d e s , a n d solar cells).

Bipolar Transistors. I n b i p o l a r devices, b o t h electrons a n d holes

participate i n t h e c o n d u c t i o n process, i n contrast to M O S F E T s , i n w h i c h
o n l y one c a r r i e r t y p e d o m i n a t e s . B i p o l a r technology has b e e n u s e d t y p i c a l l y
for h i g h - s p e e d - l o g i c applications.
F i g u r e 10 shows a t h r e e - d i m e n s i o n a l v i e w of an n - p - n b i p o l a r transistor
a n d a schematic d i a g r a m for a c o m m o n base configuration. T h e transistor
consists o f two back-to-back p - n j u n c t i o n s ; the i n t e r m e d i a t e p-type r e g i o n
is k n o w n as the base, a n d the two η-type regions are the emitter a n d collector.
T h e e m i t t e r r e g i o n has t h e highest d o p i n g (heavy η-type d o p i n g is i n d i c a t e d
b y n ) , whereas the collector has the lowest η-type d o p i n g .
+

U n d e r n o r m a l o p e r a t i o n , the e m i t t e r - b a s e j u n c t i o n is forward b i a s e d ,
whereas the c o l l e c t o r - b a s e j u n c t i o n is reverse biased ( F i g u r e 11). T h e v o l t ­
age across the e m i t t e r - b a s e j u n c t i o n is v a r i e d b y an i n p u t signal. Because
the d o n o r c o n c e n t r a t i o n i n the e m i t t e r is h i g h e r t h a n the acceptor c o n c e n ­
tration i n the e m i t t e r , the c u r r e n t t h r o u g h the j u n c t i o n is p r i m a r i l y d u e to
electrons i n j e c t e d i n t o the base. T h e base w i d t h is s m a l l e r t h a n the m e a n

Figure 9. Current-voltage (I-V) char­

acteristics of a Si p-n junction.

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
 Emitter Base Collector

Figure 10. Top, three-dimensional view of an oxide-isolated bipolar transistor.

(Reproduced with permission from reference 13. Copyright 1988 Mc-
Graw-Hill.) Bottom, schematic of a common base n-p-n transistor circuit.
Abbreviations are defined as follows: n-epi, n-type-doped epitaxial-grown sil-
icon; and p-CHAN-STOP, p-type channel stop.

free p a t h of the electrons, a n d t h u s , essentially a l l of the i n j e c t e d electrons

flow across the collector j u n c t i o n . T h e r e f o r e , the collector c u r r e n t , i , is c

o n l y slightly less than the e m i t t e r c u r r e n t , J , a n d any change i n the e m i t t e r

e

c u r r e n t is m i r r o r e d i n the collector c u r r e n t . H o w e v e r , because of the l o a d

resistor a n d p o w e r s u p p l y ( F i g u r e 10, bottom), the variation i n voltage across
the c o l l e c t o r - b a s e j u n c t i o n can b e m u c h larger than the c o r r e s p o n d i n g v a r i -

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22 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

>>
E>
Φ
c
UJ
c
e
φ
UJ

Figure 11. Energy diagram for an n-p-n transistor with standard operating
bias voltages.

ation o v e r the e m i t t e r - b a s e j u n c t i o n . T h u s , the transistor acts as a voltage

and p o w e r a m p l i f i e r .
T h e voltage gain is d u e to the i n j e c t i o n of electrons f r o m the e m i t t e r
r e g i o n , t h r o u g h the base, a n d i n t o the collector r e g i o n , w h e r e the voltage
d r o p is large c o m p a r e d to a s m a l l e m i t t e r - b a s e voltage ( F i g u r e 11). T h u s ,
the base w i d t h must be smaller than the electron m e a n free p a t h , or r e c o m ­
b i n a t i o n w i l l o c c u r a n d the p - n j u n c t i o n w i l l act as two separate j u n c t i o n s .
F u r t h e r m o r e , few o r no i m p u r i t i e s s h o u l d exist i n the base; o t h e r w i s e i m ­
p u r i t y scattering a n d c a r r i e r r e c o m b i n a t i o n w i l l destroy d e v i c e performance.
I n d e e d , b o t h feature size a n d p u r i t y constraints are issues that w i l l be
b r o u g h t u p r e p e a t e d l y i n subsequent chapters.
T h e f u n c t i o n of the c o m p l e m e n t a r y p - n - p transistor m a y be e x p l a i n e d
b y analogy to the n - p - n transistor b y r e v e r s i n g polarities a n d c o n s i d e r i n g
hole rather t h a n electron transport (7, 8). I n a d d i t i o n , a large v a r i e t y of

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1. HESS & JENSEN Microelectronics Processing 23

o p e r a t i n g regimes a n d c i r c u i t configurations are possible. Q u a n t i t a t i v e a n a l -

yses o f these systems are g i v e n i n textbooks o n device physics (2, 7, 8, 12).

MOSFETs. T h e metal-oxide-semiconductor field effect transistor

( M O S F E T o r M O S transistor) (8) is t h e most i m p o r t a n t d e v i c e for v e r y -
large-scale i n t e g r a t e d c i r c u i t s , a n d i t is u s e d extensively i n m e m o r i e s a n d
microprocessors. M O S F E T s c o n s u m e little p o w e r a n d c a n b e scaled d o w n
readily. T h e process technology for M O S F E T s is typically less c o m p l e x than
that for b i p o l a r devices. F i g u r e 12 shows a t h r e e - d i m e n s i o n a l v i e w o f an n -
c h a n n e l M O S ( N M O S ) transistor a n d a schematic cross section. T h e d e v i c e
can b e v i e w e d as t w o p - n j u n c t i o n s separated b y a M O S capacitor that
consists o f a p-type s e m i c o n d u c t o r w i t h a n oxide film a n d a m e t a l film o n
top o f t h e oxide.
U n d e r s t a n d i n g t h e b e h a v i o r o f a M O S capacitor is useful i n u n d e r s t a n d -
i n g t h e o p e r a t i o n o f a M O S transistor. W h e n a negative voltage is a p p l i e d
to t h e c o n d u c t o r o r m e t a l , t h e e n e r g y bands i n t h e p - t y p e s e m i c o n d u c t o r

p-TYPE SUBSTRATE

Figure 12. Top, three-dimensional view of an NMOS transistor. (Reproduced

with permission from reference 13. Copyright 1988 McGraw-Hill.) Bottom,
schematic of an NMOS transistor. (Reproduced with permission from reference
8. Copyright 1985 Wiley.) p CHAN denotes heavily p-type-doped channel.
+

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24 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

b e n d u p w a r d at the s e m i c o n d u c t o r - o x i d e interface, a n d holes accumulate

near the interface. T h e situation is c a l l e d accumulation (for a c c u m u l a t i o n of
majority carrier; F i g u r e 13a). I f a s m a l l p o s i t i v e voltage is a p p l i e d , the holes
are r e p e l l e d or d e p l e t e d f r o m t h e s e m i c o n d u c t o r surface a n d the bands b e n d
d o w n . T h i s situation is c a l l e d depletion ( F i g u r e 13b). W i t h f u r t h e r increases
i n a p p l i e d positive voltage, the i n t r i n s i c e n e r g y l e v e l crosses the F e r m i l e v e l .
U n d e r this c o n d i t i o n , m o r e electrons than holes are present near the
s e m i c o n d u c t o r surface, that i s , electrons r a t h e r than holes have b e c o m e the
majority c a r r i e r i n the p - t y p e s e m i c o n d u c t o r surface. T h i s situation is c a l l e d
carrier inversion ( F i g u r e 13c).
T h e o p e r a t i o n o f the N M O S transistor s h o w n schematically i n F i g u r e
12 can b e c o n s i d e r e d i n the light of t h e p r e v i o u s discussion o f a M O S
capacitor. W h e n no voltage is a p p l i e d to the gate, the source a n d d r a i n
electrodes c o r r e s p o n d to p - n j u n c t i o n s c o n n e c t e d t h r o u g h the ρ r e g i o n ;
therefore o n l y a s m a l l reverse c u r r e n t can flow f r o m source to d r a i n . O n the

(α) (b) Λ

(c)

Figure 13. Energy band diagrams and charge distributions of an ideal MOS
capacitor using p-type Si: (a) accumulation, (b) depletion, and (c) inversion.
Ei denotes the intrinsic Fermi level. (Reproduced with permission from ref­
erence 8. Copyright 1985 Wiley.)

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1. HESS & JENSEN Microelectronics Processing 25

other h a n d , i f a large positive voltage is a p p l i e d to the gate, an i n v e r s i o n

layer is f o r m e d adjacent to t h e s e m i c o n d u c t o r - o x i d e interface, analogous to
the i n v e r s i o n case for t h e M O S capacitor. T h e s e m i c o n d u c t o r i n v e r s i o n layer
connects t h e h e a v i l y d o p e d (n ) source a n d d r a i n regions w i t h a n η c h a n n e l
+

so that a c u r r e n t c a n easily flow. T h e conductance of this c h a n n e l m a y b e

m o d u l a t e d b y c h a n g i n g the gate voltage. I f a s m a l l d r a i n voltage is a p p l i e d ,
electrons w i l l flow from the source to the d r a i n , w i t h t h e c h a n n e l acting as
a resistor. T h u s t h e d r a i n c u r r e n t is p r o p o r t i o n a l to t h e a p p l i e d voltage.
F u r t h e r increases i n t h e d r a i n voltage e v e n t u a l l y l e a d to a p o i n t at w h i c h
the w i d t h o f the i n v e r s i o n l a y e r becomes zero. A t this "pinch-off" p o i n t , t h e
d r a i n c u r r e n t b e c o m e s saturated a n d becomes i n d e p e n d e n t o f t h e a p p l i e d
d r a i n voltage.
T h r e e other major M O S transistor configurations are available, i n a d ­
d i t i o n to t h e η-channel e n h a n c e m e n t m o d e (normally off) just d e s c r i b e d
( F i g u r e 14). I n t h e η-channel d e p l e t i o n m o d e , t h e device is fabricated (by
appropriate doping) so that w i t h zero bias o n the gate a n η c h a n n e l exists
b e t w e e n t h e source a n d d r a i n . I n this case a negative voltage m u s t b e a p p l i e d
to t h e gate to m o d u l a t e t h e conductance. I f this voltage is sufficiently large,
the c h a n n e l is d e p l e t e d o f electrons a n d t h e device turns off. D e v i c e s w i t h
ρ channels are s i m i l a r to η-channel devices, except that p - c h a n n e l devices
are t y p i c a l l y slower because o f t h e l o w e r m o b i l i t y o f holes c o m p a r e d w i t h
electrons.
N M O S a n d P M O S (p-channel M O S ) transistors are u s e d side b y side
i n c o m p l e m e n t a r y m e t a l - o x i d e - s e m i c o n d u c t o r ( C M O S ) technology to f o r m
logic elements. T h e s e structures have the advantage of e x t r e m e l y l o w p o w e r
c o n s u m p t i o n a n d are i m p o r t a n t i n ultralarge-scale integration ( U L S I ) a n d
very-large-scale integration ( V L S I ) (13).
Quantitative descriptions of M O S devices are available (2, 8, 9,12). T h i s
short s u m m a r y of solid-state physics was i n t e n d e d to illustrate the i m p o r ­
tance o f c a r r i e r concentrations, transport, generation, a n d r e c o m b i n a t i o n i n
device performance. T h e s e p r o p e r t i e s , i n t u r n , d e p e n d critically o n m a t e r i a l
parameters r e s u l t i n g from a large n u m b e r o f c h e m i c a l process sequences.

Unit Operations
A l t h o u g h m o r e than 100 i n d i v i d u a l process steps are used i n the manufacture
of e v e n s i m p l e i n t e g r a t e d c i r c u i t s , t h e fabrication sequence invokes m a n y
of t h e same operations n u m e r o u s times. A list of " u n i t operations" that
compose t h e technological arsenal for the fabrication of solid-state materials
and devices can b e made. C l e a r l y , these u n i t operations are d i s t i n c t l y dif­
ferent from those associated w i t h t r a d i t i o n a l c h e m i c a l manufacture. N e v e r ­
theless, the purpose of d e f i n i n g such a list is the same: to establish t h e
necessary c h e m i c a l a n d p h y s i c a l operations so that a c o m p l i c a t e d process
may b e d e s i g n e d a n d c a r r i e d o u t f r o m i n d i v i d u a l , m o r e easily c o n t r o l l e d

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26 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

TYPE CROSS SECTION

n-CHANNEL
ENHANCEMENT
(NORMALLY
OFF)

n-CHANNEL
DEPLETION
(NORMALLY
ON)
n-CHANNEL

p-CHANNEL
ENHANCEMENT r q -
(NORMALLY
OFF)

p-CHANNEL
DEPLETION
(NORMALLY
ON) η Ρ*

p-CHANNEL

Figure 14. Schematics of MOS transistors. l denotes the drain current. (Re­
D

produced with permission from reference 8. Copyright 1985 Wiley.)

a n d b e t t e r u n d e r s t o o d steps c o m m o n to a l l m a n u f a c t u r i n g sequences. F o r
instance, t h e fabrication o f solid-state devices can b e d e s c r i b e d b y various
c o m b i n a t i o n s o f the operations g i v e n i n L i s t I.

Overview of Unit Operations. T o m a x i m i z e the e l e c t r o n or h o l e

(carrier) m o b i l i t y a n d thus d e v i c e speed, I C s are b u i l t i n single-crystal s u b ­
strates. M e t h o d s o f b u l k crystal g r o w t h are therefore n e e d e d . T h e most
c o m m o n of these m e t h o d s are the C z o c h r a l s k i a n d float-zone t e c h n i q u e s .
T h e C z o c h r a l s k i t e c h n i q u e is a c r y s t a l - p u l l i n g or m e l t - g r o w t h m e t h o d ,
whereas the float-zone t e c h n i q u e involves l o c a l i z e d m e l t i n g o f a s i n t e r e d
bar o f t h e m a t e r i a l , f o l l o w e d b y c o o l i n g a n d , thus, crystallization.

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1. HESS & JENSEN Microelectronics Processing 27

List I. Unit Operations

in Microelectronic Device Fabrication
• B u l k crystal g r o w t h
Czochralski
F l o a t zone
• C h e m i c a l reactions w i t h surfaces
Cleaning
Oxidation
Etching
• T h i n - f i l m formation
Evaporation
Sputtering
Epitaxy
C h e m i c a l vapor deposition
S p i n casting
• Lithography
• Semiconductor doping
Solid-state diffusion
Ion implantation

A f t e r g r o w t h , t h e single-crystal b o u l e is s l i c e d into wafers o r disks b y

diamond-coated w i r e s o r saws (14). T h e i n d i v i d u a l slices are subsequently
c h e m o m e c h a n i c a l l y p o l i s h e d (14-16), a n d sorted according to electrical r e ­
sistivity. Before t h e wafers are subjected to h i g h - t e m p e r a t u r e processes,
they are exhaustively c l e a n e d i n various acids, solvents, o r b o t h to r e m o v e
organic, inorganic, a n d particulate contaminants (17). O t h e r c h e m i c a l r e ­
actions p e r f o r m e d o n solid surfaces i n c l u d e t h e t h e r m a l oxidation o f s i l i c o n
to f o r m amorphous S i 0 a n d l i q u i d - o r plasma-etching techniques to define
2

patterns i n film o r substrate materials.

Because I C s are b u i l t - u p o f t h i n - f i l m layers, a variety o f film deposition
methods (18-20) are n e e d e d to satisfy specific r e q u i r e m e n t s at p a r t i c u l a r
points i n t h e o v e r a l l process sequence (e.g., film c o m p o s i t i o n , l o w deposition
t e m p e r a t u r e , u n i f o r m step coverage, cleanliness, deposition rate, film m o r ­
phology, a n d crystal structure). I n general, t h e methods can b e classified as
e i t h e r p h y s i c a l (evaporation, s p u t t e r i n g , a n d s p i n coating) o r c h e m i c a l ( c h e m ­
ical vapor deposition), although combinations such as reactive evaporation
or reactive s p u t t e r i n g are sometimes i n v o k e d . T h e combinations i n v o l v e t h e
a d d i t i o n o f a reactive gas such as Ο o r Ν to a n evaporative o r s p u t t e r i n g
2 2

(plasma) atmosphere so that t h e film a n d target are o x i d i z e d o r n i t r i d e d

d u r i n g d e p o s i t i o n (e.g., T i N c a n b e f o r m e d from s p u t t e r i n g T i i n a n A r - N 2

atmosphere).
L i t h o g r a p h y is t h e process o f generating a stencil o r p a t t e r n i n a r a d i a ­
tion-sensitive m a t e r i a l . T h e s t e n c i l subsequently serves as a mask to p e r m i t

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28 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

e t c h i n g o n l y i n selected areas of the film or substrate. D u r i n g the fabrication

of devices or I C s , the d o p i n g type (p or n) a n d l e v e l (resistivity) m u s t b e
altered. ( F o r instance, transistors a n d diodes r e q u i r e p - n j u n c t i o n s , a n d
polycrystalline s i l i c o n resistors d e m a n d p r e c i s e l y c o n t r o l l e d dopant c o n c e n ­
trations.) D o p a n t s can be i n t r o d u c e d into s i l i c o n or other semiconductors
b y b r i n g i n g a vapor c o n t a i n i n g the dopant into contact w i t h the s e m i c o n ­
d u c t o r surface at an elevated t e m p e r a t u r e . Solid-state difiusion t h e n d r i v e s
the dopant i n t o the s o l i d to the r e q u i r e d d e p t h . A l t e r n a t i v e l y , gaseous dopant
ions can b e generated, accelerated, a n d , finally, i m p l a n t e d into a s o l i d s u r ­
face.

Example: N M O S Fabrication. T h e i n d i v i d u a l steps l i s t e d i n L i s t

I can b e s e q u e n c e d to give a s i m p l e process for the fabrication of an N M O S
transistor ( F i g u r e s 12 a n d 15) A l t h o u g h the example is a M O S transistor,
the techniques also a p p l y to the fabrication o f b i p o l a r transistors, diodes,
capacitors, resistors, a n d I C s .
F i r s t , a p - t y p e s i l i c o n wafer is i m m e r s e d i n a sulfuric a c i d - h y d r o g e n
p e r o x i d e m i x t u r e to r e m o v e major organic contaminants. A c i d residues are
r e m o v e d b y r i n s i n g the wafer i n d e i o n i z e d (DI) water (>18 M Ω - c m , a
bacterial count of < 5 0 / L , a n d < 1 0 particles p e r l i t e r larger than 0.3 μπι.
3

R e s i d u a l organic residues a n d metals are r e m o v e d b y i m m e r s i o n i n an a m ­

m o n i u m h y d r o x i d e - h y d r o g e n peroxide b a t h at 7 5 - 8 0 ° C , followed b y a D I -
w a t e r r i n s e . A short d i p i n a h y d r o f l u o r i c a c i d solution followed b y a D I -
w a t e r r i n s e is often u s e d to r e m o v e the " n a t i v e " oxide layer g r o w n w h e n
silicon is exposed to air. T h e r e m a i n i n g atomic a n d i o n i c contaminants are
t h e n r e m o v e d f r o m the wafer surface b y i m m e r s i o n i n a h y d r o c h l o r i c
a c i d - h y d r o g e n p e r o x i d e solution at 75-80 °C. A f t e r another D I - w a t e r r i n s e ,
the wafer is d r i e d w i t h hot n i t r o g e n gas. T h e cleaned substrate is t h e r m a l l y
o x i d i z e d at temperatures above 700 °C i n a resistance-heated quartz t u b e
into w h i c h oxygen, water vapor, or b o t h are flowing ( F i g u r e 15a).
Because the diîusivities of n o r m a l s i l i c o n dopants (boron, p h o s p h o r u s ,
a n d arsenic) are orders o f m a g n i t u d e larger i n S i t h a n i n S i 0 , a S i 0 l a y e r
2 2

can b e u s e d as a mask against dopant i n c o r p o r a t i o n . T h e r e f o r e , selected

areas o f the p-type S i substrate (source a n d d r a i n regions) can be d o p e d b y
generating openings or patterns i n the S i 0 film. T h e precise p a t t e r n i n g is
2

accomplished by lithography.
T h e l i t h o g r a p h i c p r o c e d u r e involves coating the wafer w i t h a r a d i a t i o n -
sensitive m a t e r i a l (usually a p o l y m e r ) c a l l e d a resist. S e l e c t e d areas are t h e n
exposed to r a d i a t i o n ( U V photons, electrons, o r X-rays). W h e n U V r a d i a t i o n
is u s e d , this selective exposure is a c h i e v e d b y a c h r o m i u m - o n - g l a s s p h o t o -
mask ( F i g u r e 15b). F o r positive resists, the radiation renders the exposed
regions m o r e soluble i n a d e v e l o p e r solution than the unexposed areas ( F i g -
u r e 15c). T h u s , differential s o l u b i l i t y p e r m i t s the formation of a resist s t e n c i l
or mask so that e t c h i n g of the film b e n e a t h occurs o n l y i n regions w h e r e

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1. HESS & JENSEN Microelectronics Processing 29

UV Light

(d) (e) (f)

(g) (h) (i)

Figure 15. Simplified process sequence for the fabrication of an NMOS tran-
sistor: (a) substrate preparation, (b) selective exposure of substrate, (c) mask
formation by differential solubility, (d) etching, (e) stripping of resist, (f) dop-
ing, (g) reoxidation of silicon surface, (h) formation of gate oxide, and (i) metal
deposition and patterning. Abbreviations are defined as follows: p-Si, p-type
silicon; PR, photoresist; S, source; G, gate; and D, drain.

the resist has b e e n r e m o v e d . T h e wafers t h e n go t h r o u g h an e t c h i n g step

to transfer the resist p a t t e r n into the u n d e r l y i n g S i O film ( F i g u r e 15d). A t
£

present, e t c h i n g is p e r f o r m e d i n a radio frequency (rf) g l o w discharge

(plasma) c o n t a i n i n g fluorine species, although h y d r o f l u o r i c a c i d solutions
have b e e n u s e d i n the past. T h e r e m a i n i n g resist is t h e n s t r i p p e d i n e i t h e r

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
30 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

organic solvents or an oxygen plasma. T h e result o f this l i t h o g r a p h i c - e t c h i n g

process is a p a t t e r n e d layer ( F i g u r e 15e).
T h e S i regions exposed b y the S i 0 e t c h are d o p e d w i t h phosphorus o r
2

arsenic to f o r m source a n d d r a i n areas ( F i g u r e 15f). U n t i l the early 1970s,

this process was a c c o m p l i s h e d b y p r e d e p o s i t i o n a n d d r i v e - i n diflusion. F o r
the past 15 years, h o w e v e r , selective i n t r o d u c t i o n of dopant atoms i n t o the
S i lattice has b e e n p e r f o r m e d b y i o n i m p l a n t a t i o n . A s i n the case o f p r e ­
d e p o s i t i o n a n d diffusion, a p a t t e r n e d S i 0 l a y e r can b e u s e d to attain selective
2

d o p i n g . A l t e r n a t i v e l y , because i o n i m p l a n t a t i o n is a l o w - t e m p e r a t u r e process
relative to p r e d e p o s i t i o n , p o l y m e r resist layers can serve as i m p l a n t a t i o n
masks.
T h e next step i n the fabrication of the η-channel transistor involves the
formation of the t h i n (10-50-nm) gate oxide b e t w e e n the source a n d d r a i n
regions. F i r s t , the S i 0 , resist, or b o t h r e m a i n i n g from the p r e v i o u s step
2

are r e m o v e d , a n d the S i surface is r e o x i d i z e d to a thickness of ~ 3 0 0 - 5 0 0

n m ( F i g u r e 15g). B y a l i t h o g r a p h i c - e t c h i n g process, an o p e n i n g is f o r m e d
i n the S i 0 , a n d the gate oxide is g r o w n i n this r e g i o n ( F i g u r e 15h). W i n d o w s
2

are t h e n e t c h e d i n the oxide o v e r the source a n d d r a i n regions i n p r e p a r a t i o n

for m e t a l d e p o s i t i o n ( F i g u r e 15i).
T h e e l e c t r i c a l contact o f the source, gate, a n d d r a i n regions is established
b y the d e p o s i t i o n o f a c o n d u c t o r film. T h e s e conductors m u s t satisfy a m u l ­
t i t u d e of r e q u i r e m e n t s , i n c l u d i n g l o w e l e c t r i c a l resistivity, l o w contact
resistance, good step coverage, good adhesion, a n d h i g h e l e c t r o m i g r a -
t i o n resistance (21, 22). Because no single m a t e r i a l meets a l l these r e q u i r e ­
m e n t s , a n u m b e r o f conductors are u s e d i n a process, o n the basis o f the
specific needs (e. g., contact barriers a n d interconnections). F o r instance, a l u ­
m i n u m , h e a v i l y d o p e d p o l y c r y s t a l l i n e s i l i c o n , tungsten, a n d tungsten s i l i -
cide are sometimes u s e d i n an i n d i v i d u a l I C process. T h e s e films are s u b ­
s e q u e n t l y p a t t e r n e d to isolate the connections ( F i g u r e 15j) a n d to p r o v i d e
the interconnections a m o n g the various c i r c u i t elements (transistors,
resistors, diodes, etc.) o n the c h i p . I n this m a n n e r , an electrical c i r c u i t is
formed.
A f t e r the final m e t a l l i z a t i o n layer is p a t t e r n e d , the transistor a n d , o n a
larger scale, the I C are e l e c t r i c a l l y c o m p l e t e . Before the wafer is d i c e d or
sectioned i n t o i n d i v i d u a l chips a n d the circuits are subsequently packaged,
a protective or passivation coating such as p h o s p h o r u s - d o p e d S i 0 , p l a s m a - 2

d e p o s i t e d s i l i c o n n i t r i d e , or p o l y i m i d e is deposited o v e r the finished I C .

T h i s layer protects the surface o f the d e v i c e from i m p u r i t i e s such as alkali
ions a n d w a t e r vapor, w h i c h can degrade the e l e c t r i c a l properties o r p r o m o t e
m e t a l c o r r o s i o n , a n d from m e c h a n i c a l damage d u e to h a n d l i n g . F i n a l l y ,
another l i t h o g r a p h i c step opens w i n d o w s i n the passivation coating so that
leads from a package can b e c o n n e c t e d to the m e t a l l i z a t i o n p a t t e r n . T h e s e
package leads connect the I C functions to the outside w o r l d .

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
1. HESS & JENSEN Microelectronics Processing 31

Organization of This Volume

T h i s v o l u m e addresses m a n y of the u n i t operations l i s t e d i n L i s t I a n d
d e p i c t e d i n F i g u r e 15. T h e c h e m i s t r y a n d c h e m i c a l e n g i n e e r i n g p r i n c i p l e s
b e h i n d these operations are d e s c r i b e d , a n d future directions a n d needs are
suggested. T h e final chapter indicates the p r o b l e m s associated w i t h the
extreme p u r i t y a n d cleanliness d e m a n d e d b y I C processing.

Abbreviations and Symbols

c total m o l a r concentration
concentration o f species A
D a electron diffusivity
hole diffusivity
DAB b i n a r y m o l a r diffusivity
Ε e l e c t r o n energy or electric field
E c
e l e c t r o n energy at m i n i m u m of c o n d u c t i o n b a n d
Eb c
e l e c t r o n energy at b o t t o m of c o n d u c t i o n b a n d
E ct electron energy at top of c o n d u c t i o n b a n d
E F F e r m i level
E^orE, intrinsic F e r m i level
E* b a n d gap
E v e l e c t r o n energy at m a x i m u m of valence b a n d
F(E) probability distribution, F e r m i - D i r a c distribution
G n rate of generation of electrons
G P
rate of generation of holes
h P l a n c k constant
h P l a n c k constant d i v i d e d b y 2ιτ
total c u r r e n t
collector c u r r e n t
drain current
emitter current
forward current
electron current
hole c u r r e n t
reverse c u r r e n t
k B o l t z m a n n constant
effective mass of e l e c t r o n
effective mass of hole
concentration of electrons
concentration of i o n i z e d acceptors
concentration of i o n i z e d donors
i n t r i n s i c c a r r i e r concentration

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32 MICROELECTRONICS PROCESSING: C H E M I C A L ENGINEERING ASPECTS

n l concentration of i m p u r i t y
n p concentration of holes
N A molar flux of species A
N B m o l a r flux of species Β
N e density of electronic states
Νι total concentration of i m p u r i t y
q electronic charge
R A rate of reaction
R n r e c o m b i n a t i o n rate of electrons
R p r e c o m b i n a t i o n rate of holes
t time
Γ temperature
v n drift velocity of electrons
up drift velocity of holes
V potential
V h built-in potential
V F f o r w a r d voltage
VR reverse voltage
χ λ m o l e fraction of species A
Xj thickness of i n v e r s i o n layer
ζ spatial coordinate
ε electric field
€ 0 d i e l e c t r i c p e r m i t t i v i t y of v a c u u m
€ s d i e l e c t r i c p e r m i t t i v i t y of solid
μ η electron mobility
μρ hole m o b i l i t y
ν frequency
σ conductivity
τ carrier lifetime

Acknowledgment
W e thank G . B . L a r r a b e e of Texas Instruments for the use of F i g u r e s 1, 2,
a n d 5.

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.
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RECEIVED for review November 16, 1988. A C C E P T E D revised manuscript February

2, 1989.

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Advances in Chemistry; American Chemical Society: Washington, DC, 1989.