145

-
CIGS
:

.

:
.
. .

A 2008

-

CIGS
:

.

:

. . . ()
. . . . ()

Priv. Doz. Dr. A. Hoffmann (TU-Berlin)
Prof. Dr. M.Ch. Lux-Steiner (HMI-Berlin)
Priv. Doz. Dr. Th. Schedel-Niedrig (HMI-Berlin)

A 2008
i

(), . . . .
. . . .
: Prof. Dr. M. Lux-Steiner Priv. Doz. Dr. Th.
Schedel-Niedrig Hahn-Meitner (HMI) , Priv. Doz. Dr.
A. Hoffmann (Technische Universitt, TU-Berlin).
,
. . .
(09/02-12/07)
. .

:

.
,
.
.
.

,
Hahn-Meitner (HMI-Berlin)
.
: 07/05-09/05, 2006 10/06-07/07 ,

(TU-Berlin) HMI-Berlin.
, . , 07/05-09/05
TU-Berlin HMI-Berlin ,
, DAAD
10/06-07/07 .
: . . M. Ch. Lux-Steiner Priv. Doz. . Th.
Schedel-Niedrig (. S. Doka, . S. Liehmann)
10/06-07/07
ii
HMI-Berlin,
. ,
TU-Berlin,
. . D. Bimberg, Priv. Doz. . A. Hoffmann . T.
Warming, . M. Dworzak M Bgler .
. S. Siebentritt (HMI) . N. Papathanasiou
(HMI) CuIn
1-x
Ga
x
Se
2
(CIGS), . R. Klenk (HMI), . S. Bakehe
(HMI) R. Mainz (HMI) CuIn
1-
x
Ga
x
S
2
(CIGS), . Ch. Kaufmann (HMI)
CuIn
1-x
Ga
x
Se
2
(CIGS) Priv. Doz. . Th. Schedel-Niedrig . S. Doka
CuGaSe
2
(CGS). . . N. Esser
(ISAS-Berlin) . Ch. Cobet (ISAS-Berlin) . Ch. Nickel (HMI)
.

, , , . .

.

25% 75%
()
EEAEK II-- (
).
(TU)

(DAAD=German Academic Exchange Committee)
Erasmus-Socrates.

iii

,
, ,
CIS, CGS CIGS.
,
( )
( )
CuInS
2
(CIS) CuGaSe
2
(CGS) CuIn
1-x
Ga
x
S
2
CuIn
1-x
Ga
x
Se
2

(CIGS) . , ,
CdS ZnSe.
CIS CIGS
(PR) Raman
(RT) / (20 K),
(ER) RT.
CIGS
(% Ga)
CuInSe
2
CuInS
2
(CIS) CuGaSe
2
CuGaS
2
(CGS).
CIGS
(20 ) PR . ER
CIGS RT ,
, , , ,
/
. T

(SE) RT. Raman,
CIGS A
1
- .
iv
A
1

. PR Raman

1
Raman.
CIGS
(PL) (PLE) (7 K).
PL (FWHM) CIGS
Ga (x=0.33 0.60)
. PLE
PL () -
PL . PL, PLE, PR,
2 ,
.
CGS, -p,
, Ge, , 3- 1-
,
. n-CGS/p-CGS/Mo/glass
PL RT 2 Raman RT. PL Raman
Ge
1-,
.
,
CIGS
CGS.

v

.
1. . 1
- (PVs)

2. 2
2.1 2
2.2 4
2.3 - 5
2.4 8

3. 11
3.1 (band-alignment) 11

4.

15

5. 18

6. 20
- CIGS 22

6.1 (RT&LT) CuIn
1-x
Ga
x
Se
2
(CIGS)
(PR) Raman
22

6.1.1 (RT&LT) CuIn
1-x
Ga
x
Se
2
(CIGS)
(PR)

21
6.1.2 (RT) CuIn
1-x
Ga
x
Se
2
(CIGS)
Raman
26

6.2 (LT) CuIn
1-x
Ga
x
Se
2
(CIGS)
(PL)
(PLE)
27

6.3 (RT) CuIn
1-x
Ga
x
Se
2
(CIGS)
(SE)
31

CIGS
6.4 (RT) CuIn
1-x
Ga
x
Se
2
(CIGS)
PR R
33

- CGS 35
6.5 (RT) ZnSe/CuGaSe
2
/Mo/glass PR 35
6.6 (RT&LT) Ge-doped-
CuGaSe
2
/CuGaSe
2
{RT) Raman (RT&LT)

36
- CIGS 40
CIGS
6.7 CuIn
1-x
Ga
x
S
2
(CIGS),
CIGS/CdS CIGS/CdS/ZnO, CIGS
PR, Raman (R)
40
6.7.1 (LT) CuIn
1-x
Ga
x
S
2
(CIGS)
CIGS/CdS CIGS/CdS/ZnO PR
40

6.7.2 (RT) CuIn
1-x
Ga
x
S
2
(CIGS)
CIGS/CdS CIGS/CdS/ZnO Raman
41
6.7.3 (RT) CuIn
1-x
Ga
x
S
2
(CIGS)
(R)
42

vi

7. 48

8. 51

1
1.
- (PVs)

, , ,
,

(Photovoltaics, PVs).
:
- ,
- ,
- ,
- ,
- ,
- ,
-

. , /

(Si).
,

.
[1.1]:
(
g
~1.5 eV)
(~10
5
cm
-1
)
(quantum efficiency)
(diffusion length)
(recombination velocity)
(-/-) Schottky
{Thin Film Solar Cells, TFSCs) [1.2].
, ,
/ (PV modules/cells)
35% , 88.6 MW 1996, 744.8 MW 2003,
[1.3].
2
(TFSCs)
.
, , ,

,
.
, ,

1.1.1. , 19.5 %
Cu(In,Ga)Se
2
(CIGS)
(coevaporation) [1.4].
, ,
33 % [1.5].

1.1.1 ( )

Absorber Energy gap
(eV) (300 K)
Actual efficiency

CuInSe
2
1.05 13.5 % [1.6]
Cu(In,Ga)Se
2
(CIGS) 1.2 19.5 % [1.4]
CuInS
2
1.5 11.4 % [1.7]
Cu(In,Ga)S
2
(CIGS) 1.53 12.3% [1.8]
CuGaSe
2
1.7 9.3 % [1.9]

2.

2.1

O , CuFeS
2
,

.
A
I
B
III
2
VI
=Cu,Ag, B=Al,Ga,In,Tl, =S,Se,Te

12
d 2
D ( , 2.1.1c)),

2
d
T (
, 2.1.1a)) [2.1],[2.2].
3

2.1.1 a)
(ZnS), b)
Zn , c)
2
.

2
, X
, , ,
.
, 2.1.2,

, , ,
. ,
, s 3p sp
3
.
() ,
.
CuGaSe
2
, Cu Ga ,
Se .
IV
Diamond structure
(Si,Ge)
III-V
Zinc-blende structure
(GaAs,InP)
II-VI
Zinc-blende structure
(ZnSe,CdS)
II-IV-V
2
Chalcopyrite structure
(ZnGeAs
2
)
I-III-VI
2
Chalcopyrite structure
(CuInSe
2
,CuGaSe
2
,CuInS
2
)

2.1.2
4

(ZnS,
), :
1) , ,
, - -,

BX AX
R R ,
2) ,
/ 2 1 c a = ,
3)
u ( 2.1.1c), :
1
2 2
2
[ (1 ) /16]
AX
R a u = + + (2.1.1)

1
2 2
2
[( 1 2) (1 ) /16]
X
R a u
= + + (2.1.2)
a .
, ,
2 2 2
( 1 4)
BX AX
a R R u a = =
, 1 4 u [2.1].

2.2

-VI (ZnS), o
A
I
B
III
2
VI
, ,
. ,
3d- 4d-
p-

VI
( p-d). ,
A
I
B
III
2
VI

-VI 1.6 eV,
(spin-orbit splitting)
,
spin-orbit p- spin-orbit d-
[2.3]. , d-

p-d [2.4]. d-
, 16 45 %.
p-d
,
, d- [2.3], [2.5].
5
Brillouin ( )
,
7
,
6

7
( 2.2.1) [2.1].
p-
, (spin)
(spin-orbit interaction,
so
)
(crystal-field,
cf
) (c/2a)
X
VI
.

, -
(quasicubic model) [2.6], [2.7].

2.2.1 : CuInSe
2
, CuInS
2

(CIS) CuGaSe
2
, CuGaS
2
(CGS) ( ()
c-
, c ( c-, E//c)) [2.8].

() (PR)
- , E
a,
E
b
E
c
,
c E//c .

2.3 -

A
I
B
III
2
VI

. 2.3.1 a) CuInS
2
[2.9], b)
CuInSe
2
[2.10] c) CuGaSe
2
[2.11] ,
6
.. CuInS
2
(Cu
2
S)
1-x
(In
2
S
3
)
x
0 x
1 ( 2.3.1a)).

2.3.1 a) CuInS
2
[2.9], b) CuInSe
2
[2.10] c) CuGaSe
2
[2.11].
a)

c)

b)

7
, Cu
2
S-In
2
S
3
,

, CuInS
2
CuIn
5
S
8
. CuInS
2

:
( <1090 C,
2.3.1a), ( <1090 C, )
983 C, (-). , CuIn
5
S
8
,
, 20-1085
C ( ) [2.9],
[2.12].
-Auger Cu CuInS
2

(Cu-rich films), ,
, (CuS). CuS
CuInS
2
,

,
(etching) (KCN)
[2.13]. Cu
x
Se CuGaSe
2

Cu: CuGaSe
2
( 2.3.1c)),

Cu
x
Se, ,
KCN.
CuInGaX
2
(X= S, Se), Cu
,
, . ,
CuSe ,
, CuS
600
C. , Cu-S,
CuInS
2
-.
(In-rich films) CuInS
2
, 52
mole % In
2
S
3
2.3.1a),
, . , Cu
CuIn
2
(=S, Se, Te)
In
Cu
3+
Cu (V
Cu
-
) . ,
, In
Cu
3+
- 2V
Cu
-
,
CuIn
3
X
5
CuIn
2
X
3.5
,
(Ordered Vacancy Compounds, OVCs) [2.14]:
X=Se X=S, Se, Te [2.13].
CuGaSe
2
,

Ga, CuGaSe
2
(
8
2.3.1c), [Cu]:[Ga] 0.5:0.5 0.42:0.58,
.
, Cu
2
Se-Ga(In)
2
Se
3
,
CuInSe
2
CuGaSe
2
,
10 mole % In
2
Se
3
Ga
2
Se
3
, .
, , CuInS
2
and CuGaS
2
,
, 1 mole % [2.12], [2.15].

O
, , ,

() Raman.

2.4

(12) : 3
V
x
(vacancies), 3 X
i
(interstitials) 6

X
(cation-cation
or cation-anion antisites). , ,
.
80, Newmann [2.16]
Van Vechten CuInSe
2
:
(point-defect formation
energies),
Fermi. , CuInSe
2

-n, InCu (10-30 meV ,
CB), -n p, V
Se
(60-80 meV CB),
-n, VCu (20-40 meV
, VB) . [2.16]. , , .. V
Cu
+In
Cu
,
. , Newmann
,
:
1)
f
(,q) ,
, ,
q [2.17]. ,
CuInSe
2
In Cu
9

f
(Cu
In
0
)= -0.5eV CuInSe
2
Cu ( C 2.4.1)
f
(Cu
In
0
)= 3.5eV CuInSe
2
In ( 2.4.1) (
, ,
).
, (band alignment)
CuInSe
2
CuGaSe
2
Wei Zunger [2.18], ,
,
Ga
Cu
0
, Cu
Ga,
In
Cu
0
.

Ga,
In, CuGaSe
2

(CBM) ( CBM CuGaSe
2

0.6 eV CuInSe
2
)
Ga
Cu
0
-. 4s Ga
0.7 eV 5s In. ,
(n-type doping) CuGaSe
2

CuInSe
2
[2.19].
2) , ,
Fermi
F
. H CuInSe
2

2.4.1: Fermi
Cu (V
Cu
)
, In
Cu. In
Cu
.
3)
. CuInSe
2
,
Cu In
Cu
(2V
Cu
-
+In
Cu
2+
)
[2.20]
f
(2V
Cu
-
+In
Cu
2+
) = -0.1eV (
2.4.1). , ,
CuInSe
2
, , ,
, .

10

2.4.1 V
Cu
, V
In
, In
Cu
, Cu
In
Cu
i

Fermi
F
CuInSe
2
( (VBM)
(CBM)) , C.
, q
[2.19], [2.20].

. ,
CuInSe
2
CuIn
1-x
Ga
x
Se
2
(CIGS) ,
, , (compensation)
Cu/In
Se
[2.21]. ,
, [Cu]/([In]+[Ga])>1, In Cu
(Cu
In
-
) In (V
In
-
)
Se (V
Se
2+
),
. , ,
In
Cu
+
V
Cu
-
[2.22].

H
() (PL), () (PLE=
Photoluminescence Excitation).
11
3.

3.1 (band-alignment)

, -n
-p. -n
. ZnO (E
g
= 3.37 eV, 300 )
[3.1] -n (window layer).
- -p,
, (absorber).
(3.5x10
4
cm
-1
CuGaSe
2
1.7 eV)
, ~2m, .
,
, ,
.
H ZnO/
( ), , ZnO

CIGS [3.2]. ,
(10-80 nm) (ZnS,
) ZnO . (buffer
layer) , CdS (E
g
= 2.42 eV, 300 [3.3])
(Chemical Bath Deposition, CBD).

, ZnO (),
.

(band-offsets)
v
E
c
E
.
CuIn
1-x
Ga
x
Se
2
(CIGS)/CdS/ZnO
(19.5% [3.4]).

- (I-V) . ,
V
oc
, I
sc

12
ff , .
[3.5]:

( )
1
qV kT
S L
I I e I = (3.1.1)
1
- p-n,
2

L
,
. ff
V
oc
, I
sc
, P
in
:

m m sc oc
ff I V I V =

sc oc in
ffI V I = (3.1.2)

, (
, x=[Ga]/([In]+[Ga]>0.3)
, V
oc
[3.6]).
1.2-1.3 eV, V
oc
,

. , V
oc

, CIGS. , ,
, ,
(ff) [3.7].
CIGS,
v
E
CIGS/CdS
1 eV. ,
c
E
(Ga), ,
, [3.8].
CIGS/CdS
0
c
E > (band alignment type-I).
3.1.1, Ga,
CIGS/CdS (spike),
CIGS
g
E , (cliff)
g
E [3.7],
[3.10]. , , 0
c
E < (cliff),

g
E , CdS
13
/
CdS. To ZnSe (
g
E = 2.7 eV, 300 K), , ,
, CdS,
, ,
.

3.1.1 (a)
(b) ZnO/CdS/CIGS [3.9].

ZnSe,
(ZnS, ZnO, (Zn,Mg)O, In(OH)
3
, In
2
S
3
, In
2
Se
3
, InZnSe
x
, SnO
2
, SnS
2
),
CdS, CIGS.
CdS,
Cd (Cd-free buffer layers) [3.11]. , ,
-Cd, ZnS
(CBD), 18.6% [3.12].
3.1.2 , ,
(ZnO/CdS/Cu(In,Ga)Se
2
(CIGS)/Mo/glass).
14

3.1.2 CIGS.

, , , (Mo)
, Na (soda lime glass, SLG, 15.6 wt. % Na
Na
2
O [3.13]),
(dc magnetron sputtering). , ,
, .. , ,
( ),
-n -p . To Na,
, , Mo, ,
,
[3.14].

Na,
,
(
oc
V ) (ff) ,
( ) [3.15].
, , Na (~0.1 at. %
Na), , ,
(NaF), ~30 nm, Mo [3.16].

( ) (ZnO) Ni/Al
.
0.5 cm
2
[3.17].

15
4.

ZnO/ZnSe//Mo/glass
n-/p-/Mo/glass. ,
,
(Thin Film Solar Cells, TFSCs),
.
, /
,
.
, . ,
CdS
ZnSe.

.

CIS, CGS CIGS
Hahn-Meitner-
Institut (HMI) .
CuIn
1-x
Ga
x
Se
2
(CIGS)
(x=0.08-0.82) (Ga)
GaAs (001) (MOVPE =
Metal-Oxide Vapor Phase Epitaxy) [4.1].
CuInS
2
(CIS) CuIn
1-x
Ga
x
S
2

(CIGS) , ,
(coevaporation) (Physical
Vapor Deposition, PVD). (CdS)
(Chemical Bath Deposition, CBD)
(ZnO) (window layer)
CIGS/CdS PVD
(dc magnetron sputtering) [4.2].
CuIn
1-x
Ga
x
Se
2
(CIGS)
, , PVD [4.3].
CIGS
16
ZnO/CdS/CIGS/Mo/glass Ni/Al
[4.2].
CuGaSe
2
(CGS),
(Ge),
(Chemical Close-Spaced Vapor Transport, CCSVT).
, (Ge)
. 10
16
ions/cm
2
Ge 150 keV
CuGaSe
2
, ,
(10
16
ions/cm
2
),
[4.4], [4.5].

ZnSe, CdS,
(e-beam Evaporation,
EBE) ,

.

1) :
1.) CuIn
1-x
Ga
x
Se
2
(CIGS)
(x=0.08-0.82) (Ga) GaAs
(001)
(Spectroscopic Ellipsometry=SE)
(RT), (Photoreflectance=PR)
(20 ), (Photoluminescence=PL)
(Photoluminescence Excitation=PLE)
2 , Raman (RT).
1.)

CuInS
2
(CIS) CuIn
1-x
Ga
x
S
2
(CIGS)
CdS/CuIn
1-x
Ga
x
S
2
ZnO/CdS/CuIn
1-x
Ga
x
S
2

-
PR (20 )
Raman RT.

2)
CuIn
1-x
Ga
x
Se
2
PR , ,
SE .

17
3)
CuIn
1-x
Ga
x
S
2
CuIn
1-x
Ga
x
Se
2

(Electroreflectance=ER)

/
.

4) , PR :
ZnSe/CuGaSe
2
/Metal/glass
CdS
ZnSe.

5) CuGaSe
2

-p , Ge (ion
implantation)
. n-CuGaSe
2
/p-CuGaSe
2
/Mo/glass
PL RT 2 Raman RT.

(PR) (ER)
()
. . . . . , ,
(PL/PLE)
(SE) (TU-Berlin)
. . . . . . A.
Hoffmann (ISAS Berlin)
. . . Esser. , ,
Raman , . .
. . . ,

(PL)
(VEPL=Variable Excitation Photoluminescence)
Raman/PL .
, PL
, Raman .

18
5.

) - - (PR&ER)
() -
(PR) (Xe lamp, XBO, 100W)
(Tungsten/Halogen lamp, 75 or 100W),
(CVI, 1200/grate, 0.25m), ,

InGaAs ( 5.1.1).
laser (Ar
+
) (Kr
+
) (CW),
.
10 Hz (RT) 30 Hz
(20 ). laser
(SPEX 1704, 1600 mm
-1
, 1 m)
.
lock-in.
.

. 5.1.1 (PR).

() (ER)
,
19
.
10 Hz 0 +1.5 V.

) Raman
Raman laser
(Ar
+
) (r
+
),
laser,

(SPEX 1403, 1800 mm
-1
, 1 m),
(PMT) GaAs. laser
.
.

.

) (PL/PLE) (7)
(PL)
(PLE) (Tungsten/Halogen lamp, 250W),

(Action Research Corp. Spectra Pro-275, 0.275m),

, , ( ) Ge.
80 Hz .
(Action
Research Corp. Spectra Pro-275, 0.3m) ,
(motorized filter wheel)
. lock-in.
7 He
(CryoVac).
.

) PL (2)
(PL) laser
(Ar
+
), laser,

20
, ( Czerny-Turner, 1m) GaAs
Ge. (Keithley 417 High speed
Picoammeter) lock-in. lock-in,
85 Hz.
.
(2), He.

)
CIGS 230-620 nm (2-
5.4 eV) SE800
Sentech Instruments GmbH. (Xe).
(step scan mode)
45

.
CCD (Charge-coupled Device, ).
(SpectraRay II).
(0.75-4.2 eV),
VASE J.A. Woolam Co. -()
(1000-1700 nm) / (quartz tungsten
halogen (QTH) lamp) InGaAs.
400-1000 nm, (Xe)
, .

6.

CIGS.
, ,

(ZnO/CdS/Cu(In
1-x
Ga
x
)Se
2
(CIGS)/Mo/glass) 19.5 % [6.1].
CIGS Ga,
x=[Ga]/([Ga]+[In]~30 % ,
0.88<[Cu]/([In]+[Ga])<0.95. CIGS
(PVD = Physical Vapor Deposition)
Mo/. Ga 30 %
21
CIGS .
CIGS, ,
Ga 12 %. , ,

.
,
Cu(In
1-x
Ga
x
)Se
2
Cu(In
1-x
Ga
x
)S
2
(CIGS)
(MOVPE = Metal-Oxide Vapor Phase
Epitaxy) / (PVD = Physical Vapor
Deposition), , Hahn-
Meitner . MOVPE

, PVD
()
ZnO/CdS/CIGS/Mo/,
. , ,
CIGS Ti,
Mo/.

.

CuIn
1-x
Ga
x
S
2
CuIn
1-x
Ga
x
Se
2

TANDEM
(ZnO/CdS/CuIn
1-x
Ga
x
S
2
(CIGS)/ZnO/CdS/CuIn
1-x
Ga
x
Se
2
(CIGS)/Mo/glass)
.
, , (1.5-2.5
eV, )
, (1-1.7 eV,
). ,

CuInS
2
(CIS) CuGaSe
2
(CGS) CuIn
1-x
Ga
x
S
2
CuIn
1-x
Ga
x
Se
2
(CIGS)
.

. n-
22
CuGaSe
2
/p-CuGaSe
2
/Mo/glass Ge
, 500 nm, .
CdS
ZnSe.

- CIGS

CuIn
1-x
Ga
x
Se
2
(CIGS)
Ga (x=0.08, 0.19, 0.33, 0.50, 0.60, 0.82) GaAs (001)

. : ( ,
, ) PR
SE,
Raman
(PL) (PLE).

6.1 (RT&LT) CuIn
1-x
Ga
x
Se
2
(CIGS)
(PR) Raman

6.1.1 (RT&LT) CuIn
1-x
Ga
x
Se
2
(CIGS)
(PR)

CIGS PR
(RT) (20 ). CIGS
Ga, x=[Ga]/([In]+[Ga])=0.08 0.19,
: 500
C, Ga, x>0.30,
570
C [6.1].
, CuGaSe
2
, 50
nm, /GaAs,
(SEM) - (XRD)
[6.2], [6.3].
(slightly Cu-rich), [Cu]/([Ga]/+[In])=1.0-1.1,
6.1.1 [6.2]-[6.4]. T 6.1.1
Ga.
,
CIGS RT (20
) PR .
23
PR
( )
.

6.1.1 CuIn
1-x
Ga
x
Se
2
(CIGS).

x=[Ga]/([Ga]+[In])
(EDX)
[Cu]/([In]+[Ga])

(nm)
CIGSe009 0.08 1.0079 440
CIGSe010 0.19 0.9918 440
CIGSe029 0.33 1.0135 360
CIGSe022 0.50 0.9883 390
CIGSe027 0.60 1.0065 290
CIGSe026 0.82 1.0697 250

(RT), PR CIGS
x<0.80,
E
a
, 2.2.
Ga, E
a
,
CuInSe
2
CuGaSe
2
, 1.0
1.7 eV RT. PR CIGS x=0.82 ,
E
a
, E
b

CIGS , E
a
, E
b
E
c
CuGaSe
2
.

RT
(Aspnes)
6.1.2, 20 .
E
a
CIGS (2
)
x Ga, :

E
a
=1.054 + 0.313 x + 0.310 x
2
eV (6.1.1)

, ,
,
E
a
E
b
E
c
[6.5], [6.6]
(bowing parameter, b)
E
a
, , / (6.1.1)
E
b
E
c
. ,

, , , ,
24
(. 6.3),

.
6.1.1 PR CIGS
Ga 20 .

. 6.1.1 PR CuIn
1-x
Ga
x
Se
2
(CIGS) 20
( x0.50, PR
CIGS CuGaSe
2
).

PR CIGS (20 )
E
a
E
b

. , , (band-edge)
E
a
,
E
b

c
A-, B- C- , . ,
, ,
1.0 1.2 1.4 1.6 1.8 2.0 2.2
CuIn
1-x
Ga
x
Se
2
20 K
R
/
R

(
x
1
0
-
3
)
x0.4
x0.4
x0.4
x0.1
E
b
E
a
E
b
E
b
E
b
E
a
E
a
E
a
E
b
E
a
E
b
E
a
E
c
E
b
E
a
0.82
0.60
0.50

0.33
0.19
x=0.08
Energy (eV)
25
. PR CIGS x0.50
, E
a
, E
b
E
c

CuGaSe
2
, CIGS/GaAs .
E
a
E
b
20
(Aspnes)
6.1.2.

6.1.2 E
a
, E
b
E
c
CIGS
[Ga]/([In]+[Ga]) RT 20 K.

[Ga]/([Ga]+[In]) 300 K 20 K
E
a

(eV)
E
b

(eV)
E
c

(eV)
E
a

(eV)
E
b

(eV)
E
c

(eV)
0.08 1.083 - - 1.080 1.101 1.312
0.19 1.141 1.146 1.156
0.33 1.152 1.175 1.254
0.50 1.301 1.318 1.340
0.60 1.369 1.371 1.407
0.82 1.514 1.568 1.554 1.610
1.00 1.676 1.789 1.994 1.704 1.824 2.034

6.1.2 E
a
E
b

CIGS [Ga]/([In]+[Ga]) 20 K. x=1,
E
a
E
b
CuGaSe
2

x=0.82. PR
CIGS RT, E
a
E
b
2

:

E
a
=1.051 + 0.359 x + 0.299 x
2
eV (6.1.2)
E
b
=1.084 + 0.298 x + 0.433 x
2
eV (6.1.3)

26
0.0 0.2 0.4 0.6 0.8 1.0
1.0
1.2
1.4
1.6
1.8
2.0
CuIn
1-x
Ga
x
Se
2
20 K

T
r
a
n
s
i
t
i
o
n

e
n
e
r
g
y

(
e
V
)
[Ga]/([Ga]+[In])
Ea
Eb

6.1.2 E
a
E
b
CIGS
[Ga]/([In]+[Ga]) 20 K.

6.1.2 (RT) CuIn
1-x
Ga
x
Se
2
(CIGS) Raman

CIGS Raman
(RT). Raman :
) 647.1 nm laser (Kr
+
) ) 514.5 nm laser (Ar
+
),
300 mW 30 m.
(fitting)
Lorentz , (Full Width at Half Maximum, FWHM)
() CIGS.
, ,
A
1
- .
1
,
CuInSe
2
(CIS) CuGaSe
2
(CGS), [6.7].

, , ,

6.1.3. PR Raman,
27
647.1 nm- laser Kr
+
,
:

E
g
(
phonon
) =103.436-1.208 +0.004
2
(6.1.4)

A
1
CIGS.

1
-
Raman.
514.5 nm- laser
r
+
:
E
g
(
phonon
) =98.716-1.149 +0.004
2
(6.1.5)

172 174 176 178 180
1.1
1.2
1.3
1.4
1.5
[Ga]/([In]+[Ga]
0.08 0.230.25 0.52 0.62 0.81
b
a
n
d
-
g
a
p

e
n
e
r
g
y

(
e
V
)
E
g
=103.436-1.208 +0.004
2
Raman-shift (cm
-1
)

6.1.3 Raman
CIGS.

6.2 (LT) CuIn
1-x
Ga
x
Se
2
(CIGS)
(PL) (PLE)

CuIn
1-x
Ga
x
Se
2
(CIGS)
(PL)
(PLE) (7 K). PL PLE
28
PR - (X-Ray
Diffraction, XRD) [6.2], [6.3].
PL ( 6.2.1) , CIGS,
, , 1.47
eV, GaAs. CIGS Ga, x=0.33
0.60, PL PL CIGS
6.2.1.

6.2.1 PL CIGS 7 K.

Ga, PL
CIGS ,
E
a
E
b
. PL
CIGS Ga, x=0.33 0.60
. -X (XRD), ,
, , (008)

0.8 1.0 1.2 1.4 1.6 1.8
750 nm
GaAs
x0.5
(a)
x2
x2
CuIn
1-x
Ga
x
Se
2
, PL 7 K
Tungsten lamp

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
0.19
0.08
0.50
0.33
x=0.82
0.60
29
, , Ga.
, , x=0.33 0.60
,
XRD [6.2], [6.3].
PL, ,
,
(Donor-Acceptor Pair (DAP) recombination).

6.2.1 PL CIGS 7 K.

[Ga]/([Ga]+[In])
-PL
(eV)
0.08 0.987 -
0.19 1.064 -
0.33 1.071 1.252
0.50 1.228 -
0.60 1.268 1.42
0.82 1.446 -

(PLE) 7 .
, PL () -PL
. 6.2.2 6.2.3 , ,
PL PLE Ga, x=0.08 0.33, .
6.2.2 PLE
PL, (),
(FWHM) PL, () (), .
, ()
, 0.987 eV.
x=0.19.
1.062 eV (onset) 1.107 1.336 eV
-DAP 0.987 eV, E
a
E
c
,
.

30
0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
1.062
CuIn
0.92
Ga
0.08
Se
2
, PL/PLE 7K
1.336
1240 nm
1258 nm
1284 nm
1.107

I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Energy (eV)
(III)
(II)
(I)

6.2.2 PL PLE CIGS x=0.08 7 K.

0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
1.14
1.52
(II)
(III)
(I)
CuIn
0.67
Ga
0.33
Se
2
, PL/PLE 7 K
1.232
1.305
1.266
1.43

1202nm
1164nm
1120nm
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)

6.2.3 PL PLE CIGS x=0.33 7 K.

Ga, x030, PLE ,
6.2.3 , ,
31
PL, (),
(FWHM) PL, () (), , x=0.33.
, , PLE PL
, 1.252 eV ( 6.2.3 ).
.
() 1.14 eV, 1.266
eV, 1.252 eV 1.34 eV 1.43 eV. ,
, () (), ,
, 1.232 1.305 eV, , ().
() (onset) () (),
. PLE
(onsets)
Ga, XRD .
,
(fluctuating potentials),
(compensation) [6.8], [6.9]. 1.43
1.52 eV, 6.2.3, , ,
GaAs .
PL, PLE PR, 2 ,

.

6.3 (RT) CuIn
1-x
Ga
x
Se
2
(CIGS)
(SE)

CIGS
2-5.4 eV (SE)
(RT). ,
1
< >

2
< > , , CIGS.
65
.
6.3.1
CIGS. [6.6],

2 2
2
/ d d E
1
(), ()
1
()
.
1
()
1
()
Brillouin () () N. x=0.33
32
0.82, ()
Brillouin. x0.33 ()
CuGaSe
2
CIGS/GaAs
.
2.7 eV,
(interferences),
.

Ga, x0.60, . ,
, SE
CIGS (1-1.7 eV).
1.5 2.0 2.5 3.0 3.5 4.0 4.5
CuIn
1-x
Ga
x
Se
2
E(X)
x0.5
x0.5
x0.5
E
1
(B)
E
1
(A)
0.82
0.60
0.50
0.33
0.19

x=0.08
d
2
2
/
d
2
E
Energy (eV)

6.3.1
2 2
2
/ d d E
CIGS
(RT).

33
CIGS
6.4 (RT) CuIn
1-x
Ga
x
Se
2
(CIGS)
PR R

CuIn
1-x
Ga
x
Se
2
(CIGS)
ZnO/CdS/CIGS/Mo/ Ga : x~30 % ,
, (=19.5% [6.1]). ,
CIGS Mo/
Ti, , ,
(Mo/)
.
PR
CuIn
1-x
Ga
x
Se
2
(CIGS) 34 % 36 % Ga
- , ,
[6.10]. ER
CIGS .
PR
(interference fringes)
,
. , PR ER
, .
6.4.1a) , , PR CIGS
-. ( 6.4.1b))
(Aspnes)
CIGS, , ,
(1-1.7 eV).
PR 6.4.1 ,
E
a
E
b
. PR , ,
CIGS .
PR CIGS (. 6.1.1) ,
.

Ga . ,
E
a
E
b
,
,
CIGS/CdS CdS/ZnO.
34
0.9 1.0 1.1 1.2 1.3 1.4 1.5
-0.04
-0.02
0.00
0.02
0.04
-0.04
-0.02
0.00
0.02
0.04
CIGS solar cell on glass substrate
PR spectrum, 300 K
(a)

Energy (eV)
R
/
R

(
x
1
0
-
3
)
E
b
E
a (b)

6.4.1 PR CIGS Mo/
(RT).

/ (6.1.1), E
a
-
Ga ,
Ga CIGS .
Mo/, -
(Energy Dispersive X-Ray Analysis, EDX).
, EDX, Ga x=0.36 ,
/ (6.1.1), x=0.23. Ga ,
,
: , Ga , ,
.
, , Ga ,
, . ,
PR CIGS/Ti foil , ,
Ga EDX. ,
35
Ga . ,
Ga. , PR
( ~120 nm) , 1.8 m,
laser
. , ER
. ER
PR
. PR/ER
XRF (X-Ray Fluorescence) [6.10].

6.5 (RT) ZnSe/CuGaSe
2
/Mo/glass PR

CdS CIGS
[6.11], [6.12]. ZnSe ,
, CdS,
18.6% [6.12].
ZnS
(e-beam Evaporation, EBE). PR ZnSe
ZnSe/CuGaSe
2
/Mo/glass 6.5.1.
351 nm-line-Kr
+
-laser.
(Aspnes) ()
ZnSe: E
g
= 2.69 eV. , ,
PR . ,
-- PR ZnSe ( 6.5.1)
.
- (XRD),
(SEM) (AFM) ,
Raman [6.13].
, , ,
CdS ZnSe CIGS.

36
1.5 2.0 2.5 3.0 3.5
-0.6
0.0
0.6
1.2
1.8
PR 300 K, 350.7 nm Kr
+
- laser
ZnSe on CuGaSe
2

R
/
R

(
x
1
0
-
3
)
Energy (eV)
2.7 eV
laser

6.5.1 PR ZnSe CuGaSe
2
/Mo/glass.

- CGS
6.6 Ge-doped-CuGaSe
2
/CuGaSe
2

Raman (RT)
RT 2 K

Ge CuGaSe
2

CuGaSe
2
p-n

.
Ge, CuGaSe
2
,
p, nm
n [6.14].
Ge-doped-CuGaSe
2
/CuGaSe
2
Raman
(RT) (Photoluminescence, PL),
(2 ),
(defects) Ge.
Raman CuGaSe
2

Ge 3- 1- , 6.6.1a), b) c).
Raman
1
,
2
(LO)
2
(TO) CuGaSe
2
RT [6.7], [6.15].
1
Ge.
37
, CuGaSe
2

Lorentz. -
1
,
2
(LO)

2
(TO) 184, 273 249 cm
-1
, .
Ge Raman
( 6.6.1b) c)):
Raman,
.
2
-

1
-,
.
(B
2
)
(A
1
). Raman , ,
, Ge 1-
.

150 200 250 300
100
200
(a)

as grown
Raman-shit (cm
-1
)
R
a
m
a
n
-
i
n
t
e
n
s
i
t
y

(
c
p
s
)
3-stage_implantation
100
(b)
B
2
(LO)
273 cm
-1
B
2
(TO)
249 cm
-1
A
1
184 cm
-1

100
(c)
(p.l.)

6.6.1 Raman a) CuGaSe
2
(as grown)
Ge b) 3- c) 1-
647.1nm/250mW Kr
+
-laser RT.
38
, -
1

2
(LO)
Fano [6.16]. Fano (Fano line-shape)

(interaction of a phonon with an electron continuum) , ,
(heavily doped samples). -
1

2
(LO)
,
.

514.5nm laser (r
+
) 180 mW,
. PL CuGaSe
2

1.67 eV, .
Ge 1-, PL ,
1.67 eV, 2.10
eV. ,
, (CuSe, Cu
2
Se, Ga
2
Se
3
)
.
.
, Ge 3- PL
1.62.3 eV.
6.6.2a), b) c) PL
CuGaSe
2
Ge 3-
1-, , 2 K.
PL, ,
. PL
Gauss , (Full Width at Half Maximum, FWHM),
PL CuGaSe
2

Ge.
, , , PL
CuGaSe
2
, (. 6.6.2a))

,
, 1.66 1.63-1.60 eV, .
PL, , ,

(Donor-Acceptor Pair (DAP) recombination).
Ge CuGaSe
2
3- (. 6.6.2b)), 1- (.
6.6.2c)), -PL ,
39
, .
-PL ,
, /
. , , PL CuGaSe
2
,
(. 6.6.2a)) Ge 3- (.
6.6.2b)) 1- (. 6.6.2c)), (1.63-
1.60 eV) Ge.
PL Raman
Ge 1-,
.
Ge .
1.4 1.6 1.8 2.0 2.2
0
2
4
6
0
1
0
1
(a)
1-stage implantation
as grown

P
L
-
I
n
t
e
n
s
i
t
y

(
n
A
)
PL-energy (eV)
1.63 eV
1.60 eV
(b)

1.62 eV
1.66 eV
1.63 eV
(c)
1.66 eV

6.6.2 PL, 2K, CuGaSe
2
a),
Ge 3- b) 1- c).

40
- CIGS
CIGS

6.7 CuIn
1-x
Ga
x
S
2
(CIGS), CIGS/CdS
CIGS/CdS/ZnO, CIGS PR,
Raman (R)

() CuIn
1-x
Ga
x
S
2
(CIGS)
ZnO/CdS/CIGS/Mo/
Ga : x~10 %,
CIGS, x~30 % [6.1], [6.17].
CIGS, CIGS/CdS CIGS/CdS/ZnO PR
(20 ) Raman RT
Ga.
CIGS (R).

6.7.1 (LT) CuIn
1-x
Ga
x
S
2
(CIGS) CIGS/CdS
CIGS/CdS/ZnO PR

CuIn
1-x
Ga
x
S
2
(CIGS)
CIGS/CdS CIGS/CdS/ZnO
(PR) 20 .
,
. CuIn
1-x
Ga
x
S
2
(CIGS)
(Ga), x=0.04 0.12. 12 %
Ga, , , [6.17],
4 % Ga
CuInS
2
(CIS). CIS

CIGS
(4 %),
[6.17].
PR CIGS
488 457.9 nm laser
Ar
+
, 30 Hz.
(Si). 20 ,
(closed-cycle He-cryostat).
PR CIGS
, ,
41
(6.1.1), E
a
E
b

. E
a
E
b
,
() Aspnes
6.7.1.

6.7.1 E
a
E
b
CIGS 20 K.

PR 20 K
a
(eV)
b
(eV)
CuInS
2
1.5330.001 1.5520.001
CuIn
1-x
Ga
x
S
2
(x=0.04) 1.5320.001 1.5800.002
CuIn
1-x
Ga
x
S
2
(x=0.12) 1.6510.002 1.6720.002

, , PR CIGS/CdS
CIGS/CdS/ZnO ,
, CdS ZnO 20 .
CIGS/CdS/ZnO,
350.7 nm (3.54 eV)- laser (Kr
+
).
PR, E
a
/ E
b
CdS ZnO,
. ,
,
, CIGS/CdS CdS/ZnO
. . 6.7.2).

6.7.2 (LT) CuIn
1-x
Ga
x
S
2
(CIGS) CIGS/CdS
CIGS/CdS/ZnO Raman

CIGS (Ga),
x=0.04 0.12 , CIGS/CdS CIGS/CdS/ZnO
Raman (RT).
: 514.5 nm-Ar
+
-laser 647.1 nm- Kr
+
-laser.
Raman CIGS
CuInS
2
(CIS) CuGaS
2
(CGS) [6.7]
(CuS)
([Cu]/([In]+[Ga]>1) .
Raman
In Ga CIS CIGS [6.18]. ,
, CIGS Ga (x0.12),
42
Ga ,
/Mo/. Raman CIGS/CdS CIGS/CdS/ZnO
CuS CuS
CdS
(KCN).

-X (XRD) [6.17] (SEM)
CIGS.

6.7.3 (RT) CuIn
1-x
Ga
x
S
2
(CIGS)
(R)

CIGS:
CIGS CdS
ZnO (ER)
. ER (RT)
.
ER PR () (. 6.7.1):
, PR CIGS
CIGS/CdS CIGS/CdS/ZnO (20 ).
R
CuIn
1-x
Ga
x
S
2
(CIGS) (x=0.04 0.12) CuInS
2

RT, 6.7.1.
ER
CuInS
2
,
(Aspnes),
Aspnes.
6.7.2.
43
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
-0.01
0.00
0.01
x=0.00
CuIn
1-x
Ga
x
S
2
solar cells
ER spectra, 300K

R
/
R

(
x
1
0
-
3
)
Energy (eV)
x=0.12
x=0.04
-0.01
0.00
0.01

-0.01
0.00
0.01

6.7.1 ER CuIn
1-x
Ga
x
S
2
(x=0,
0.04, and 0.12) RT .

6.7.2 E
a
E
b
CIGS
RT.

ER RT
a1
(eV)
b1
(eV)
a2
(eV)
b2
(eV)
CuInS
2
1.535
0.001
1.535
0.001

CuIn
1-x
Ga
x
S
2
(x=0.04) 1.486
0.001
1.521
0.001
1.552
0.002
1.580
0.004
CuIn
1-x
Ga
x
S
2
(x=0.12) 1.552
0.010
1.589
0.003
1.614
0.002
1.640
0.001

, ,

: CuIn
1-x
Ga
x
S
2
(x=0.04
0.12), (Ga) ,
-
44
(Energy Dispersive X-ray fluorescence, EDX) [6.17]. H
Ga
(-, Ga-rich region) (-,
Ga-poor region), , Ga,

. , ,
a1
b1
-
,
a2
b2
-
.

Ga (CIGS),
CIGS/CdS CdS/ZnO :

) Ga
Ga -
-
-
. - (X-Ray Diffraction, XRD Analysis) [6.17],
CuIn
x
Ga
1-x
S
2
(=5.5094 ,
x=0.04 =5.4962 , x=0.12 [6.19]) CuInS
2
(=5.516 ,
x=0.00 [6.19]). XRD
Ga ( x).
,
-CuInS
2
(- )
-CuIn
x
Ga
1-x
S
2
( ) .

a1
,
b1
,
a2

b2
,
/
(Mo/).
.
,
4% 12% Ga,
/.

ER (. 6.7.2).

[6.20], [6.21].
45

[100] [010] (bisotropic stress):
= =
yy xx
, 0
zz
=
(6.7.1)
0
zx yz xy
= = =
,

b
,
Brillouin (k=0), [6.22]:

11 12 11 12
11 11
2
2
a
C C C C
E a b
C C
( | | | | +
=
( | |
\ \
(6.7.2)

11 12 11 12
11 11
2
2
b
C C C C
E a b
C C
( | | | | +
= +
( | |
\ \
(6.7.3)

b

CIGS,
bulk
E

= ,
b b bulk
E = ,

b

bulk
,,
, b (hydrostatic and
shear deformation potentials), .
bulk

(strain-free conditions),
CuInS
2

ER RT ( 6.7.2).

ij
C CuInS
2
J. Lazewski et al.
[6.23] :
11
C =83.7 GPa
12
C =54.4 GPa.
CuInS
2
,
CuInSe
2
( = -2.23 eV). ,
[6.24].
b - I-III-VI
2

Yoodee et al. [6.25], :
( 0.8 0.2)
p
b eV = (6.7.4)
( 4.3 1.5)
d
b eV = (6.7.5)
b
p
b
d
p d,
, [6.26]:
a (1 a)
p d
b b b = + (6.7.6)
1-a d p-d.
46
Shay Tell [6.27] d- 45 %
CuInS
2
. /. (6.7.4)-(6.7.6) b=-2.375 eV. Yoodee et. al.
[6.25] d-, 1-=0.413. /.
(6.7.4)-(6.7.6), b=-2.246 eV.
, Shay Tell [6.27] b
I-III-VI
2

cf
, :
1.5 (2 )
cf
c
b
a
= (6.7.7)
c . CuInS
2
,

cf
=0.05 [6.27], /
(6.7.7) b=-2.36 eV.
CIGS CIGS
, b, and C
ij
/. (6.7.2)-(6.7.3)
6.7.3.
R CIGS 4 % Ga
CIGS 12 % Ga.

ER , ER (
a1
,
b1
,
a2
,
b2
) .
, , 1% (0.5-
0.8%).

6.7.3 CIGS
( b
C
ij
CuInS
2
[6.25], [6.26]
[6.27].

(
)

(
b
)
CuIn
1-x
Ga
x
S
2

x=0.04
-0.0070

-0.0070
-0.0073
*
0.0036
0.0036
0.0039
*
CuIn
1-x
Ga
x
S
2

x=0.12
0.0024
0.0024
0.0025* -0.014
-0.014
-0.015*
[6.27]
[6.26], [6.27]
*
[6.25], [6.26].

47
) CIGS/CdS
CdS/ZnO
(Scanning
Electron Micrographs, SEM) CIGS 3
m. CdS ZnO 50
350 nm, . CdS ZnO
,.
.
, ,
E
a
- E
b
- ER
( 6.7.1), CdS ZnO.
ER
1.4-4.0 eV , ,
CdS ZnO. , CdS,
, E
a
E
b

(2.2180.018) eV (2.4560.008) eV, .
[6.28].
ZnO :
a
=(3.2110.013),
b
=(3.4440.062) eV. ZnO,
, [6.29] E
g,o
= 3.37 eV RT,
E
a
ER.
CdS ZnO
. ZnO
ZnO
3.25
[6.30]), CdS (
CdS
= 4.14 [6.30])
CIGS (=5.5094 ,
x=0.04 =5.4962 , x=0.12 [6.19]). , ,

- - [6.31].

48
7.

,
, .
,
, ,

.

:

1) CuIn
1-x
Ga
x
Se
2
(CIGS)
(x=([Ga]/([Ga]+[In]=0.08-0.82), GaAs(100),
(PR) (RT)
(20 ), : CIGS
(RT) 20
. PR
( )
,
2) Raman ( : 647.1 nm Kr
+
-laser 514.5 nm Ar
+
-
laser) CIGS
,
CuInSe
2
(CIS) CuGaSe
2
(CGS). A
1
-
. PR Raman

1
-
Raman.
3) PL PLE (7 K)
- (X-Ray Diffraction, XRD).
PL (FWHM) CuIn
1-x
Ga
x
Se
2
(CIGS)
Ga (x=0.33 0.60)
. (PLE)

PL () -PL .
PL, PLE PR 2 ,
49

.
3) (ER)
CuIn
1-x
Ga
x
Se
2
(CIGS) 34% Ga,
(-) ( ) ,
(=19.5%). ER
CIGS.
E
a
Ga
Ga CIGS, ,
.
XRF (X-Ray Fluorescence) .
4) ER
CuIn
1-x
Ga
x
S
2
(CIGS) 12%
Ga, E
a

E
b
CdS
ZnO n- p-n. ,
ER ,
. ,
PR (20 ),
.
Ga (CIGS),
CIGS/CdS CdS/ZnO. ER
CIGS E
a
- E
b
-,
1% (0.5-0.8%)
, .
6) Raman CuGaSe
2

Ge, 3- 1- a,

1
,
2
(LO),
2
(TO)
RT. Raman Ge
.
1
-
2
(LO)-
Fano q ,

. PL ( Ge)
(2 K) ,
Ge.
50
PL
/ (defect-
related PL) 1-
. PL Raman
Ge 1-,
.

, CIGS
, , , ,
. ( , ,
)
E (SE) (PR)
. ER, , , ,
(, CdS ZnO)
CIGS.
Ga CIGS

Ga.
,
(
) ,

.
, ,
, , CIGS
, ,
. , , ,
,
.

51
8.

. 1

1.1 A. Goetzberger, C. Hebling, H.W. Schock, Photovoltaic materials, history, status and
outlook, Materials Science and Engineering R 40 (2003) 1-46
1.2 K.L. Chopra, P.D. Paulson, V. Dutta, Thin Film Solar Cells: An Overview, Progress in
Photovoltaics: Research and Applications 12 (2004) 69-92
1.3 N.G. Dhere, R.G. Dhere, Thin-Film Photovoltaics, Journal of Vacuum Science and
Technology A 23(4) (2005) 1208-1214
1.4 M.A. Contreras, K. Ramanathan, J. AbuShama, F. Hasoon, D. L. Young, B. Egaas, R. Noufi,
Diode Characteristics in State-of-the-Art ZnO/CdS/Cu(In
1-x
Ga
x
)Se
2
Solar Cells, Progress in
Photovoltaics and Research Applications 13 (2005) 209-216
1.5 J.H. Werner, J. Mattheis, U. Rau, Efficiency limitations of polycrystalline solar cells: case of
Cu(In,Ga)Se
2
, Thin Solid Films 480-481 (2005) 399-409
1.6 M.A. Contreras, J. Tuttle, A. Gabor, A. Tennant, K. Ramanathan, S. Asher, A. Franz, J.
Keane, L. Wang, J. Scofield, R. Noufi, 1
st
World Conference of Photovoltaic Solar Energy
Conversion, Hawaii, 1994, pp. 6875
1.7 K. Siemer, J. Klaer, I. Luck, J. Bruns, R. Klenk, D. Brunig, Efficient CuInS
2
solar cells from
a rapid thermal process (RTP), Solar Energy Materials and Solar Cells 67(14) (2001) 159
166
1.8 R. Kaigawa, A. Neisser, R. Klenk, M.-Ch. Lux-Steiner, Improved performance of thin film
solar cells based on Cu(In,Ga)S
2
, Thin Solid Films 415 (2002) 266271
1.9 V. Nadenau, D. Hariskos, H.W. Schock, CuGaSe
2
based Thin Film Solar Cells with
Improved Performance, 14
th
European Photovoltaic Solar Energy Conference and
Exhibition, Barcelona, 1997, pp. 12501253

. 2

2.1 L. Shay and J.H. Wernick, Ternary Chalcopyrite Semiconductors: Growth, Electronic
Properties and Applications, Pergamon (Oxford, 1974)
2.2 J.E. Jaffe and A. Zunger, Electronic structure of the ternary chalcopyrite semiconductors
CuAlS
2
, CuGaS
2
, CuAlSe
2
, CuGaSe
2
and CuInSe
2
, Physical Review B, 28 (10) (1983) 5822-
5847
2.3 J.L. Shay, B. Tell, Energy Band Structure of I-III-VI
2
Semiconductors, Surface Science 37
(1973) 748-762
2.4 M.I. Alonso, K. Wakita, J. Pascual, M. Garriga, and N. Yamamoto, Optical functions and
electronic structure of CuInSe
2
, CuGaSe
2
,

CuInS
2
, and CuGaS
2
, Physical Review B 63
(2001) 075203-1-13
2.5 J.E. Jaffe and A. Zunger, Theory of the band-gap anomaly ABC
2
chalcopyrite compounds,
Physical Review B 29(4) (1984) 1882-1906
2.6 J.J. Hopfield, Fine Structure in the Optical Absorption Edge of Anisotropic Crystals, Journal
of Physics and Chemistry of Solids, 15 (1960) 97-107
2.7 S. Shirakata, S. Chichibu, Photoreflectance of Cu-based IIIIVI
2
heteroepitaxial layers
grown by metalorganic chemical vapor deposition, Journal of Applied Physics 79(4) (1996)
2043-2054
2.8 M.I. Alonso, M. Garriga, C.A. Durante Rincn, E. Hernndez, M. Len, Optical functions of
chalcopyrite CuGa
x
In
1x
Se
2
alloys, Applied Physics A 74 (2002) 659664
2.9 J.J.M. Binsma, L.J. Giling, J. Bloem, Phase Relations in the system Cu
2
S-In
2
S
3
, Journal of
Crystal Growth 50 (1980) 429-436
2.10 U.C. Boehnke, G. Khn, Phase Relations in the ternary system Cu-In-Se, Journal of
Materials Science 22 (1987) 1635-1641
52
2.11 J.C. Mikkelsen, Ternary Phase Relations of the Chalcopyrite Compound CuGaSe
2
, Journal
of Electronic Materials 10(3) (1981) 541-558
2.12 Y. Tomm, S. Fiechter, Crystal growth of materials for photovoltaics, Journal of Ceramic
Processing Research 6(2) (2005) 141-145
2.13 R. Scheer, H.J. Lewerenz, Formation of secondary phases in evaporated CuInS
2
thin films:
A surface analytical study, Journal of Vacuum and Science Technology A 13(4) (1995)
1924-1929
2.14 D. Schmid, M. Ruckh, F. Grunewald, H.W. Schock, Chalcopyrite/defect chalcopyrite
heterojunctions on the basis of CuInSe
2
, Journal of Applied Physics, 73 (1993) 2902-2909
2.15 P. Villars, A. Prince, and H. Okamoto (Ed.), Handbook of Ternary Phase Diagrams, (ASM
International, 1995)
2.16 H. Newmann, Influence of intrinsic defects on the electrical properties of A
I
B
III
C
2
VI

compounds, Crystal Research Technology 18(4) (1983) 483-490
2.17 S. Zhang, S.. Wei, . Zunger, H.K. Yoshiba, Defect Physics of the CuInSe
2
chalcopyrite
semiconductor, Physical Review B 57(16) (1998) 9642-9656
2.18 S.H. Wei, S.Zunger, Band offsets and optical bowings of chalcopyrites and Zn-based II-VI
alloys, Journal of Applied Physics, 78(6) (1995) 3846-3856
2.19 . Zunger, S. Zhang, and S. Wei, Revisiting the Defect Physics in CuInSe
2
and CuGaSe
2
,
Proc. 26th IEEE Photovoltaic Specialists Conference, VSEC (1997) 313-318,
10.1109/PVSC.1997.654091
2.20 S.B. Zhang, S.H. Wei, and A. Zunger, Stabilization of Ternary Compounds Via Ordered
Defect Arrays of Defect Pairs, Physical Review Letters 78 (1997) 4059-4062
2.21 A. Tell, J.L. Shay, H.M. Kasper, Room-Temperature Electrical Properties of Ten I-III-VI
2

Semiconductors, Journal of Applied Physics 43(5) (1972) 2469-2470
2.22 D.J. Schroeder, G.D. Berry, A.A. Rockett, Gallium diffusion and diffusity in CuInSe
2

epitaxial layers, Applied Physics Letters 69(26) (1996) 4068-4070

. 3

3.1 P. L. Washington, H. C. Ong, J. Y. Dai, and R. P. H. Chang, Determination of the optical
constants of zinc oxide thin films by spectroscopic ellipsometry, Applied Physics Letters 72
(25) (1998) 3261-3263
3.2 A. Romeo, M. Terheggen, D. Abou-Ras, D.L. Btzner, F.J. Haug, M. Klin, D. Rudmann,
A.N. Tiwari, Development of Thin-film Cu(In,Ga)Se
2
and CdTe Solar Cells, Progress in
Photovoltaics Research and Applications 12 (2004) 93-111
3.3 S. Ninomiya, S. Adachi, Optical properties of wurtzite CdS, Journal of Applied Physics
78(2) (1995) 1183-1190
3.4 M.A. Contreras, K. Ramanathan, J. AbuShama, F. Hasoon, D.L. Young, B. Egaas, R. Noufi,
1-x
Ga
x
)Se
2
3.5 S.M. Sze, Physics of Semiconductor Devices, 2
nd
ed., John Wiley & Sons (New York, 1981)
3.6 W.N. Shafarman, R. Klenk, B.E. McCandless, Device and material characterization of
Cu(In,Ga)Se
2
solar cells with increasing band gap, Journal of Applied Physics 79(9) (1996)
7324-7328
3.7 R. Herberholz, V. Nadenau, U. Rhle, C. Kble, H.W. Shock, and B. Dimmler, Prospects of
wide-gap chalcopyrites for thin film photovoltaic modules, Solar Energy Materials and Solar
Cells 49 (1997) 227-237
3.8 U. Rau, H.W. Schock, Electronic properties of Cu(In,Ga)Se
2
heterojunction solar cells-
recent achievements, current understanding, and future challenges, Applied Physics A 69
(1999) 131-147
3.9 M. Gloeckler, J.R. Sites, Efficiency limitations for wide-band-gap chalcopyrite solar cells,
Thin Solid Films 480-481 (2005) 241-245
53
3.10 R. Klenk, Characterisation and modelling of chalcopyrite solar cells, Thin Solid Films
387 (2001) 135-140
3.11 D. Hariskos, S. Spiering, M. Powalla, Buffer layers in Cu(In,Ga)Se
2
solar cells and
modules, Thin Solid Films 480-481 (2005) 99-109
3.12 A. Contreras, T. Nakada, M. Hongo, A.O. Pudov, J.R. Sites,
ZnO/ZnS(O,OH)/Cu(In,Ga)Se
2
/Mo Solar cell with 18.6% efficiency, Proc. 3
rd
World
Conference of Photovoltaic Energy Conversion, Osaka, Japan 2003, pp. 570-573
3.13 L.I. Maissel, R. Glang, Handbook of Thin Film Technology, McGraw Hill (New York,
1970)
3.14 L. Kronik, D. Cahen, H.W. Schock, Effect of Sodium on Polycrystalline Cu(In,Ga)Se
2
and
its Solar Cell Performance, Advanced Materials 10(1) (1998) 31-36
3.15 D. Rudmann, A.F. da Cunha, M. Kaelin, F. Kurdesau, H. Zogg, A.N. Tiwari, G. Bilger,
Efficiency enhancement of Cu(In,Ga)Se
2
solar cells due to post-deposition Na
incorporation, Applied Physics Letters 84(7) (2004) 1129-1131
Technology A 23(4) (2005) 1208-1214
3.17 R. Caballero, D. Guilln, M.T. Gutirrez, C.A. Kaufmann, CuIn
1-x
Ga
x
Se
2
-based Thin-Film
Solar Cells by the Selenization of Sequentially Evaporated Metallic Layers, Progress in
Photovoltaics: Research and Applications, 14 (2006) 145-153

. 4

4.1 N. Rega, S. Siebentritt, J. Albert, M.-Ch. Lux-Steiner, Photoluminescence of CuIn
1-x
Ga
x
Se
2

epitaxial thin films grown by MOVPE, Materials Research Society (MRS) Symposium
Proceedings 763 (2003) 183-188
4.2 R. Kaigawa, A. Neisser, R. Klenk, M.Ch. Lux-Steiner, Improved Performance of thin film
2
, Thin Solid Films 415 (2002) 266-271
4.3 C.A. Kaufmann, A. Neisser, R. Klenk, R. Scheer, Transfer of Cu(In,Ga)Se
2
thin film solar
cells to flexible substrates using an in situ process control, Thin Solid Films 480481 (2005)
515-519
4.4 M. Rusu, S. Wiesner, D. Fuertes Marrn, A. Meeder, S. Doka, W. Bohne, S. Lindner, Th.
Schedel-Niedrig, Ch. Giesen, M.Ch. Lux-Steiner, CuGaSe
2
thin films prepared by a novel
CCSVT technique for photovoltaic application, Thin Solid Films 451-452 (2004) 556-561
4.5 S. Doka, M. Rusu, A. Meeder, E. Arushanov, N. Fabre, S. Fiechter, Th. Schedel-Niedrig,
M.Ch. Lux-Steiner, Effects of Ge-Implantation on the Photoluminescence of CuGaSe
2
Thin
Films, Materials Research Society Symposium Proceedings 865 (2005) F5.27.1-F5.27.5

. 6

1-x
Ga
x
)Se
2
1-x
Ga
x
Se
2

epitaxial thin films grown by MOVPE, MRS Symp. Proc. 763 (2003) 183-188
6.3 N. Rega, PhD thesis, Photoluminescence of Cu(In,Ga)Se
2
epitaxial layers, Freie Universitt
Berlin, Berlin 2004
6.4 N. Rega, S. Siebentritt, J. Albert, S. Nishiwaki, A. Zajogin, M.-Ch. Lux-Steiner, R. Kneise,
M.J. Romero, Exitonic luminescence of Cu(In,Ga)Se
2
, Thin Solid Films 480-481 (2005) 286-
290
6.5 M. I. Alonso, M. Garriga, C.A. Durante Rinon, E. Hernndez, and M. Len, Optical
functions of chalcopyrite CuGa
x
In
1x
Se
2
alloys, Applied Physics A 74 (2002) 659664]
54
6.6 P.D. Paulson, R.W. Birkmire, and W.N. Shafarman, Optical characterization of CuIn
1-x

Ga
x
Se
2
alloy thin films by spectroscopic ellipsometry, Journal of Applied Physics 94 (2)
(2003) 879-888
6.7 F.W. Ohrendorf, H. Haeuseler, Lattice Dynamics of Chalcopyrite Type Compounds. Part I.
Vibrational Frequencies, Crystal Research and Technology, 34(3) (1999) 339-349
6.8 B.I. Schklovskji, A.L. Efros, Electronic Properties of Doped Semiconductors, Springer-
Verlag (Berlin, 1984)
6.9 M.A. Reshchikov, G.C. Yi, B.W. Wessels, Behavior of 2.8- and 3.2- eV photoluminescence
bands in Mg-doped GaN at different temperatures and excitation densities, Physical Review
B 59 (20) (1999) 13176-13183
2
thin film solar
cells to flexible substrates using an in situ process control, Thin Solid Films 480481
(2005) 515-519
Technology A 23(4) (2005) 1208-1214
2
solar cells and
6.13 D. Papadimitriou, G. Roupakas, S. Theodoropoulou, Ch.N. Panagopoulos, M. Georgiou,
A.G. Mamalis, D.E. Manolakos, Growth and Characterization of ZnSe Thin Films on
CuGaSe
2
Photovoltaic Absorbers (submitted)
2
Thin
6.15 C. Xue, PhD thesis, Structural and Optical Investigation of CuGaSe
2
Thin Films for Solar
Cell Device Applications, NTUA, Athens 2003
6.16 U. Fano, Effects of Configuration Interaction on Intensities and Phase Shifts, Physical
Review 124 (6) (1961) 1866-1878
2
, Thin Solid Films 415 (2002) 266-271
6.18 A. Neisser, I. Hengel, R. Klenk, Th.W. Matthes, J. Alvarez-Garcia, A. Perez-Rodriguez, A.
Romano-Rodriguez, M.Ch. Lux-Steiner, Effect of Ga incorporation in sequentially
prepared CuInS
2
thin film absorbers, Solar Energy Materials and Solar Cells 67 (2001) 97-
104
6.19 T. Kato, S. Hayashi, T. Kiuchi, Y. Ishihara, Y. Nabetani, T. Matsumoto, Structural
properties of Cu(Ga
1-x
In
x
)
y
S
z
bulk alloys, Journal of Crystal Growth 237-239 (2002) 2005-
2008
6.20 A. Gavini and M. Cardona, Modulated Piezoreflectance in Semiconductors, Physical
Review B 1(2) (1970) 672-682
6.21 E. Anastasakis and M. Cardona in: High Pressure in Semiconductor Physics II,
Semiconductors and Semimetals, Academic Press (New York, 1998)
6.22 H. Asai and K. Oe, Energy band-gap shift with elastic strain in Ga
x
In
1-x
P epitaxial layers
on (001) GaAs substrates. Journal of Applied Physics 54 (1983) 2052-2056
6.23 J. Lazewski, P.T. Jochym and K. Parlinski. Band Structure, Born effective charges, and
lattice dynamics of CuInS
2
from ab initio calculations, Journal of Chemical Physics 117(6)
(2002) 2726-2731
6.24 S.H. Wei, A. Zunger, I.H. Choi, P.Y. Yu, Trends in band-gap pressure coefficients in
chalcopyrite semiconductors, Physical Review B 58(4) (1998) R1710-R1713
6.25 K. Yoodee, J.C. Wooley, V.Sa-yakanit, Effects of p-d hybridization on the valence band of
I-III-VI
2
chalcopyrite semiconductors, Physical Review B 30(10) (1984) 5904-5915
6.26 L. Artus, Y. Bertrand, C. Ance, Crystal-field and spin-orbit interactions at the fundamental
gap of AgGaSe
2
chalcopyrite compound, Journal of Physics C: Solid State Physics 19
(1986) 5937-5943
55
6.27 J.L. Shay, B. Tell, Energy band structure of I-III-VI
2
semiconductors, Surface Science 37
(1973) 748-762
6.28 S. Ninomiya, S. Adachi, Optical properties of wurtzite CdS, Journal of Applied Physics
78(2) (1995) 1183-1190
6.29 G.E. Jellison, Jr. and L.A. Boatner, Optical functions of uniaxial ZnO determined by
generalized ellipsometry, Physical Review B 58 (1998) 3586-3589
6.30 H.T. Grahn, Introduction to Semiconductor Physics, World Scientific (Singapore, 1999)
6.31 T. Yao, Y. Okada, S. Matsui, K. Ishida, I. Fujimoto, The effect of lattice deformation on
optical properties and lattice parameters of ZnSe grown on (100) GaAs, Journal of Crystal
Growth 81 (1987) 518-523

:

:

:

2008-2003: PhD
*

.
2003-2001: Sc
*

.
2001-1996: BSc
*

.

:

(Proficiency of Michigan)

______________________________________
09/2003-12/2007: : CIGS
.
. . (,
, ).

09/2002-06/2003: (MSc.) :
-
, . . (,
) . . . (,
, ).

10/1999-02/2001: :

, .
. . ( ,
, ).

:

1. Alcoholic beverages and Mediterranean diet in human health. Wine phenolics and ethyl
alcohol as antioxidants and scavengers of oxygen free radicals. Toxicological implications
for moderate and high alcohol consumption, A. Valavanidis, V. Zonaras, S.
Theodoropoulou, Review of Clinical Pharmacology & Pharmacokinetics. Epitheorese
Klinikes Farmakologias kai Farmacokinetikes, International Edition 15(2) (2001) 85-96.

2. Red Wine and the French Paradox. Beneficial Effects to Human Health. Myth or Reality?
A comparative study of the antioxidant potential of alcohol and polyphenols in red and
white wine. S. Theodoropoulou, V. Zonaras, M. Charalabaki, E. Nicolopoulos and A.
Valavanidis, Pharmakeftiki 15(4) (2002) 107-118.

3. Structural and Optical Characterization of Pyrolytic Carbon derived from Novolac Resin.
S. Theodoropoulou, D. Papadimitriou, L. Zoumpoulakis, J. Simitzis, Analytical and
Bioanalytical Chemistry, Special Issue (Springer-Verlag 2004, 10.1007/s00216-003-2453-
5).

4. Optical Properties of Carbon materials formed by pyrolysis of Novolac-resin/Biomass
Composites. S. Theodoropoulou, D. Papadimitriou, L. Zoumpoulakis, I. Simitzis, Diamond
and Related Materials 13(2) (2004) 371-375.

5. Photoreflectance Spectroscopy: A Powerful Tool Applied in the Bandgap Measurement of
Photovoltaic Absorbers, D. Papadimitriou, S. Theodoropoulou, H.Y. Xu, C. Xue, Proc.
ISTM 2005, vol. 1, 998-1001.

6. Raman and Photoreflectance Study of Cu(In
,
Ga)S
2
Films and Solar-Cells, S.
Theodoropoulou, D. Papadimitriou, S. Bakehe, R. Klenk, M.Ch. Lux-Steiner, IASME
TRANSACTIONS, vol. 2(3) (2005) 287-293.

7. Raman and Photoreflectance Study of CuIn
1-x
Ga
x
Se
2
Epitaxial Layers, S.
Theodoropoulou, D. Papadimitriou, N. Rega, S. Siebentritt, and M.Ch. Lux-Steiner, Thin
Solid Films 511-512 (2006) 690-694.

8. Structural Properties of Ge doped CuGaSe
2
Films Studied by Raman and
Photoluminescence Spectroscopy, S. Theodoropoulou, D. Papadimitriou, S. Doka, Th.
Schedel-Niedrig, M.Ch. Lux-Steiner, Thin Solid Films 515(15) (2007) 5904-5908.

9. Test and Measurement of Chalcopyrite based Solar cells by Optical Modulation
Techniques, S. Theodoropoulou, D. Papadimitriou, Proc. ISTM 2007, vol. 4, 2881-2885.

10. Band-gap energies and strain effects in CuIn
1-x
Ga
x
S
2
based solar cells, S.
Theodoropoulou, D. Papadimitriou, A.G. Mamalis, D.E. Manolakos, R. Klenk, M.Ch. Lux-
Steiner, Semiconductor Science & Technology 22 (2007) 933-940.

11. Lattice Defect Analysis in Chalcopyrite Semiconductor Heterostructures by
Photoluminescence Excitation Spectroscopy, S. Theodoropoulou, D. Papadimitriou, and A.
Hoffmann (in preparation).
12. Optical Properties of CuIn
1-x
Ga
x
Se
2
Epitaxial Layers sensed by Spectroscopic
Ellipsometry, S. Theodoropoulou, D. Papadimitriou, Ch. Cobet, and N. Esser (in
preparation).

13. Performance of rigid- and flexible-substrate chalcopyrite thin film solar-cells, S.
Theodoropoulou, D. Papadimitriou, Ch. Kaufmann (in preparation).

:

1. Comparative study of the antioxidant activity of red and white wines in the presence of
oxygen free radicals by means of EPR and other spectroscopic methods, 2
nd
Panhellenic
Conference of Free Radicals and Oxidant Stress, 2000.

2. Structural and optical properties of pyrolytic carbon derived from novolac resin
International Conference on NSTRUMENTAL ETHODS OF NALYSIS (IMA)
2003, 2003.

3. ptical Properties of carbon materials formed by pyrolysis of novolac-resin/biomass
composites, UROPEAN MATERIALS RESEARCH SOCIETY (EMRS) Spring
Meeting 2003, 2003.

1-x
Ga
x
Se
2
Epitaxial Layers, UROPEAN
MATERIALS RESEARCH SOCIETY (EMRS) Spring Meeting 2005,
2005.

,
Ga)S
2
Films and Solar-Cells, 2005
IASME/WSEAS International Conference on ENERGY, ENVIRONMENT,
ECOSYSTEMS&SUSTAINABLE DEVELOPMENT, 2005.

2
Photoluminescence Spectroscopy, UROPEAN MATERIALS RESEARCH SOCIETY
(EMRS) Spring Meeting 2006, Nice 2006.

7. Characterization of ZnSe Thin Films Grown by EBE on Glass and Chalcopyrite-
Semiconductor Substrates, G. Roupakas, G. Kastrinaki, S. Theodoropoulou, M. Kokkoris,
D. Papadimitriou, M. Giorgiou, Ch. Panagopoulos, XXII
, 2006.

8. :
, . , .
, . , . ,
o (TEE): & , 2006.

9.
, . , . , Ch. Cobet, .
, . , . , W. Richter, :
, 2007.

1-x
Ga
x
Se
2
Quaternary Alloys for Solar-Energy Conversion, S.
Theodoropoulou, D. Papadimitriou, K. Anestou, Ch. Cobet, and N. Esser, XXIII
,
2007.

:

:
Composites, S. Theodoropoulou, D. Papadimitriou, L. Zoumpoulakis, I. Simitzis, Diamond
and Related Materials (2004), 13 (2) 371-375.
1-x
Ga
x
Se
2
Solid Films 511-512 (2006) 690-694.
2
Schedel-Niedrig, M. Ch. Lux-Steiner, Thin Solid Films 515(15) (2007) 5904-5908.

:

1. -:

CIGS .
,
, 8/11/02 - 7/11/05

2. ERASMUS-SOCRATES, - TU-Berlin 01/07/05-31/09/05

3. DAAD, CIGS Thin Film Photovoltaic Technology. Energy Band Gap and Lattice Defect
Analysis in Chalcopyrite Semiconductor Heterostructures, Hahn-Meitner Institute Berlin
1/10/06-31/07/07

NATIONAL TECHNICAL UNIVERSITY OF ATHENS
FACULTY OF APPLIED SCIENCES
DEPARTMENT OF PHYSICS

CIGS
Thin Film Photovoltaic Technology:

Energy Band-Gap and Lattice Defect Analysis
in Chalcopyrite Semiconductor Heterostructures

Dipl. Chem. Sofia Theodoropoulou

Doctoral Thesis

Supervisor:
Dr. Dimitra Papadimitriou
Assist. Prof. NTUA

ATHENS 2008
NATIONAL TECHNICAL UNIVERSITY OF ATHENS
FACULTY OF APPLIED SCIENCES
DEPARTMENT OF PHYSICS

CIGS
Thin Film Photovoltaic Technology:

Energy Band-Gap and Lattice Defect Analysis
in Chalcopyrite Semiconductor Heterostructures

Dipl. Chem. Sofia Theodoropoulou

Doctoral Thesis

Co-Supervisors:

Prof. Dr. J. Simitzis (NTUA)
Assoc. Prof. Dr. I. Zouboulis (NTUA)

Priv. Doz. Dr. A. Hoffmann (TU-Berlin)
Prof. Dr. M.Ch. Lux-Steiner (HMI-Berlin)
Priv. Doz. Dr. Th. Schedel-Niedrig (HMI-Berlin)

ATHENS 2008

i
Preface

This PhD thesis is focused on the CIGS Thin Film Photovoltaic Technology, in
particular on the Energy Band Gap and Lattice Defect Analysis in Chalcopyrite Semiconductor
Heterostructures performed in the Physics Department of the National Technical University of
Athens (NTUA) under the supervision of Assist. Prof. Dr. Dimitra Papadimitriou. Part of the
measurements referred in this thesis have been performed at the Hahn-Meitner-Institute (HMI)
Berlin, under the co-supervision of Prof. Dr. M.-Ch. Lux-Steiner and Priv. Doz. Dr. Th. Schedel-
Niedrig, and at the Technical University (TU-Berlin), under the co-supervision of Priv. Doz. Dr.
A. Hoffmann.
Firstly, I would like to express my deep appreciation and respect to my supervisor Assist.
Prof. Dr. Dimitra Papadimitriou who has greatly contributed in the accomplishment of my PhD-
thesis. Our cooperation, lasting more than 5 years, has been always harmonic and fruitful since it
has been characterized by respect and belief to each others abilities and ethical values. In our
relationship, common interest in science and reliable experimental work has been always the
best-combined parameters towards the best result. She has been supportive and encouraging in
all the cases I needed her help by treating me as a colleague and not as just a student. Her passion
for serving the physics science and the development of technology has been an inspiration and a
motivation for more extended effort and work.
Prof. Papadimitriou has also supported my studies on Solar Energy Materials and
Technology at the Hahn-Meitner Institute (HMI) Berlin. With her recommendation, I
participated in the ERASMUS-Socrates Exchange Program, in the period 07/05-09/05, and as a
visiting research scientist at HMI, elaborated my skills in Thin Film Photovoltaics with the kind
encouragement of Prof. Dr. M.-Ch. Lux-Steiner, head of the SE
2
-Department, and Priv. Doz. Dr.
Th. Schedel-Niedrig. I owe Prof. Schedel-Niedrig a lot and I am grateful for his continuous
excellent guidance during my stay at HMI in this time period and in the period 10/06-07/07. I
would also like to thank Dr. S. Doka and Dr. S. Liehmann from Prof. Schedel-Niedrigs group
for their support.
Due to lack of access in the experimental equipment of the Physics Department at
NTUA, my supervisor and me relied on our scientific cooperation with the work-groups of Prof.
D. Bimberg, head of the Department of Solid State Physics at the Technical University (TU-
Berlin), and Priv. Doz. Dr. A. Hoffmann in order to perform experimental measurements
acquired for my thesis. In April 2006, we joined our partner-group and performed the PL/PLE
measurements at TU-Berlin. In addition, I was nominated by Prof. Papadimitriou and Prof.
Schedel-Niedrig for a DAAD-scholarship and a research position at HMI-Berlin in the time
ii
period 10/06-07/07. During this period, I have been able to complete my measurements at TU-
Berlin and accomplish my PhD-degree under the guidance of a highly distinguished scientist and
researcher, Prof. A. Hoffmann. Prof. Hoffmann supported my efforts with all his heart and he is
greatly acknowledged for his significant contribution in my PhD-thesis. Prof. Bimberg is greatly
acknowledged for providing labor-equipment and measurement-time. I would also like to thank
the members of Prof. Bimbergs and Prof. Hoffmanns group, Dr. Till Warming, Dr. M.
Dworzak, and M Bgler for their help.

Prof. Papadimitrious continuous guidance and substantial support and the support of my
co-supervisors in Berlin: Prof. Dr. M. Ch. Lux-Steiner (HMI-Berlin), Priv. Doz. Dr. Th. Schedel-
Niedrig (HMI-Berlin), and Priv. Doz. Dr. A. Hoffmann (TU-Berlin) were essential for the
accomplishment of this thesis and are all greatly acknowledged for their help.
I greatly acknowledge the support of Prof. Dr. N. Esser (Director of ISAS-Berlin), Dr.
Ch. Cobet (ISAS-Berlin) and Dr. Ch. Nickel (HMI) in the Ellipsometric measurements.
I am also grateful to all the researchers at HMI: Dr. R. Klenk, Dr. S. Bakehe, Dr. R.
Mainz, Prof. S. Siebentritt, Dr. N. Papathanasiou, and Dr. Ch. Kaufmann for the samples studied
and relevant information provided.

Last, but not least, I ought to thank the members of my group, K. Anestou and N.
Karkatzinou for the pleasant environment and our harmonic cooperation, which enhanced our
friendship and of course my family and friends for their ever-lasting approval of my choices.

This work has been co-funded by the European Social Fund (75%) and National
Resources (25%) in the frame of the Scientific program EPEAEK II-Herakleitos-Research
Scholarships in the National Technical University of Athens (Fundamental Research).
Scientific exchange visits to HMI and TU-Berlin have been financially supported by
DAAD (German Academic Exchange Committee) and the Erasmus-Socrates Co-operations
Agreement.

iii
ABSTRACT

In the frame of the present PhD thesis, homo- and heterojunction solar cells based on
chalcopyrite absorbers are investigated with emphasis given on the improvement of the structural
and optical properties of the absorber layer and the replacement of the CdS-buffer layer by the
more environmental friendly ZnSe buffer.
In particular, the optical band gaps and the lattice defects of ternary CuInS
2
(CIS) and
CuGaSe
2
(CGS) and quaternary CuIn
1-x
Ga
x
S
2
and CuIn
1-x
Ga
x
Se
2
(CIGS) chalcopyrite
compounds are investigated as well as a possible substitution of the CdS by a ZnSe buffer.
The CIS and CIGS absorbers are analyzed as independent components of the
heterostructures using Photoreflectance (PR) and Raman Spectroscopy at room temperature (RT)
and/or low temperatures (20 K), and also as the most important component of solar cell devices
using Electroreflectance (ER) Spectroscopy at RT. The band gaps of the CIGS quaternary
compounds determined by PR, ER, and complementary spectroscopic Ellipsometry techniques
depend on the absorber composition (% Ga) and vary in their energies between the band gaps of
the corresponding ternary end-members: CuInSe
2
or CuInS
2
(CIS) and CuGaSe
2
or CuGaS
2

(CGS).
The low temperature fundamental band gaps of CuIn
1-x
Ga
x
Se
2
(CIGS) are determined
for a large composition range, for the first time, in this thesis. Evaluation of the ER spectra of
CIGS solar cells at RT gives, apart from the absorber band gap energy, the residual elastic
stresses due to the lattice mismatch or/and the different thermal expansion coefficients of the
different components of the heterostructure. The strain evolution in the absorber layers has been
analysed with respect to the band separation and was found to be smaller than 1% (0.50.8%).
Modulation spectroscopy is proven to be a highly sensitive tool for structural and optical
analysis. The higher band gaps of the CIGS absorbers are obtained indirectly using
Spectroscopic Ellipsometry (SE) at RT. Evaluation of the Raman spectra recorded at RT results
in a linear shift of the A
1
mode of the CIGS layers with the composition. By combining the PR-
and the Raman- results, an analytical expression has been derived which correlates the band gap
energy with the Raman frequency of the A
1
-mode for a given composition of the quaternary
compound.
The lattice defects of CIGS layers have been studied by Photoluminescence (PL) and
Photoluminescence Excitation (PLE) Spectroscopy at 7 K. The emission of two different PL
bands for the layers with intermediate Ga-contents (x=0.33 and 0.60) is associated with the
presence of two different phases in these films. PLE studies the incorporation of defects in the
quaternary alloy system by recording the luminescence signal with the detection energy set

iv
alternately to the PL band maximum and its flanks. By combining the PL, the PLE, and the PR
results at low temperatures, down to 2 K, the energies of the donor and acceptor states
contributing to the luminescence mechanism of the CIGS layers are determined.
Moreover, the preparation of homojunction cells based on CGS absorbers, which are p-
type semiconductors by inverting the surface conductivity of the absorber layer using Ge-ion
implantation (in three- and one- stages) is investigated. The n-CGS/p-CGS/Mo/glass structures
are studied by PL spectroscopy at 2 K and RT and by Raman spectroscopy at RT. Both PL and
Raman analysis support an increased structural disorder of the films subjected to the one-stage
Ge-implantation process.
In general, the present PhD-thesis contributes to the optimisation of CIGS heterojunction
solar cell device performance and the development of CGS homojunction solar cell technology.

v

TABLE OF CONTENTS

Page
1. INTRODUCTION 1
1.1 Photovoltaics (PVs)-Solar Cells 1
1.2 p-n junction and Photovoltaic (PV) effect 5
1.3 Thin-film solar cells (TFSCs) 11
1.4 Chalcopyrite-based solar cells 13

2. BULK CHALCOPYRITES 16
2.1 Physical Properties 16
2.1.1 Structure 16
2.1.2 Phase diagrams 18
2.1.3 Lattice defects 22
2.1.4 Lattice vibrations 23
2.2 Dielectric function- refractive indices 28
2.3 Electronic properties 29
2.4 Optical properties 32

3. CHALCOPYRITE HOMO- AND HETEROSTRUCTURES 36
3.1 Heterostructures 36
3.1.1 Band offset: band-alignment 36
3.1.2 Mismatch strain and thermal strain 40
3.2 Homostructures 42

4. GROWTH TECHNIQUES 45
4.1 MOVPE grown CuIn
1-x
Ga
x
Se
2
epitaxial layers (x=0.08 - 0.82) 45
4.2 PVD grown CuIn
1-x
Ga
x
S
2
polycrystalline films (x=0.00, 0.04, 0.12) 46
4.3 CdS/CuIn
1-x
Ga
x
S
2
/Mo/glass

and ZnO/CdS/CuIn
1-x
Ga
x
S
2
/Mo/glass 47
heterostructures
4.4 Solar cells based on CuIn
1-x
Ga
x
S
2
absorbers 47
4.5 CCSVT grown CuGaSe
2
films and Ge-doped CuGaSe
2
films 48
4.6 ZnSe/CuGaSe
2
/Mo/glass heterostructrures 50
4.7 PVD grown CuIn
1-x
Ga
x
Se
2
polycrystalline films and solar cells 51

5. SPECTROSCOPIC ANALYSIS TECHNIQUES 53
5.1 Spectroscopic Ellipsometry (SE) 53
5.2 Modulation spectroscopy: Photo- and Electroreflectance (PR&ER) 55
5.2.1 Modulation spectra and the dielectric function 57
5.2.2 Photoreflectance-spectra in the low-field regime 59
5.2.3 Temperature dependence of transition-energies 60
5.3 Photoluminescence (PL) spectroscopy 61
5.3.1 Photoluminescence emission 61
5.3.2 Photoluminescence from semiconductors 63
5.4 Photoluminescence Excitation (PLE) spectroscopy 65
5.5 Raman spectroscopy 66
5.5.1 Theory of Raman scattering in molecules 66
5.5.2 Raman tensors in solids 68

vi
6. EXPERIMENTAL 70
6.1 Experimental set-ups 70
6.1.1 Photoreflectance (PR) and Electroreflectance (ER) spectrometer 70
6.1.2 Raman spectrometer 71
6.1.3 Photoluminescence (PL) and Photoluminescence Excitation (PLE)
spectrometer
72

6.1.4 Spectroscopic ellipsometers (SE) 73

7. RESULTS AND DISCUSSION 75
- CHALCOPYRITE SELENIDE HETEROSTRUCTURES 75
Epitaxial layers
7.1 (RT&LT) Study of CuIn
1-x
Ga
x
Se
2
epitaxial layers by Photoreflectance
(PR) spectroscopy
76
7.2 (RT) Study of CuIn
1-x
Ga
x
Se
2
epitaxial layers by Raman spectroscopy 82
7.3 (LT) Study of CuIn
1-x
Ga
x
Se
2
epitaxial layers by Photoluminescence
Excitation (PLE) spectroscopy
90
1-x
Ga
x
Se
2
epitaxial layers by spectroscopic
Ellipsometry (SE)
119
Polycrystalline thin films and solar cells
1-x
Ga
x
Se
2
polycrystalline films and solar cells by
Photoreflectance and Electroreflectance spectroscopy
129
7.6 (RT) Study of ZnSe/CuGaSe
2
/Mo/glass heterostructrures by
Photoreflectance spectroscopy
140
- CHALCOPYRITE SELENIDE HOMOSTRUCTURES 141
7.7 Raman (RT) and PL-study (RT&LT) of as- grown and Ge-doped CuGaSe
2

films
141
- CHALCOPYRITE SULFIDE HETEROSTRUCTURES 149
1-x
Ga
x
S
2
polycrystalline films and CuIn
1-x
Ga
x
S
2
/CdS
and CuIn
1-x
Ga
x
S
2
/CdS/ZnO heterostructures by Photoreflectance
spectroscopy
149
7.8.1 CuIn
1-x
Ga
x
S
2
polycrystalline films 149
7.8.2 CuIn
1-x
Ga
x
S
2
/CdS and CuIn
1-x
Ga
x
S
2
/CdS/ZnO heterostructures 152
1-x
Ga
x
S
2
1-x
Ga
x
S
2
/CdS
and CuIn
1-x
Ga
x
S
2
/CdS/ZnO heterostructures by Raman spectroscopy
156
1-x
Ga
x
S
2
based solar cells by Electroreflectance (ER)
spectroscopy
161

8. CONCLUSIONS 170

9. REFERENCES 175

1
1. INTRODUCTION

1.1 Photovoltaics (PVs)-Solar Cells

Photovoltaic materials (PVs) are inorganic semiconductors, which form suitable junctions
with other materials and exhibit a photovoltaic effect (see 1.2) when exposed to light. The
Photovoltaic (PV) Technology was based on science that began with Alexandre Edmond
Becquerels discovery of light-induced voltage in electrolytic cells over 150 years ago. However,
significant development really began following Bell Labs invention of the silicon (Si) solar cell in
1954. PVs first major application was to power manmade earth satellites in the late 1950s, an
application where simplicity and reliability were paramount and cost was nearly ignored. Enormous
progress in PV performance and cost reduction, driven at first by the U.S. space programs needs,
has been made over the last 40-plus years. Since the early 1970s, private/public sector collaborative
efforts in the U.S., Europe, and Japan have been the primary technology drivers. Data reported for
the period 1990-2005 (Fig. 1.1.1) show a tremendous increase of the worldwide cell/module
production [1.1].

Fig. 1.1.1 World cell/module production, consumer and commercial, 1990-2005 (MW) [1.1].
The best worldwide Photovoltaic Companies in 2005 are given in Fig. 1.1.2. It is evident
that, on the world market share of photovoltaic devices, four of the Top Ten companies are
Japanese.

2

Fig. 1.1.2 Top 10 Photovoltaic companies in 2005 (total shipments in 2005: 1759 MW) [1.1].
Please note that BP Solar, Schott Solar and Shell Solar have cell production capacities in
more than one country.

In Europe, the support measures for Photovoltaics in the European Union Member States
were determinative in the development of photovoltaic technology. In 2006, 15 out of the 25
Member States had already introduced in their national law what is known as feed-in tariff,
concerning the PV-prices in /kWh. Only in those countries in which the tariff has been high, and a
set cap realistic enough, have PV installations increased and competition in production and trade
developed substantially. From the socio-economic data at hand, feed-in tariffs should be designed to
potentially enable a pay-back of the initial investment within 10 to 12 years and should be combined
with a built-in sun-set. Such a decrease of the guaranteed tariff by a certain percentage each year
compensates early technology users, enforces realistic price reductions if well designed, and offers a
long-term perspective for investors and producers of solar systems [1.2].
Stable political and socio-economically viable frame conditions do not only convince private
and commercial investors to install photovoltaic power plants, but also stimulate the investment in
new production capacities for solar cells and modules. Especially in Germany and Spain, the most
dynamic markets in Europe, the production capacities for solar cells and modules have increased
faster than in the other European countries (Fig. 1.1.3).

3

Fig. 1.1.3 Annual production of the European PV manufacturers with sales larger than 10 MWp in
2005 [1.1].

As reported in Marketbuzz 2007 [1.3], the world production of photovoltaics (PVs) in 2006
grew 41% to 2,520 megawatts (MW) (Fig. 1.1.4). That correlated to the installation of 1,744 MW
worldwide, an increase of 19%. The PV-production in 2006 was dominated by Japan, which
accounted for 37% of all manufactured cells. However, Germany still dominated installations with
960 MW, or 55% of the world total. Japan and Germany, the manufacturing and installation leaders,
respectively, are no longer guaranteed their spot at the top. They must now fight to maintain their
positions. Japan's output of solar modules actually shrunk in the last year- it lost 7% of its market
share -while U.S. production rose 30% and Europe's 42%. In Spain, installations were up over
200%.
It is predicted that Italy will move into the top three for installed capacity in the next three
years, with Turkey and Greece also coming on strong. The potential in the developing world is not
to be ignored either.

4

Fig. 1.1.4 PV installations in 2006 (ROW and ROE stand for Rest of the World and Rest of
Europe, respectively) [1.3].

Concerning the materials used in the solar cell technology, the workhorse of the photovoltaic
industry over the past decades is bulk crystalline silicon solar cells (Fig. 1.1.5). The main reason is
that silicon technology had been highly developed before the advent of photovoltaics and high
quality material had been already produced in large quantities for the microelectronic market.
Recent investments in research and development of monocrystalline and multicrystalline silicon
wafer-based technologies as well as for related silicon ribbon and sheet approaches ensure this role
will last for a while. However, the silicon wafer-based approach has to withstand the challenge made
by thin-film polycrystalline cells of CdTe and Cu(In,Ga)Se
2
as well as thin-film cells based on
amorphous silicon and its alloys. Currently all silicon technologies have market share at the level of
about 97%. The remaining 3% is divided between thin films not involving silicon, especially cells
based on the chalcogenides Te and Se in the form of polycrystalline thin-films of CdTe and CuInSe
2

(CIS). In fact, the great ultimate cost of the silicon technology has been always an important
drawback: with respect to single crystal Si technology, the most important factor in determining the
cost of production is the cost of the 250300 m-thick Si wafer used for the fabrication of solar
cells. Unless a much thinner wafer, and thus less amount of Si, is used and the production process is
made cheaper and simpler, any further decrease in Si cells cost will be only by small increments
[1.4].

5
Which cell(s) and which technologies will ultimately succeed commercially continue to be
anybodys guess, but it would surely be determined by the simplicity of manufacturability and the
cost per reliable watt.

Fig.1.1.5 Market shares of different photovoltaic materials [1.5].

1.2 p-n junction and Photovoltaic (PV) effect

- p-n junction

In intrinsic semiconductors, both type of carriers, electrons and holes, are equal in quantity.
For applications, semiconductors are dominated by only one type of carrier by doping. The n-type
semiconductor is doped with donor impurities, and the p-type semiconductor with acceptor
impurities. Most semiconductor devices contain at least one junction between p-type and n-type
semiconductor regions. When one p-type and one n-type semiconductor are brought into contact, a
p-n junction is formed (Fig.1.2.1).

6

Fig. 1.2.1 Schematic diagram of a p-n junction

The actual p-n junction may be formed from a single crystal semiconductor in which one
region is doped p-type and the adjacent region is n-type. Initially, without a potential between the p-
and n-type regions, a great density gradient in both, electron and hole concentrations, exists at the
interface. The diffusions of electrons from n-type to p-type and holes from p-type to n-type induce
an electric field in the space charge region (or depleted region) near the junction. In this way, the
system is brought into equilibrium where no current exists. A distinct character of a p-n junction is
that it will conduct current in the forward direction but not in the reverse direction.
If a forward-bias voltage is applied across the p-n junction (p-region positive with respect
to the n-region), see Fig.1.2.2, the majority of electrons from the n-side are injected across the space
charge region into the p-material, and holes from the p-side are injected into the n-material. As long
as the potential is applied, the injection of carriers continues and a current is created in the p-n
junction. If a reverse-bias voltage (n-region positive with respect to the p-region) is applied to the
p-n junction, the total potential barrier is increased. This results in no diffusion of carriers, thus there
is no or little current [1.6].

7

Fig. 1.2.2 Forward- and reverse-biased p-n junction

- Photovoltaic effect

With zero bias applied to a p-n junction connected with a resistance R as shown in Fig.1.2.3,
an electric field is built in the space charge region. Incident photon illumination can create electron-
hole pairs (EHPs) in the space charge region of the junction. Under closed circuit conditions, the
minority carriers, if generated within a certain distance of the junction (called a diffusion length),
can diffuse to the junction, be swept to the other side, producing the photocurrent
L
I in the reverse-
bias direction (from the n- to the p-side), and be collected by appropriate contacts [1.6]:
E-Field
I
L
hv
I
I
F
+ V -
R
n P

Fig. 1.2.3 A p-n junction solar cell with resistive load [1.7].

The photocurrent
L
I produces a voltage drop V across the resistive load R , which forward
biases the p-n junction. The forward-bias voltage V produces a forward-bias current (from the p-
to the n-side)
F
I :

8

|
|
\
|
|
|
\
|
= 1
T k
eV
exp I I
B
S F
, (1.2.1)
where
S
I is the reverse-bias diode saturation current; e, k
B
, and T are the electron charge, the
Boltzmann constant and the temperature, respectively. The net p-n junction current, in the reverse-
bias direction, is:

(
|
|
\
|
= = 1
T k
eV
exp I I I I I
B
S L F L
, (1.2.2)
The photocurrent
L
I is always in the reverse-bias direction.
- In a short circuit condition (R=0), V=0 and the current is called short-circuit current
sc
I :

sc L
I I I = = . (1.2.3)

- In an open-circuit condition ( R ), I=0 and the voltage is referred to the open-circuit
voltage
oc
V , that is:
0 exp 1
oc
L S
B
eV
I I I
k T
( | |
= =
( |
\
, (1.2.4)
ln 1
L
oc t
S
I
V V
I
| |
= +
|
\
, (1.2.5)
where
e
T k
V
B
t
= is the thermal voltage [1.7].
A plot of the diode current density J as a function of the diode voltage V, known as I-V
characteristic, in the dark and under illumination, is shown in Fig.1.2.4.
The details of the electrical behavior depend on the type of cell and the properties of the
material. The efficiency of the cell can be expressed in terms of the short circuit current (
sc
I ) and
the open circuit voltage (
oc
V ) of the device, once the fill factor ff is defined [1.6]:

m m
sc oc
I V
ff
I V
= (1.2.6)

Here
m
V and
m
I represent the voltage and the current for the conditions of maximum output power
of the device, as shown in Fig. 1.2.4. Therefore, the cell conversion efficiency or efficiency ,
defined as the ratio of the generated power with respect to the power of the incident radiation output
(
in
P ), may be written as:

9

100% 100% 100%
m m m sc oc
in in in
P I V I V ff
P P P
= = = (1.2.7)

Fig. 1.2.4 Schematic illustration of the current density-voltage characteristics of a solar cell in the
dark and under illumination. Indicated are the short-circuit current density
sc
J , the open-
circuit voltage
oc
V , and the maximum power point ( , )
m m
V J [1.7].

The integrated power of the incident light depends on the angle of incidence of the radiation
and on the atmospheric conditions. These differences are taken into account by defining the air
mass (AM) conditions at a concrete location. The AMm factors have been defined by the IEEE
Standard Dictionary of Electrical and Electronics Terms as the mass of air between a surface and the
sun; m=1/cos is the air mass number and thus measures the atmospheric path length relative to path
length when the sun is directly overhead. The air mass affects the spectral distribution and intensity
of sunlight [1.8]. Under AM0 conditions (normal incidence without atmosphere) the value of the
integrated incident power is 137 mW/cm
2
, and this value decreases to about 100 mW/cm
2
on the
surface of the Earth under AM1.5 conditions. AM1.5 spectral distribution is at the time the most
widely used terrestrial standard, corresponding to = 48 [1.9].
All solar cells can absorb sunlight and consequently radiate light. However, the efficiencies
of real solar cells cannot by no means reach the 100 % of sunlight photon energy conversion into

10
electricity; there are many extrinsic limitations including losses due to reflection, contact,
shadowing, series resistance, incomplete collection of photogenerated carriers, absorption in inactive
window layers, nonradiative recombination and above ambient cell temperature. Even if these losses
are eliminated, there remain two intrinsic losses, which then determine the efficiencies of ideal
solar cells:
1) losses because of the inability of a single energy gap solar cell to properly match the broad
solar spectrum. If the solar spectrum is approximated by a black body of 5900 K which results in a
very broad spectrum ranging from the ultraviolet to the near infrared, then, the curve of efficiency
versus semiconductor bandgap goes through a maximum, as shown in Fig. 1.2.5 [1.10]. Solar
photons with energies h less than the energy gap
g
E are not absorbed and solar photons with
g
E h generate electron-hole pairs, which immediately lose almost all energy in excess of
g
E
and,
2) losses due to radiative recombination [1.11], [1.12].

Fig. 1.2.5 Dependence of the conversion efficiency on the semiconductor bandgap [1.10].

11
1.3 Thin-film solar cells (TFSCs)

A large number of semiconductor materials show a PV effect, but only a few of these are of
sufficient commercial interest because they must satisfy the constraints for minimizing thickness
and wide availability. Ideally, the absorber material of an efficient terrestrial solar cell should be a
direct bandgap semiconductor with a bandgap of ~1.5 eV with a high solar optical absorption
(~10
5
cm
-1
), high quantum efficiency of excited carriers, long diffusion length, low
recombination velocity, and should be able to form a good electronic junction
(homo/hetero/Schottky) with suitably compatible materials.
With high optical absorption, the optimum thickness of an absorber in a solar cell is of the
order of the inverse of the optical absorption coefficient and thus it must be a thin-film material,
in the sense that only about 1 m of active material is required [1.4].
Silicon (Si), dominating the today market, is an indirect bandgap material with a gap ~1.1
eV; it is though by no means an ideal material. This has serious consequences from a materials point
of view: for a 90% light absorption it takes only 1 m of GaAs (a direct semiconductor) versus 100
m of Si. The photogenerated carriers have to reach the pn-junction, which is near the front surface.
The diffusion length of minority carriers has to be 200 m or at least twice the silicon thickness.
Thus, the material has to be of very high purity and of high crystalline perfection. In view of these
physical limitations it is quite surprising that silicon has played such a dominant role in the market.
The main reason is that silicon technology has already been highly developed before the advent of
photovoltaics and high quality material is being produced in large quantities for the microelectronics
market [1.10].
In fact, there is quite large number of possible and viable thin film materials for solar cells,
well known as Thin Film Solar-Cells, TFSCs. Some of the most attractive candidates, based on a-
Si:H, CdTe and CuInSe
2
(CIGS) materials have been the subject of intense R&D and exploration of
manufacturing technologies for the last three decades.
The best, till now, research PV cell-efficiencies, reported by the National Renewable Energy
Laboratory (NREL) in U.S.A., are shown in Fig. 1.3.1 [1.13].

12

Fig. 1.3.1 The Best Research-cell efficiencies (NREL).

13
1.4 Chalcopyrite-based solar cells

Chalcopyrites of type Cu(In,Ga)(S,Se)
2
(CIGSS) are ideal candidates for thin-film solar cells
(TFSCs): They have direct band gaps and optical absorption coefficient >10
5
for photons with energy
above their band gap and require a thickness of only 1 m for almost complete absorption of relevant
solar spectrum. It is essential to employ a heterojunction partner with high bandgap toward the light-
incident side so as to minimize the loss of photogenerated charge carriers. A solar cell based on a
Cu(In,Ga)Se
2
(CIGS) absorber (Fig. 1.4.1) has, usually, the following layer sequence [1.14]: Glass,
stainless steel, or titanium foils are used as substrates. A molybdenum layer is used as a back contact
because it can withstand the harsh conditions much better compared to the conventional contact
materials aluminum, gold, copper, and silver. Besides it does not add n-type dopants to compensate p-
type doping of CIGS. Molybdenum layers are usually deposited by dc-magnetron sputtering.
Inadvertent addition of minute amounts of sodium (Na) from the substrate, diffusing through the Mo
film, has been found to improve crystallographic properties and doping in CIGS films. However, the
properties deteriorate in regions with excessive amounts of sodium diffusing through grain boundaries
and through defects in the Mo films in localized regions. Therefore, it is customary to minimize Na
outdiffusion by providing a thin buffer layer between the glass substrate and the molybdenum film and
adding an optimum, minute amount of Na by depositing a very thin layer of a sodium compound such
as NaF.

Fig. 1.4.1 Layer sequence of CIGS thin film solar cells.

The absorber film can be deposited using various methods: The most successful technique for
highest-efficiency CIGS cells is the simultaneous evaporation of the constituent elements from multiple
sources in single or sequential processes, where Se is offered in excess during the whole deposition

14
process. The variation of the Cu content strongly affects the film growth so, in most cases a
homogenous Cu distribution throughout the layer is established. Alternately, sequential processes,
presented in Fig.1.4.2, are used, especially in case of large-area film deposition with good control of
the composition and film thickness. Such processes consist of the deposition of a precursor material,
followed by thermal annealing in controlled reactive or inert atmosphere for optimum compound
formation via the chalcogenization reaction.

Fig. 1.4.2 Schematic of the various processes for selenization of precursor materials [1.15].

The heterojunction partner layer, the n-type layer, which is known as buffer layer, is usually
CdS prepared by Chemical Bath Deposition (CBD). Because of concerns with small amounts of
cadmium, Cd free buffer layers are being developed, even though the CdS layer is only ~50 nm thick.
The alternative materials being studied are ZnInSe
x
, In
x
Se
y
, ZnMgO, SnO
2
, and SnS
2
, or compounds
based on ZnS, ZnSe, In(OH)
3
, and In
2
S
3
, The best efficiencies reported on Cd-free buffer layers are
18.6% for ZnS-based layer deposited by CBD [1.16]. On top of the buffer layer, a ZnO/ZnO:Al
window bilayer is deposited as a Transparent Conducting Oxide (TCO); it is deposited by rf or dc
magnetron sputtering, MOCVD techniques etc. A deposition process that results in minimum damage
during the preparation of the window layer is the pulsed dc sputtering. This method can provide very
uniform, high-quality films at high deposition rates, high throughput, and yield, combined with
efficient production, system flexibility, lower upfront costs and reduced substrate damage and target
contamination. As a front contact, a grid made from a nickel aluminium (Ni/Al) bilayer is finally

15
deposited. The Ni/Al grid is there mainly for laboratory use in order to facilitate contacting the solar
cell for characterizing purposes. In modules, it will be omitted and replaced by a more suitable
structure for the whole layer pattern.
In the photovoltaic modules, three laser or mechanical scribing steps are employed, generally,
to define, interconnect and isolate the cells. The manufacturing of thin-film modules can include
monolithic interconnection, being an advantage over crystalline silicon modules. The first scribe is
applied on the molybdenum back-contact layer using a laser scriber and is followed by a mechanical
scribing of CIGS, CdS and ZnO layers. The third scribe takes place again with a mechanical scriber
after deposition of the ZnO:Al layer. In this fashion, the TCO layer of one cell is connected to the
metallic back-contact layer of the adjacent cell, thus adding the voltage of cell strips [1.14].
The highest efficiencies of chalcopyrite-based solar cells, recently reported, are accumulatively
shown in Table 1.4.1. The best efficiency of 19.5% has been achieved with polycrystalline CIGS films
deposited by coevaporation [1.17].

Table 1.4.1 Actual efficiencies (total area) for the most common Cu chalcopyrite solar cells

Absorber Energy gap
(eV) (300 K)
Actual efficiency

CuInSe
2
1.05 13.5 % [1.18]
Cu(In,Ga)Se
2
(CIGS) 1.2 19.5 % [1.17]
CuInS
2
1.5 11.4 % [1.19]
Cu(In,Ga)S
2
(CIGS) 1.53 12.3% [1.20]
CuGaSe
2
1.7 9.3 % [1.21]

Wide gap materials such as CuInS
2
and CuGaSe
2
and solar cells based on these materials have
reached only the half of the efficiency of CIGS solar cells, so far. Part of the reason for this inferior
behavior is the technological head start of CIGS, which has been studied more intensively and for a
longer period of time. However, there are basic differences in the behavior of volume doping, of
recombination, and of interface formation between the wide gap materials and Cu(In,Ga)Se
2
[1.22].
Some of the material- and growth- related problems affecting the performance of the different
chalcopyrite-based solar cells, will be discussed in the main part of this thesis. Proper understanding of
thin-film deposition processes and material (structural and optical) properties can help in achieving
high-efficiency devices over large areas, as has been demonstrated commercially for different cells.
Research and development in new, exotic and simple materials and devices, and innovative, but simple
manufacturing processes need to be pursued in a focused manner. Cheap and moderately efficient
Thin Film Solar Cells (TFSCs) are expected to receive a due commercial place under the sun.

16
2. BULK CHALCOPYRITES

2.1. Physical Properties

2.1.1 Structure

Chalcopyrite (CH) is a copper iron sulfide mineral that crystallzes in the tetragonal
system; it has the chemical composition CuFeS
2
. In general, the ternary compound
semiconductors of type A
I
B
III
2
VI
or I-III-VI
2
or ABX
2
with =Cu,Ag, B=Al,Ga,In,Tl, =S,Se,Te
crystallize in the chalcopyrite structure. This is an isoelectronic analog of the II-VI binary
compound semiconductors having the well-known zinc-blende (ZB) structure. The crystal
structure of the ternary chalcopyrites belongs to nonsymmorphic space group
12
d 2
D (eight atoms
per primitive unit cell, Fig. 2.1.1a), which is a superlattice of zinc-blende structure
2
d
T (two
atoms per primitive unit cell, Fig. 2.1.1b) [2.1], [2.2]. One can define a binary analog to each
ternary compound by taking the cation that is situated in the Periodic table between the A and B
atoms (e.g. ZnS is the binary analog of CuGaS
2
or Zn
0.5
Cd
0.5
S is the binary analog of CuInS
2
).
Despite the overall structural similarity between the ternary I-III-VI
2
compounds and their II-VI
binary analogs, the band gaps of the former compounds are substantially smaller than those of
the latter (by amounts of up to 1.6 eV in case of CuInSe
2
[2.3]). This strong red shift of the
ternary band gap makes some of the AB
2
compounds such strong absorbers of sunlight [2.4]
(see Fig. 2.4.1). The difference between the binary gap and the ternary gap is known as the
band-gap anomaly
g
and has been assigned to: a chemical factor
chem
g
E and a structural
factor
S
g
E .
chem
g
E is controlled by a p-d hybridization effect, described in 2.3, and, by a
cation electronegativity (CE) effect. The CE term reflects the fact that in a chalcopyrite structure,
e.g of type CuBX
2
, even if the d-electrons of the Cu
I
-atom, were chemically inactive, charge
could separate differently on the two dissimilar cations (Cu, B) thereby affecting the bandgap. In
ternary chalcopyrites, the CE contribution to
g
are ~0.1-0.2 eV, and thus much smaller than
the p-d hybridisation contribution and the structural contribution
S
g
E .
S
g
E concerns the
existence of bond alteration (
BX AX
R R ) in the ternary chalcopyrite system, compared to the
binary analog (see Fig. 2.1.1) [2.4], manifested by the non-ideal anion displacement 1/ 4 0 u ,
as discussed in the following:

17

Fig. 2.1.1 Crystal structure of a) chalcopyrite (CH) and b) zinc-blende (ZB) lattices [2.4].

In a ternary chalcopyrite ABX
2
, there are three significant structural differences with
respect to the zinc-blende structure: 1) there are two cation sublattices rather than one; starting
from the A atom and translating in the vertical direction in Fig. 2.1.1a) through intervals of c/2
we find the sequence ABAB, whereas translating horizontally with an interval of a we find the
sequence AAA, 2) the unit cell is tetragonally distorted with a distortion parameter
1 a 2 c (tetragonal deformation), which differs from 1 by as much as 12%, and 3) the
anions are displaced from the ideal tetrahedral (zinc-blende) site by an amount u (anion
displacement). This reflects the fact that in binary AX zinc-blende each cation A has four anions
X as nearest neighbors (and vice versa), whereas in a ternary chalcopyrite ABX
2
each cation A
and B has four anions X as nearest neighbors, and each anion has two A and two B cations as
nearest neighbors.
As a result, the anion X usually adopts an equilibrium position closer to one pair of
cations, leading to unequal bond lengths
BX AX
R R (bond alteration). The two near-neighbor
bond distances are given by [2.1]:

1
2 2
2
[ (1 ) /16]
AX
R a u = + + (2.1.1)
and
1
2 2
2
[( 1 2) (1 ) /16]
X
R a u
= + + (2.1.2)
where a is the cubic lattice constant. Hence, the anion displacement u is given by:

2 2 2
1 4 ( ) /
AX BX
u R R a = (2.1.3)

18
and measures the extent of bond alteration in the system. For a zinc-blende undistorted anion
sublattice, 1 4 u . Table 2.1.1 gives a compilation of the experimental data for , , a u of ternary
Cu
I
-chalcopyrites [2.4]. It should be noted that the structural anomalies -1 and u-1/4 of the
chalcopyrites, relative to the zinc-blende structure (=1 and u=1/4) are significant.

Table 2.1.1 Experimental structural parameters a and c (lattice constants, measured in ),
u (anion displacement) and 2 / c a (tetragonal deformation) for the ternary
2
system [2.4].

Chalcopyrite a () c () 2 / c a u
calc
u

CuInSe
2
5.784(1) 11.616(5) 2.008 0.224(3) 0.237
CuGaSe
2
5.614(1) 11.03(1) 1.965 0.250(1) 0.264
CuInS
2
5.523(4) 11.12(2) 2.013 0.214(7) 0.236
CuGaS
2
5.356(1) 10.435(5) 1.948 0.275(5) 0.264

In the case of CuGaSe
2
, for instance, the lattice constants are a=b=0.5612 nm and c=1.1032
nm. Each of the metal atoms is coordinated by four Se atoms, whereas each Se atom is
coordinated by two Cu atoms and two Ga atoms. There are no Cu-Ga bonds. Since each one of
the sublattices contains a different kind of cations, the unit cell doubles with respect to the zinc-
blende unit cell [2.1].

2.1.2 Phase diagrams

The phase diagrams of related pseudo-binary systems such as Cu
2
S-In
2
S
3
or Cu
2
Se-
In(Ga)
2
Se
3
(Figs. 2.1.2a), b) and c)), show either a congruent or an incongruent melting behavior
of the chalcopyrite phase as well as solid-solid-phase transitions. Studying the phase relations
of CuInS
2
, the pseudo-binary cut Cu
2
S-In
2
S
3
- shown in Fig. 2.1.2a), adapted from [2.5] -
includes two solid-solid phase transitions.
Passing the liquidus from the melt, the material first crystallizes in a wurtzite-like
structure at 1090 C. At the solid-solid phase transition at 1047 C, the wurtzite-type phase
converts into the sphalerite structure. Below 983 C, the room temperature modification of a
chalcopyrite-type (CuInS
2
, -phase) structure is formed. The homogeneity region at room
temperature for CuInS
2
itself, has appeared to be confined to the region 50-52 % mol % In
2
S
3
. In
fact, the homogeneity ranges for both CuInS
2
and CuGaS
2
sulfides, seem to be more narrow, e.g.
smaller than < 1 mole % (see [2.6], [2.7]). The second semiconductor, CuIn
5
S
8
, has the spinel
structure over the whole temperature range of 20
o
C

to the melting point at 1085 C.

19
In the ternary system involving Cu, In(Ga) and S, an excess of copper and sulfur
would promote the formation of a phase primarily involving these two elements [2.8] [2.9]:
Cu
x
S, in the bulk form, is known to exist in five stable phases in the room temperature
range with chalcocite or digenite (orthorhombic Cu
2
S) on the copper rich side and covellite
(CuS) on the copper deficient side. Mixed phases are known to exist at intermediate
compositions [2.10]. The crystal structure of CuS, or covellite, is hexagonal (space group 194,
P63=mmc). According to Wyckoff [2.11] a = 3.796 and c =16.36 and the unit cell contains
six formula units with two inequivalent sites for both Cu and S. Two thirds of the sulfur atoms in
CuS form dimers, while the remaining S atoms are single [2.12]. In fact, the binary phase
diagram involving Cu and S elements suggests the formation of chalcocite Cu
2
S, at growth
temperatures and the formation of covellite, CuS, at room temperature. The expected lines from
a powdered sample of covellite agree with those present in the XRD spectra of Cu-rich CuGaS
2
layers, but unfortunately, a number of these reflections coincide with those attributed to CuGaS
2
.
This creates some uncertainty as to the extent of CuS present. Expected lines from a powdered
sample of chalcocite do not match up with reflections in the XRD spectra of Cu-rich CuGaS
2

films, and although it is likely that the chalcocite phase forms during growth, it re-crystallises
into the covellite phase upon cooling [2.9]. The optical band gap, E
g
, of the Cu
x
S material is
known to vary with x; CuS shows an indirect gap of 1.55 eV [2.10]. The Cu chalcogenide
phase formed on top of Cu-rich chalcopyrite films can be effectively removed from the front
surface of the as-deposited films by etching in a chemical bath containing a 10% potassium
cyanide solution [2.13]. According to the pseudobinary Cu
2
SIn
2
S
3
phase diagram, (Fig. 2.1.2a))
the In-rich (Cu-poor) compositions correspond to >52 mol % In
2
S
3
.
In general, a Cu deficit (x>0 in the general formula Cu
1-x
In
1+x/3
X
2
) in CuInX
2
(X=S, Se,
Te) could be accommodated within the structure by a combination of
3
Cu
In
+
antisites and Cu
vacancies
Cu
V
according to the formula 3[Cu

1-x
In
1+x/3
X
2
]=Cu
3
+
[V
Cu
-
]
3x
In
3
3+
[In
Cu
3+
]
x
X
6
2-
. If the
impurities
3
Cu Cu
In V
+
+ order in a specific manner, compounds like CuIn
3
X
5
or CuIn
2
X
3.5
may
result where the former has been prepared with X=Se and the latter with X=S, Se, Te [2.8]. The
existence of such ordered compounds has been attributed by Zhang et. al. at the low defect
formation energies of defect pairs such as
2
( 2 )
Cu Cu
In V
+
+ and
2 2
( 2 )
Cu In
In Cu
+
+ in the CuInSe
2

compound [2.14], [2.15]. The defect physics in the chalcopyrite system is discussed in detail in
2.1.3.
The Tx diagram for the Cu
2
SeIn
2
Se
3
pseudobinary system for the range between 47
and 100 %, is shown in Fig. 2.1.2b) and is described in Ref. [2.16]; the full stoichiometric range

20
was later on assessed [2.17]. At 750
o
C the homogeneous region of ordered CuInSe
2
with
chalcopyrite structure (-phase) extends from 47.5 to 55.0 mol % In
2
Se
3
[2.16].
On the Cu-rich side of the phase diagram, CuInSe
2
coexists with the Cu-rich phase
Cu
2x
Se. As Cu
2x
Se is metallic in nature, Cu-rich compositions are avoided in solar cell
fabrication due to the formation of Cu
2x
Se shunt paths along CuInSe
2
grain boundaries,
which reduce cell performance. On the Cu-poor (In-rich) side of the phase diagram, there is
no clear phase boundary observed implying a variety of vacancy-stabilized chalcopyrites may
exist (e.g. CuIn
3
Se
5
, CuIn
5
Se
8
) [2.18].
The CuGaSe
2
phase-diagram is shown in Fig. 2.1.2c) [2.19], with the crystal phase
(Cu
2
Se)
1-x
(Ga
2
Se
3
)
x
existing between 1 0 x . As in the case of the Cu
2
Se-In
2
Se
3
system, the
Cu-rich ([Cu]/[Ga]>1) samples consist of a near-stoichiometric ternary CuGaSe
2
phase and
Cu
x
Se segregating due to the Cu excess [2.20].
Considering the binary join Cu
2
Se-In(Ga)
2
Se
3
, it can be concluded that the
homogeneity range of the selenides, CuGaSe
2
and CuInSe
2
, extends up to 10 mole% into
the direction of Ga
2
Se
3
and In
2
Se
3
, respectively.

Table 2.1.2 shows the melting points and phase transition temperatures of the four basic
ternary Cu-based chalcopyrites [2.7].

Table 2.1.2 Melting points and phase transition temperatures of CuBX
2
chalcopyrites (B=In,Ga;
X=S,Se) [2.7].

21

Fig. 2.1.2 Phase diagrams of the a) Cu
2
S-In
2
S
3
(according to Binsma [2.5]), b) Cu
2
Se-In
2
Se
3
([2.16]) and c) Cu
2
Se-Ga
2
Se
3
([2.19]) pseudobinary systems.

c)

b)

22
2.1.3 Lattice defects

The role of defects in the ternary compound CuInSe
2
, and even more in Cu(In,Ga)Se
2
, is
of special importance because of the large number of possible intrinsic defects and, because of
the role of deep recombination centers for the performance of the solar cell devices. In the
ternary semiconductors, twelve intrinsic point defects are possible: in CuInSe
2
, for example,
there are 3 lattice vacancies,
Cu
V ,
In
V and
Se
V , 3 interstisials,
i
Cu ,
i
In and
i
Se , and 6 cationcation
or cation-anion antisite disorders (
Cu
In ,
In
Cu ,
Cu
Se ,
Se
Cu ,
In
Se , and
Se
In ). These defects can
also appear with different electrical charges [2.21].
Zhang et. al. have intensively studied the defects in the CuInSe
2
chalcopyrite
semiconductor, using the first-principles self-consistent electronic structure theory [2.14],
[2.22]. The defect physics of chalcopyrites have been discussed with respect to their binary II-VI
analogs. The following are found:
1) Due to the monovalent nature of Cu as compared with the divalent Zn, and due to the
weaker Cu-Se than Zn-Se covalent bonds, it is much easier to form a Cu vacancy in
CuInSe
2
(i.e.
Cu
V ), than to form a cation vacancy in II-VI compounds. For
Cu
V in Cu-poor
and stoichiometric material even a negative formation energy is calculated. This would
imply the spontaneous formation of large amounts of this defect under equilibrium
conditions. Low (but positive) formation energies are also found for the Cu on In anti-
site
In
Cu in Cu-rich material (a shallow acceptor which could be responsible for the p-
type conductivity of Cu-rich, non-Se deficient CuInSe
2
).
2) The formation energy ( , ) H q of a defect with a charge q is not constant, but varies
considerably both with the electronic potential (i.e. the position of the Fermi level), and
with the chemical potential of the atomic species. The dependence of the defect
formation energies on the electron Fermi-level (see Eq. (3.2.1)) could explain the
strong tendency of CuInSe
2
for self-compensation and the difficulties in achieving
extrinsic doping. Self compensation refers to the observation that certain semiconductors
resist being doped in a certain type or to sufficient doping levels, as discussed in detail
in 3.2 [2.23].
3) Pairing of defects can alter the electrical activity. For example, an isolated
Cu
V is a
shallow acceptor, while an isolated
Cu
In is a deep donor, but a defect pair based on
Cu
V
and
Cu
In is electrically inactive. In fact, the formation energies of defect complexes as
(2 , )
Cu Cu
V In , ( , )
In Cu
Cu In and (2 , )
i In
Cu Cu are lower than those of the respective isolated
defects. The (2 , )
Cu Cu
V In does not exhibit an electronic transition within the forbidden

23
gap, in contrast to the isolated
Cu
In anti-site which is a deep recombination center;
ordered arrays of this complex can be thought of as the building stones of a series of Cu-
In-Se compounds such as CuIn
3
Se
5
and CuIn
5
Se
8
[2.15].
The work of Zhang et al. [2.14] on formation energies of defects was not able to
reproduce the proper band gap energy of CuInSe
2
, and does not cover Se-related defects, which
are considered to be important. Another work by Neumann [2.24] used the simpler macroscopic
cavity model. Table 2.1.3 summarizes the ionization energies and the defect formation energies
of the 12 intrinsic defects in CuInSe
2
. Note that the data given for the cation defects in [2.25]
differ significantly from those computed in [2.14].

Table 2.1.3 Electronic transition energies (difference to the valence/conduction band energy for
acceptor/donor states) and the formation energies E of the 12 intrinsic defects in
CuInSe
2
. Transition energies in italics are derived from [2.25] and the formation
energies in italics from [2.24]. All bold numbers stem from [2.14]. Here the defect-
formation energy is that of the neutral defect in stoichiometric material.

In the Cu(In,Ga)Se
2
system, the challenge of defect physics is to explain three unusual
effects in this material: 1) the ability to dope Cu(In,Ga)Se
2
with native defects, 2) the structural
tolerance to large off-stoichiometry, and 3) the electrical benign nature of the structural defects.
Answering these questions can significantly contribute to the explanation of the photovoltaic
performance of this material [2.14].

2.1.4 Lattice vibrations

The structural properties of chalcopyrite semiconductors can be studied by Raman
scattering [2.26], [2.27], [2.28].

24
There is a four-to-one relationship between the Brillouin zone (BZ) of the unrelaxed (=1
and u=0.25) chalcopyrite-structure compounds and the BZ of the corresponding ZB-structure
materials, because of the two types of cations and the four times larger volume of the unit cell
with respect to that of ZB materials. Thus, points ((0, 0, 2 / )) X , ((2 / , 0, / )) W , and
((0, 2 / , / )) W of the ZB-structure materials are folded to the central point of the BZ of
the chalcopyrite-structure compounds. For better understanding, they are often labeled by
[ ]
X
and
[ ] W , and distinguished from
[ ] , which is the central point (Brillouin-zone center) for
both materials.
The chalcopyrite-structure compounds have eight atoms per unit cell. Thus, 24
vibrational eigenmodes are expected: 6 zone-center ( -like or
[ ] ) modes, as in the cubic
compounds, 6 [ ] X modes and 12 [ ] W modes:

1 2 3 4 5
1 2 3 4 7 + + + + ,

(2.1.4)
where all the
5
modes are doubly degenerated. Fig. 2.1.3 gives the schematic drawing of the
compatibility relations, which link the vibrational modes of the chalcopyrite with respect to the
corresponding ZB material [2.28]. The symbols l (lower mode) and u (upper mode) in the
subscripts are added to distinguish the modes with the same representations.

Fig. 2.1.3 Schematic drawing of the compatibility relations between the dispersion curve of the
phonon branches in the related zinc-blende-structure (ZB) materials and the
chalcopyrite zone-center phonon modes. The energy ordering of the phonon modes is
according to experimental results given in Ref. [2.28].

25
These modes include 3 acoustic modes
4 5
3
+
, and 21 optic modes:

1 2 3 4 5
9 12
1 2 3 3 6 + + + +

. The symmetry coordinates of all optical zone-center modes are
listed in Table 2.1.4.
Taking off two silent modes
2
2
2
2
A
and taking into account the long-range electrostatic interaction

which splits, for the
4
and
5
modes, the longitudinal optical (LO) and transversal optical
(TO) frequencies leading to nine additional LO components, chalcopyrite compounds have
[2.27]:
22 Raman active modes

1
1A
1
3B
2
6B 12E
( ) ( ) ( ) ( )
1 3 4 4 5 5
1 3 3 3 6 6 LO TO LO TO + + + + +
` ` ` `
, (2.1.5)

and 18 IR active modes
( ) ( ) ( ) ( ) TO LO TO LO
5 5 4 4
6 6 3 3 + + + (2.1.6)

26
Table 2.1.4 Symmetry coordinates of the 21 optical zone-center phonon modes in CuInSe
2
.
Atomic positions are given by (1)(0, 0, 0),
I
A
1 1
(2)(0, , ),
2 4
I
A
1
(1)(0, 0, ),
2
III
B
1 1 1 1 1 1
(2)(0, , ), (1)( , , ), (2)( , , ),
2 4 4 8 4 8
III VI VI
B C x C x
1 1 1 1
(3)( , , ), (4)( , , )
4 8 4 8
VI VI
C x C x [2.28].

The activity and the selection rules of the modes of the chalcopyrites together with the
ZnS-type modes are given in Table 2.1.5.
A
I
(Cu) B
III
(In) C
VI
(Se)
1
(1)
[W
1
] 0 0 +y
1
-y
2
-x
3
+x
4
2
(2)
[W
1
] 0 0 +x
1
-x
2
-y
3
-y
4

2
(3)
[X
1
] 0 0 +z
1
+z
2
-z
3
-z
4
3
(4)
[X
3
] +z
1
-z
2
+z
1
-z
2
0
3
(5)
[W
2l
] +z
1
-z
2
-z
1
+z
2
-y
1
+y
2
-x
3
+x
4

3
(6)
[W
2u
] +z
1
-z
2
-z
1
+z
2
+y
1
-y
2
+x
3
-x
4

4
(7)
[
15
] +z
1
+z
2
+z
1
+z
2
- z
1
-z
2
-z
3
-z
4

4
(8)
[W
2l
] +z
1
+z
2
-z
1
-z
2
+x
1
-x
2
-y
3
+y
4

4
(9)
[W
2u
] +z
1
-z
2
+z
1
-z
2
+x
1
-x
2
-y
3
+y
4

5
(10)
[
15
] +x
1
+x
2
+x
1
+x
2
-x
1
-x
2
-x
3
-x
4

5
(11)
[X
5l
] +y
1
-y
2
+y
1
-y
2
-x
1
-x
2
+x
3
+x
4

5
(12)
[X
5u
] +y
1
-y
2
+y
1
-y
2
+x
1
+x
2
-x
3
-x
4

5
(13)
[W
3
] +x
1
+y
1
+x
2
-y
2
+x
1
+y
1
+x
2
-y
2
0
5
(14)
[W
4l
] +x
1
-y
1
+x
2
+y
2
-x
1
+y
1
-x
2
-y
2
+z
1
-z
2

5
(15)
[W
4u
] +x
1
-y
1
+x
2
+y
2
-x
1
+y
1
-x
2
-y
2
-z
1
+z
2

5
(16)
[
15
] +y
1
+y
2
+y
1
+y
2
+y
1
-y
2
-x
3
+x
4

5
(17)
[X
5l
] -x
1
+x
2
-x
1
+x
2
+y
1
-y
2
-x
3
+x
4

5
(18)
[X
5u
] -x
1
+x
2
-x
1
+x
2
+y
1
-y
2
-x
3
+x
4

5
(19)
[W
3
] -x
1
+y
1
+x
2
+y
2
+x
1
-y
1
-x
2
-y
2
0
5
(20)
[W
4l
] +x
1
+y
1
-x
2
+y
2
-x
1
-y
1
+x
2
-y
2
-z
3
+z
4

5
(21)
[W
4u
] +x
1
+y
1
-x
2
+y
2
-x
1
-y
1
+x
2
-y
2
+z
3
-z
4

silent modes

27
Table 2.1.5 Combination of the ZnS-type modes in AgGaSe
2
, activity and related selection rules. Within this simple scheme, all modes should
be grouped in three bands with i) at high energy a group of six modes with
3 4 5
2 3 + + symmetry, ii) in the intermediate range,
a group of three optically active components with symmetry
1 3 5
+ + and iii) at low energy, a last group of four modes with
symmetry
3 4 5
2 + + . This is opposite to the experimental findings [2.27].

28
2.2 Dielectric function - refractive indices

The linear response of a nonmagnetic medium to transverse electromagnetic radiation
( 0, 0 D B = = ) is completely described by the dielectric tensor or by the conductivity
tensor ( / 4 )( 1) i = , where is the angular frequency. These tensors depend, in general,
on the frequency and the wavevector of the radiation. The causal nature of the response to an
electromagnetic field imposes a relationship between the real ( )
r
and the imaginary ( )
i

parts of : no response to an applied field can appear before the field is applied. This
relationship is, in the absence of magnetic fields:
'
'
' 2 2
0
( ) 2
( ) 1
i
r
P d

(2.2.1)

and its inverse:
'
2 ' 2
0
( ) 2
( )
r
i
P d

(2.2.2)

where P
designates the Cauchy principal part of the integral. Eqs. (2.2.1) and (2.2.2) are called
the Kramers-Kronig relations.
For isotropic and cubic materials, and reduce to scalars. The propagation of a plane
electromagnetic wave is isotropic and is determined by the scalar complex refractive index:
1/ 2
( ) ( ) ( )
r i
n n in = + = (2.2.3)
The real and imaginary parts of n are related to those of by:
2 2
( ) ( ) ( )
( ) 2 ( ) ( )
r r i
i r i
n n
n n

=
=
(2.2.4)
where the real part of the refractive index ( )
r
n is the refractive index ) ( n , while the
imaginary part ( )
i
n is the extinction coefficient ( ) k . Using these notations, equations (2.2.4)
give the ) ( n and ( ) k [2.29]:

2
+
=
r
n ,
2
r
k
+
= . (2.2.5)

The electric field E of a plane wave propagating along the x direction has the form:

[ ]
0
( / ) (2 / ) ( )
0 0
( , )
c
i n c x t k x i x t
E x t E e E e e

= =
, , ,
(2.2.6)

29
The expression 2 / k describes the attenuation of the field. Since the absorption coefficient is
usually defined by the attenuation in intensity written in the form of Lamberts law:

0
( ) *
x
I x EE I e

= =
, ,
(2.2.7)
one obtains for the relationship between k and :

4 k
= (2.2.8)
where the
1
is known as the optical penetration depth [2.30].

2.3 Electronic properties

The dielectric function of a semiconductor is closely linked to its electronic band
structure. The features observed in ( ) at optical energies are related to interband transitions
characterized by large or singular joint density of states (DOS), i.e. critical points (CPs). The
behavior of ( ) near a CP is given by:
( ) ( )
i n
C Ae E i
= + (2.3.1)
where A is the amplitude, the phase angle, E the energy threshold and the broadening.
The exponent n takes the value 1/2, 0 and 1/2 for one (1D), two (2D) and three-dimensional
(3D) CPs, respectively [2.31]. Conclusions about the bands can be drawn by evaluating
experimental ( ) spectra, and, by using equation (2.3.1) to determine CP parameters.
Usually, fitting procedures are run on numerically calculated derivatives of ( ) < >. In
particular, the second derivative of the dielectric functions,
2 2
/ d d , of chalcopyrite
compounds give the critical-point energies by fitting.
However, the interband transitions in these materials can be directly designated in their
optical spectra: even though the optical functions of ternary CH compounds (see also 2.1.1) are
similar to those of their binary analogs (ZB), the symmetry differences between ZB and CH
structures and the contribution of Cu-3d states, in case of the Cu-based chalcopyrites denoted as
Cu-III-VI
2
, to the upper valence band do result in distinctive features in the optical spectra
[2.31]. In fact, the hybridization of anion p-levels and noble metal d levels in the Cu-III-VI
2

chalcopyrites have been observed in electroreflectance (ER) studies of these compounds. This
hybridization concept is supported by a correlation between the downshift of the energy band
gap relative to the binary analog, due to a repulsive interaction between Cu-3d states and VI-
anion p states, and the percentage of the d-like character [2.4]. Quantitative estimates of the d-
like character range from 16% to 45% over this series of compounds (see Table 2.3.1) [2.3].

30
The structure of the fundamental absorption edge of chalcopyrites is well understood
[2.1]. These crystals are semiconductors with a direct fundamental gap at the Brillouin-zone
center . The threefold valence-band maximum is composed of three nondegenerate states
7
,
6

and
7
for CuGaSe
2
or CuGaS
2,
known as CGS-like materials (or
7
,
7
and
6
for CuInSe
2
or
CuInS
2
, known as

CIS-like materials), as shown in Fig. 2.3.1, giving rise to three transitions
called E
0
(A), E
0
(B), and E
0
(C) from smaller to larger energy. Experimental measurements of
these transition energies, denoted as E
a
, E
b
, and E
c
, respectively, and of their selection rules
allow us to determine the symmetry of the three valence states and to calculate the crystal-field
(
cf
) and the spinorbit (
so
) parameters, using the quasi-cubic model [2.32]. The energy of the
two
7
valence bands relative to the
6
valence band,
1
0
c b
E E E = >

and
2
0
a b
E E E = < , is
expressed as [2.3]:
2 1/ 2
1,2
8
[( ) ]
3
2 2
so cf so cf
so cf
E

+
+
= (2.3.2)
or

2 2 1/ 2 1 2
1 2 1 2
1
( 4 ) ,
2 2
so
E E
E E E E
+
= + +
(2.3.3)

1 2
( )
cf so
E E = +

The polarization selection rules can be understood in relationship to their well-known
binary analogs, as described in [2.33] and depicted in Fig. 2.3.1. In short, starting from a
threefold-degenerate
15
state in zinc blende, the introduction of a tetragonal crystal field gives
rise to one
4
plus a twofold-degenerate
5
level. The possible dipolar inter-band transitions to
the
1
conduction-band minimum are
4

1
, allowed in E//c, and
5
1
, allowed in Ec.
Spinorbit interaction further splits the
5
levels and the selection rules are somewhat relaxed, as
given in Fig. 2.3.1. Although only one of the transitions (
6

6
in the double group) has a pure
Ec polarization and the other two are mixed, it is approximately true that each transition keeps
its original polarization, i.e. before introducing the spinorbit interaction.
Even if all three transitions result from two simultaneous interactions, in the present
compounds, where
so cf
> , it is useful to make a simplification. In this simplified view, E
0
(A)
and E
0
(B) can be regarded as a crystal-field split gap, where each of these transitions has a
different polarization as determined by the sign of
cf
. The most usual situation in chalcopyrite
compounds is that 0
cf
< and then E
0
(A) is allowed in E//c and E
0
(B) in Ec. This is the case
of CGS. However, in CIS, 0
cf
> and the situation is reversed: E
0
(A) is allowed in Ec and
E
0
(B) in E//c. In this simplified schema, the higher energy E
0
(C) transition corresponds to the
spin-orbit split gap.

31

Fig. 2.3.1 Schematic evolution of the energy states at the band gap of chalcopyrites starting
from a zinc blende-like gap without spinorbit coupling. Solid (dashed) arrows
represent transitions allowed by symmetry in Ec (E//c) polarization, respectively.
Note that the ordering of the topmost valence bands is different in CIS and CGS
[2.33].

In polycrystals, the ordinary polarization Ec is expected to dominate the spectra [2.33].
Thus, the component (A or B) with Ec will give the main contribution to the first observed
peak. As sketched in Fig. 2.3.1, this polarization corresponds to E
0
(A) in a CIS-like and E
0
(B) in
a CGS-like band arrangement. Notice that in CIS, with a small distortion from cubic symmetry,
the A and B peaks are so close that they are never resolved at room temperature.
The energy gaps observed in the four Cu-based chalcopyrite compounds are listed in
Table 2.3.1 together with the crystal field and spin-orbit parameters derived from experimental
and theoretical values of the E
a
-, E
b
- and E
c
-gaps, using Eq. (2.3.3). In the same table, the % of
the d-like character of the same compounds is included [2.3].

Table 2.3.1 E
a
-, E
b
- and E
c
-energy gaps, and values of crystal field
cf
, and spin-orbit
so

parameters of the valence bands of Cu-based chalcopyrite crystals at room
temperature [2.3].

Energy gaps (eV) -

cf
(eV)
so
(eV) Chalcopyrite
E
a
E
b
E
c
Theory

Exp. Theory

Exp.
Estimated
% d-like
CuInSe
2
*
1.04 1.04 1.27 0.04 -0.006 0.48 0.23 34
CuInS
2
1.53 1.53 1.53 0.05 <0.005 0.07 0.17 45
CuGaSe
2
1.68 1.75 1.96 0.03 0.09 0.44 0.23 36
CuGaS
2
2.40 2.52 2.52 0.12 0.12 0.13 - 35

*
at 77 K

32
2.4 Optical properties

Accurate knowledge of the optical functions ) (
c
n and ) ( of chalcopyrite materials is
very important for the understanding and modelling of solar cell devices based on these
materials. For this reason, several ellipsometric studies of chalcopyrites have been reported. In
Table 2.4.1, the refractive indices n and extinction coefficients k of CuInSe
2
, CuGaSe
2
, CuInS
2
,
and CuGaS
2
compounds, in the two different polarizations, are listed. The ( n , k ) values are
obtained on single crystals of CuInSe
2
, CuGaSe
2
, CuInS
2
, and CuGaS
2
using spectroscopic
Ellipsometry at room temperature [2.31].

33
Table 2.4.1 Values of refractive indices n and extinction coefficients k of A) CuInSe
2
,
B) CuGaSe
2
, C) CuInS
2
and D) CuGaS
2
at intervals of 0.1 eV [2.31].

34

The absorption coefficients of chalcopyrite compounds can be determined using Eq.
(2.2.8) and the extinction coefficient values ( k
, k
|
) at the band gap energy of each material,
according to the data given in Table 2.4.1. The energy band gaps, the extinction and the
absorption coefficients of four Cu-based ternary chalcopyrites are listed in Table 2.4.2.

35
Table 2.4.2 Energy band gaps (
g
E ), extinction coefficients ( k
, k
|
) and absorption
coefficients ( 4 / k = ) of the most common Cu-based chalcopyrite
compounds.

Chalcopyrite Energy
band gap,
g
E (eV)
k
k
|
( ) / 2 k k k
= +
|

4 / k =
3
4 10 /1239.84 kE =
(x10
4
cm
-1
)
CuInSe
2
1.0 0.165 0.179 0.172 1.743
CuGaSe
2
1.7 - 0.200 0.200 3.466
CuInS
2
1.5 0.352 0.341 0.3465 5.268
CuGaS
2
2.4 0.101 0.222 0.1615 3.929

Out of them, CuInSe
2
is, probably, the strongest absorbing semiconductor under sunlight,
as shown in Fig. 2.4.1 [2.4].

Fig. 2.4.1 Absorption spectrum of CuInSe
2
compared with that of other photovoltaic
semiconductors. For comparison, the air mass AM1.5 (see 1.2) solar-emission
spectrum is given. -Si
0.16
is amorphous hydrogenated silicon and x-Si is crystalline
silicon.

36
3. CHALCOPYRITE HOMO- AND HETEROSTRUCTURES

3.1 Heterostructures

3.1.1 Band offset: band-alignment

As it has been already mentioned, the best efficiencies have been reached for chalcopyrite-
based heterojunction solar cells. Valence and conduction band offsets are among the most
important parameters, which characterize a heterojunction. In particular, the band offset between
the absorber and the buffer layer plays an important role in determining the solar cell efficiency
[3.1], [3.2]. The band alignment at the interface of the most commonly used buffer layer, n-CdS,
and the lower band-gap chalcopyrite absorber, p-CuInSe
2
, has been thoroughly studied by Wei
and Zunger [3.3]. Till then, the traditional view was that in such heterojunction cells the
conduction-band minimum (CBM) is on CdS (negative conduction-band offset 0
c
E < , and that
the valence-band maximum (VBM) is on CuInSe
2
, (positive valence-band offset 0
v
E > ). This
type-II band alignment was thought to be essential for electron transport from CuInSe
2
, to
CdS, and to eliminate the unfavorable conduction-band spike, (see below) which would have
resulted from 0
c
E > . However, theoretical calculations using the local density formalism, as
implemented by the highly precise linear augmented plane wave (LAPW) method [3.4], yielded,
for both ZnSe/CuInSe
2
and CdS/CuInSe
2
systems, 0
c
E > (hence a type-I band alignment),
as shown in Fig. 3.1.1. For the relaxed CdS/CuInSe
2
interface, 0.31 0
c
E eV = > and
1.07 0
v
E eV = > was found. The theoretical values
c
E and
v
E , shown in Fig. 3.1.1, were
confirmed by a synchrotron radiation soft x-ray photoemission investigation, reported by Nelson
et al. [3.5].

Fig. 3.1.1 Schematic of the calculated band line-up of the ZnSe/CuInSe
2
and CdS/CuInSe
2

heterojunctions. Energies are in eV.

37
Further experimental studies of the band offsets between CdS and CuInSe
2
chalcopyrite
layers, using photoemission spectroscopy, agree with the theoretical value 0.3
c
E eV = + [3.6],
[3.7]. In fact, the study of the band-alignment of polycrystalline Cu(In,Ga)Se
2
(CIGS) alloys has
shown that the valence-band offset,
v
E , is almost independent of the Ga-content and amounts
to about 1 eV [3.8]. Thus, the increase of the absorber band-gap following the addition of Ga to
CuInSe
2
leads to a change of
c
E from positive to negative values. The band offset between the
CdS buffer and the ZnO window layer has been determined by I-V curve analysis and
admittance spectroscopy to be 0.3 eV [3.9].
The beneficial positive conduction-band offset, 0
c
E > , leading to a high device
performance, has been explained by Klenk [3.2], as follows:
High open circuit voltages can be achieved if the bucking current due to recombination at
the interface is minimized. The recombination rate R within the field zone of the diode is
approximated by: /[ ( )] R np n p = + , where n and p denote the concentrations of electrons and
holes, respectively, and is the carrier lifetime. The recombination rate as a function of position
has its maximum where n=p and decreases rapidly for a high electron density or high hole
density. In order to minimize recombination for a given interface recombination velocity
1/ S , the heterojunction layout has to be such that the Fermi-level at the interface is close to
either the conduction or the valence band (see 3.2). This can be achieved by asymmetric
doping. Then the open-circuit voltage loss is only in the order of a few mV even for very high
interface recombination velocity.
The current losses at the interface can be neglected if the asymmetric doping is such that
the interface is inverted. For a chalcopyrite-based cell with a p-type absorber, this means that
the Fermi-level at the interface should be close to the conduction band. In this case, the minority
carriers collected from the bulk are majority carriers at the interface and are not subject to
significant recombination.
In consequence, the performance of a carefully designed heterojunction solar cell is
almost independent from the interface recombination velocity. The situation changes if the
conduction bands are not aligned at the interface (Fig. 3.1.2). A small spike, 0
c
E > , can be
beneficial because it tends to increase the inversion. On the other hand, a cliff is undesirable
because it reduces the inversion and it also opens a recombination path due to the decreased
barrier
b g c
E E E = [3.2]. The barrier
b
E hinders the holes from recombining with the
photogenerated electrons; a decrease of
b
E , thus, increases the recombination at the
buffer/absorber interface [3.10]. The open circuit voltage is also decreased.

38

Fig. 3.1.2 Band diagrams in the vicinity of the interface [3.2].

In this case, in order to re-establish the full barrier, the absorber band gap should be
widened in the vicinity of the interface and the valence band edge should be moved to lower
energies. In chalcopyrite-based cells, this would be achieved by an Ordered Vacancy Compound
(OVC) layer or by increasing the sulfur concentration at the absorber surface, provided that the
interface between the absorber bulk and surface has a low defect density. The latter may be
difficult to achieve with high-gap chalcopyrites [3.2].
In fact, with reference to the conduction band offset, CdS is a suitable buffer material for
CuInSe
2
and Cu(In,Ga)Se
2
with low Ga content. The band-diagrams for both low-Ga (small E
g
)
and high-Ga (small E
g
) ZnO/CdS/Cu(In,Ga)Se
2
solar cells calculated in thermodynamic
equilibrium are shown in Fig. 3.1.3. The baseline used for the calculations is the Cu(In,Ga)Se
2
(CIGS) compound with E
g
=1.15 eV [3.11]. The band diagrams show that with increasing Ga
content the electrical pn-junction, i.e. the point p=n, moves closer to the heterojunction. The loss
of the type inversion and the additional evolution of a barrier for the injection of electrons at the
heterojunction both increase the probability of junction-related recombination mechanisms
[3.12]. In high-gap cells based on CuInS
2
and CuGaSe
2
, the band line-up is not directly in favour
of an inverted interface and there is a conduction band cliff between the absorber and the CdS
buffer layer, leading to a reduced barrier for recombination
b
E . Nevertheless, an efficiency of

39
11.4 % (see Table 1.4.1) has been experimentally achieved with CuInS
2
-based solar cells [3.13].
This could be explained by a lower interface recombination velocity or by an inverted interface
achieved by a highly doped buffer layer with sufficient thickness or by charges present at the
interface (Fermi-level pinning) [3.2]. In the CuGaSe
2
solar cells with a rather large conduction
band cliff the CuGaSe
2
/CdS interface is not the dominating recombination path [3.12]. At the
CuGaSe
2
/ZnSe interface, although the band alignment shows the favourable spike configuration,
it has not been possible so far to produce good quality CuGaSe
2
/ZnSe solar cells [3.14].

Fig. 3.1.3 Conduction and valence band for a small a) and a large b) bandgap ZnO/CdS/CIGS
solar cell [3.11].

Consequently, a high interface recombination velocity can be tolerated if the
interface recombination is minimized by: i) inverted surface and ii) a favorable conduction
band spike. However, type inversion of the absorber surface by n-type doping is not the only
prerequisite for the heterojunction enhancement: the cell performance is limited by bulk
properties while the tunneling assisted recombination plays a significant role in chalcopyrite
solar cells especially those with high gap absorbers (e.g. CuGaSe
2
) [3.15], [3.2]. It has been
reported that in all Cu-poor Cu(In,Ga)Se
2
-based solar cells, the limiting factor for the open
circuit voltage V
oc
is the recombination in the bulk of the absorber material while
Cu(In,Ga)S
2
and those CuGaSe
2
devices where the films are prepared under Cu-rich
conditions are dominated by interface recombination. Therefore, it seems well possible that
the borderline between bulk and interface recombination is a matter of Cu-poor and Cu-rich

40
preparation rather than a result of the difference between small-gap and wide-gap materials as
argued earlier [3.16].

3.1.1 Mismatch strain and thermal strain

a) mismatch strain

In the heterostructure systems, the lattice matching conditions should be satisfied in order
to obtain good quality heterostructures. The lattice mismatches cause undesirable lattice defects,
such as misfit dislocations, cracks and internal strains in the epitaxial layers [3.17].
With respect to the misfit parameter f
m
that represents the lattice mismatch between the
substrate and the epilayer, the mismatch strain is defined as:
sub epi
m
epi epi
a a
a
f
a a
= = = , (3.1.1)
where
epi
a and
sub
a are the lattice constants of the unstrained epilayer and substrate, respectively.
The analysis that follows is based on the well-described theory of elastic strain in zinc-
blende type semiconductors [3.18]:
According to Hookes law, the strain is related to the stress by [3.19]:
j ij i
C =
(3.1.2)

where the constants
ij
C are called the elastic stiffness of the material.
In the cubic system of a zinc-blende (ZB) structure the elastic stiffness
ij
C is a 66
matrix, in which
11 22 33
C C C = = ,
12 13 23
C C C = = ,
44 55 66
C C C = = and
14 15 16 24 25 26 34 35 36 45 46 56
0 C C C C C C C C C C C C = = = = = = = = = = = = [3.19]. The matrice is
symmetrical about the leading diagonal:

11 12 12
12 11 12
12 12 11
44
44
44
0 0 0
0 0 0
0 0 0
0 0 0 0 0
0 0 0 0 0
0 0 0 0 0
ij
C C C
C C C
C C C
C
C
C
C
| |
|
|
|
=
|
|
|
|
|
\
(3.1.3)
Mismatch strain is usually generated by a planar stress defined as [3.18]:

= =
yy xx
, 0
zz
=
and (3.1.4)
0
zx yz xy
= = =

41
In a material of cubic symmetry, the strain tensor due to an in-plane biaxial stress with
two equal components (bisotropic, Eq. (3.1.4)) has the following elements:

xx yy
= =
and
12 12
11 11
2 2
= =
zz xx
C C
C C
(3.1.5)
The relationship between strain and stress, in this case, is given by:

( )
2
11 12 12 11
2
(
= +

xx
C C C C (3.1.6)
The application of strain/stress reduces the symmetry of the material and results in
significant changes in the electronic bands [3.20]. In zinc-blende (ZB) type semiconductors, the
application of uniaxial stress, for example, splits and shifts the p-like upper valence band into
three sub-bands [3.21], [3.22] called the light-hole (LH), heavy-hole (HH), and split-off hole
(SO) bands. The upper most valence band resulting in this configuration is HH-like (LH-like), if
a compressive (tensile) stress is applied.
Under the application of a bisotropic stress (Eq. (3.1.4)) parallel to the [100] and [010]
crystallographic directions, the calculated energy difference between the conduction and the two
upper most valence bands, noted as

and
b
in the case of chalcopyrites, at k=0, to first
order in strain, is given by [3.17]:

11 12 11 12
11 11
2
2
a
C C C C
E a b
C C
( | | | | +
=
( | |
\ \
(3.1.7)

11 12 11 12
11 11
2
2
b
C C C C
E a b
C C
( | | | | +
= +
( | |
\ \
(3.1.8)
where

and
b
are the lower band gap energies of chalcopyrites,
bulk
E

= ,
b b bulk
E = , are the energy separations with respect to the band gap energy of the bulk
bulk
, and , b are the hydrostatic and shear deformation potentials, respectively.
bulk
represents
the band energy under strain-free conditions.

b) thermal strain

With the temperature varying, the misfit parameter should include the changes of the
lattice constants induced by thermal effects. Two different models have been used for describing
the temperature changes of the epilayer and substrate lattice constants in the CuAl(S
x
Se
1-
x
)
2
/GaAs system: Considering that the lattice parameter a and/or half of c(c/2) of the chalcopyrite
structure nearly matches the lattice parameter a of the zinc-blende structure, the chalcopyrite

42
epilayer on a zinc-blende substrate can grow in such a manner that the a axis is normal to the
substrate surface (a-axis growth) or the c axis is normal to the substrate surface (c-axis growth).
Then, the lattice parameters of the epilayers used in Eq. (3.1.1) can be calculated according to
the following models [3.23]:
1) The first model assumes coherent (pseudomorphic) growth, in which the epilayer has
lattice parameter a or c/2 equal to that of the substrate. In this case the thermal expansion of the
lattice parameters of epilayer and substrate can be given by:
( ) 1
RT
a a T = + , (3.1.9)
where
RT
a is the lattice parameter at room temperature, is the linear thermal expansion
coefficient of the material, and T is the difference between the temperature of the
measurement and room temperature.
2) The second model assumes the development of thermal stresses: strains are fully
relaxed at the growth temperature; the epilayer is elastically strained during cooling to room
temperature because of the mismatch in the thermal expansion coefficients of epilayer and
substrate. In this case, the change of the in-plane lattice constant of the epilayer, at temperature
T, is given by:
|
|
\
|
+

= 1
1
1
T
T
a a
sub
a
epi RT
epi epi
, (3.1.10)
where
RT
epi
a is the lattice parameter of the epilayer at room temperature,
a
epi
is the thermal
expansion coefficient of the epilayer along one in-plane axis (a-axis, Fig. 2.1.1),
sub
is the
thermal expansion coefficient of the substrate.

3.2 Homostructures

As it has been already discussed, an inverted surface of the absorber can minimise the
interfacial recombination and therefore increase the open circuit voltage of the corresponding
cell. By converting the p-type absorber into n-type, and thus by preparing a homojunction
photovoltaic device an improved solar cell performance may be achieved, especially in the case
of the large band-gap chalcopyrite cells.
One fundamental difference between CuInSe
2
and CuGaSe
2
is the difficulty of preparing
n- type conduction in CuGaSe
2
, whereas CuInSe
2
can easily be converted from p- to n- type and
reversed by annealing in vacuum or Se pressure. Many studies focused on donor doping of
CuGaSe
2
during crystal growth by post-growth diffusion or ion implantation. Nevertheless, until
now, only strong electrical compensation, but no p- to n- type conversion of CuGaSe
2
has been

43
observed. Then, while CuInSe
2
and CuInS
2
can be doped both p- and n- type, as we add Ga into
CuInSe
2
to form the Cu(In
1-x
Ga
x
)Se
2
alloy, the system can no longer be doped n- type for large x
[3.24], [3.25]. The doping limits (also known as dopability) of semiconductors have been
tentatively explained by the doping pinning rule [3.26].
Doping limits exist because intentional doping by donors (acceptors) moves the Fermi
energy
F
E towards the conduction band minimum, CBM (valence band maximum, VBM), thus
lowering the formation energy of spontaneously formed acceptors (donors), which compensate
the intentional donor (acceptor) dopants. The failure to dope is related not merely to the
existence of a large band-gap, but to the position of the VBM with respect to the p-like pinning
energy
( ) p
pin
and the position of the CBM with respect to the n-like pinning energy
( ) n
pin

[3.27], [3.25].
This can be understood by noticing that the formation energy ( , ) H q (see also 2.1.3)
of a defect of charge q is:
( , ) ( .)
F
H q Const qE = + (3.2.1)
where the constant term is usually on the order of a few eV, and depends only on parameters
such as the atomic chemical potentials during crystal growth but not on the Fermi energy
F
E .
The Fermi energy, measured from the valence band maximum, varies over the range of the band
gap from the VBM to the CBM, typically also in eV range, and, its contribution to ( , ) H q is
magnified by a factor of q via Eq. (3.2.1). For acceptor-like defects, q is negative while for
donor-like defects, q is positive. When we introduce donors,
F
E moves towards the CBM, and
consequently, by Eq. (3.2.1), the formation energies ( , ) H q for =acceptors (q<0) are
lowered by amounts often comparable to the respective constant terms in Eq. (3.2.1).
Lower formation energies result in higher (spontaneously formed) acceptor
concentrations, thus compensating the intentionally introduced donors (see also 2.1.3). In a
fully compensated material, the electron and hole concentration are equal (as in the intrinsic
case). However, the electrons and holes originate from donors and acceptors in this case [3.28].
This leads to the pinning of the Fermi energy near the CBM at the
( ) n
pin
energy. Likewise, doping
by acceptors lowers
F
E towards the VBM, so by Eq. (3.2.1), ( , ) H q for =donors (q>0) are
lowered. This results in high concentrations of spontaneously formed donors that compensate the
intentionally introduced acceptors, and pins the Fermi energy near the VBM at the
( ) p
pin
energy.
These two processes thus set the upper and lower bounds for
F
E ,
( ) ( ) p n
pin F pin
E . The maximal

44
doping limit is hence decided by the value of
F
E at which there are enough spontaneously
generated defects to compensate the intentional dopants [3.25].
For the CuInSe
2
-based solar cells, it has been suggested that the real p-n heterojunction of
a successful solar cell may not be the traditional n-CdS/p-CuInSe
2
, heterojunction but a
homojunction between p-type bulk CuInSe
2
(CIS) and the In-rich n-type defect chalcopyrite, also
known as Ordered Vacancy Compound (OVC) [3.29], [3.6], [3.30]. The OVC crystal structure
has been found to be an ordered-vacancy chalcopyrite, CuIn
3
Se
5
(see Phase diagrams in 2.1.2)
[3.31]. High-efficiency Cu(In,Ga)Se
2
(CIGS) devices based on low-gap Cu-poor CIGS absorbers
exhibit a Cu-deficient-surface layer on top of the absorber; this layer has a larger band gap with
respect to the bulk material and it shows a Cu(In,Ga)
3
Se
5
composition [3.32]. It has been found
that, the band gap widening towards the surface is accommodated by a bulk/surface valence band
offset, which is found to increase directly the barrier
b
E (see Fig. 3.1.2) and thus eliminate the
interfacial recombination. Therefore, the enlargement of the band gap energy towards the
film surface is an important and operative element in all Cu-poor Cu(In,Ga)(Se,S)
2
films
[3.16].
In homojunction solar cells, however, the region between the semiconductor surface and
the junction must be sufficiently thin to ensure that the photon-generated carriers in this region
have a high probability of reaching the junction before recombining. The output voltage of the
cell is then determined by the doping concentrations in the n- and p- regions and by the lateral
resistance loss, which in turn is determined by the resistivity and thickness of the n- and p-
regions. Because of this constraint on the thickness of the illuminated regions, the theoretically
predicted efficiency of homojunction cells cannot be achieved [3.33].

45
4. GROWTH TECHNIQUES

The ternary CuInS
2
(CIS), CuGaSe
2
(CGS) and quaternary CuIn
1-x
Ga
x
Se
2
, CuIn
1-x
Ga
x
S
2

(CIGS) chalcopyrite films and/or solar cells studied in this thesis are prepared at the Hahn-Meitner
Institute Berlin by the work-group of Prof. Dr. M.-Ch. Lux-Steiner in the Department for Solar-
Energie-Research (SE
2
). The ZnSe films are deposited on CuGaSe
2
/Mo/glass using the E-beam
Evaporation (EBE) technique in the laboratory for Material Growth and Optical Characterization of
Assist. Prof. Dr. D. Papadimitriou at the National Technical University (NTUA) of Athens.

4.1 MOVPE grown CuIn
1-x
Ga
x
Se
2
epitaxial layers (x=0.08 - 0.82)

CuIn
1-x
Ga
x
Se
2
(CIGS) epitaxial layers, with Ga fraction varying between 0.08 and 0.82
(x=[Ga]/([Ga]+[In])=0.08, 0.19, 0.33, 0.50, 0.60 and 0.82), were grown by Metal-Organic Vapor
Phase Epitaxy (MOVPE) on epi-ready GaAs (001) substrates (Wafer Technologies Inc.). The
prepared samples are listed in Table 4.1.1. A horizontal MOVPE reactor (AIXTRON 200) was used,
equipped with a graphite substrate holder and an infrared heating system to allow fast temperature
ramps [4.1].

Table 4.1.1 CuIn
1-x
Ga
x
Se
2
epitaxial layers.

Code x=[Ga]/([Ga]+[In])
(EDX)
[Cu]/([In]+[Ga])

Thickness
(nm)
CIGSe009 0.08 1.0079 440
CIGSe010 0.19 0.9918 440
CIGSe029 0.33 1.0135 360
CIGSe022 0.50 0.9883 390
CIGSe027 0.60 1.0065 290
CIGSe026 0.82 1.0697 250

The EPICHEM metalorganic precursors were: TriMethyl Gallium, ((CH
3
)
3
Ga, TMGa),
riethyl ndium ((CH
3
)
3
In, TMI), Di-TertiaryButyl-Selenium ((C
4
H
9
)
2
Se, DTBSe) and
Cyclopentadienyl Copper TriEthyl Phosphine (C
5
H
5
CuP(C
2
H
5
)
3
, CpCuTEP). During the process 5
l/min Pd-purified H
2
was used as a carrier gas at a pressure of 30mbar. The growth temperature was
500 C or 570 C. The amount of deposited material was controlled by the flux of H
2
through the
precursors and by their vapor pressure. Due to its low vapor pressure, CpCuTEP has to be heated to
60C. The other precursors may be used at room temperature or below. The Cu-precursor was kept
at maximum output and the Se-precursor was provided at 10 times the concentration of the other

46
precursors. The composition of the films was controlled by the ratio of the Ga and In fluxes,
[Ga]/([Ga]+[In]). The deposition time was 4 h. There is a linear dependence between the
[Ga]/([Ga]+[In]) flux ratio during the process and the EDX measured [Ga]/([Ga]+[In]) ratio, x, in
the film. Changes of temperature do not affect this dependence much. The EDX measurements were
performed in an Oxford IMCA system within a LEO440 SEM. A at 7 keV electron beam was used
to avoid signals from the underlying GaAs, since the CIGS

layers are only 250-450 nm thick (see
Table 4.1.1). No As signal was detected at this excitation energy. The measurements were calibrated
with a polycrystalline Cu(In,Ga)Se
2
standard from NREL. The error is about 1 %.
The optimizing of the growth process of CuIn
1-x
Ga
x
Se
2
started with the parameter set known
for CuGaSe
2
, which is grown in high quality at 570 C. High quality CuInSe
2
can be grown at 500
C without measurable Ga diffusion from the substrate. Therefore, various growth temperatures
were used to obtain CIGS

with different Ga contents: low temperatures (500 C) for low Ga (x<0.3)
and high temperatures (570 C) for high Ga (x>0.3) content [4.1]. Each sample is grown in such
conditions to establish slightly Cu-rich CIGS layers with a ratio of [Cu]/([Ga]/+[In])=1.0-1.1 (Table
4.1.1) [4.2].

4.2 PVD grown CuIn
1-x
Ga
x
S
2
polycrystalline films (x=0.00, 0.04, 0.12)

CuIn
1-x
Ga
x
S
2
(CIGS) polycrystalline layers, with two different Ga compositions, x=
[Ga]/([In]+[Ga]) =0.04 and 0.12, were prepared in a Pfeiffer Classic 570 high vacuum system
equipped with a graphite substrate heater, three Createc molecular beam epitaxy (MBE) effusion
cells modified for operation at high temperatures in sulfur atmosphere and a custom built sulfur
effusion source [4.3]. A large distance between sources and substrate and tilting the sources towards
the center of the substrate resulted in negligible variation of the composition over the 5x5 cm
2

substrate. Soda lime glass (SLG) coated with a thin (1 m) film of sputtered molybdenum has been
used as a substrate.
Two different two-stage preparation sequences have been used: for the lower band gap
absorber (x=0.04) evaporation of In, Ga, and S at lower substrate temperature (typically 250
o
C) is
followed by evaporation of Cu and S at higher (typically 500
o
C) substrate temperature (sequence
M
2
), while for the absorber with x=0.12, a certain amount of Cu (close to, but always below
stoichiometry) is included already during the first stage (sequence M
3
).
The sulfur rate has not been intentionally varied in any of the processes and the total amount
of sulfur evaporated exceeded significantly the amount required for stoichiometry. Film thicknesses
were between 2 and 3 m after a total evaporation period close to 2 h. In both sequences, films were

47
generally Cu-deficient in the first stage and were converted to Cu-rich films in the second stage.
This conversion is accompanied by a change in the films emissivity. We have used this effect for
in-situ monitoring by observing the substrate and heater temperature with separate thermocouples.
The nominal Cu-excess in the final film has been adjusted to 10% by continuing stage 2 evaporation
after detection of the stoichiometry transition [4.3]. CuInS
2
polycrystalline films were also prepared
using a procedure similar to the one applied in the preparation of the lower band gap quaternary
chalcopyrite (sequence M
2
).
According to Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM)
results, the films are generally compact, with grain sizes in the order of one m. Prior to etching, the
film is covered homogeneously with CuS, which is important in view of the growth assistance
provided by this phase. In contrast to films grown from metallic precursors, a low surface roughness
is observed here after removing the CuS segregation.
Chalcopyrite and CuS (covellite) have been the only phases, identified after preparation, by
XRD. The incorporation of gallium was found to depend on the preparation sequence. A more or
less homogeneous gallium incorporation should lead to a quaternary Cu(In,Ga)S
2
alloy where the
lattice constant is decreased in comparison to CuInS
2
. In this case, the maxima in the XRD spectrum
should shift to higher angles. This is found indeed for sequences M
3
, but not for sequence M
2
.
Energy dispersive X-ray fluorescence (EDX) data on films with a higher gallium content, grown
using a M
2
recipe, confirm that the In-rich (in terms of the [In]/([In]+[Ga]) ratio) phase is
stacked on top of the Ga-rich phase [4.3].

4.3 CdS/CuIn
1-x
Ga
x
S
2
/Mo/glass

and ZnO/CdS/CuIn
1-x
Ga
x
S
2
/Mo/glass

heterostructrures

CdS is usually chosen as an n-type material in CIGS-based heterojunction solar cells. CdS
buffer layers were prepared by chemical bath deposition (CBD) at 60-80
o
C. On top, ZnO used as a
window layer is deposited by dc magnetron sputtering. In the investigated CdS/CIGS

and
ZnO/CdS/CIGS heterostructures, the CIGS

films were grown by PVD, under Cu-excess, on
Mo/SLG substrates (see 4.2).

4.4 Solar cells based on CuIn
1-x
Ga
x
S
2
absorbers

CuIn
1-x
Ga
x
S
2
(CIGS)-based solar cells have been fabricated depositing a standard window
layer which consists of CdS deposited by CBD and sputtered ZnO/ZnO:Ga bilayer used as a
transparent conducting oxide (TCO) top contact onto freshly etched absorber films (see 4.2 and

48
4.3). Ga-doped zinc oxide (ZnO:Ga) minimizes spreading resistance for the passage of current
toward the contacts in the cell [4.4]. Ni/Al has been evaporated through a shadow mask to obtain a
front contact grid. A single layer antireflective coating of evaporated magnesium fluoride has also
been applied in some cases. A schematic diagram and a photo of a CIGS solar cell are illustrated in
Figs. 4.4.1a) and b), respectively.

(a) (b)

Fig. 4.4.1 a) Schematic diagram and b) picture of a CIGS solar cell.

4.5 CCSVT grown CuGaSe
2
films and Ge-doped CuGaSe
2
films

CuGaSe
2
polycrystalline films were grown using a novel efficient Chemical Close-Spaced
Vapor Transport (CCSVT) technique [4.5]. The CCSVT reactor, presented in Fig. 4.5.1, consists of
a graphite reaction-cell placed in a quartz box, which has an inlet tube for the gaseous transport
agents (I
2
, HCl) used for volatilization of the Ga
2
Se
3
source material. A spacer is used for the
adjustment of the distance between the source drawer and the substrate holder where substrates up to
10x10 cm
2
can be mounted. The source material in the form of fine-grained powder synthesized
from 6 N pure elements fills the source drawer, which allows an easy refilling. The complete
i-CdS
i-ZnO
Ni/Al
350 nm
Cu(In
1-x
Ga
x
)S
2

[p-type]
Mo contact
n-ZnO
Glass
Light
1 m
3 m
50 nm

49
CCSVT quartz box is placed in a quartz tube that can be evacuated or filled with H
2
.The reactor
pressure can be varied from 10
-2
mbar up to 1000 mbar. Collectively arranged infrared units (12
infrared lamps-1000 W each) are used as heaters for the source drawer and the substrates. The
temperatures can be set independently and are controlled by thermocouples at the source and
substrate side.
Gaseous HCl diluted in H
2
is used as transport agent, while additional hydrogen serves as
ambience in the quartz tube that surrounds the reaction cell. The HCl and H
2
gas quantities are
externally controlled by mass-flow controllers. Substrates consisting of 250-nm-thick Cu films
evaporated on clean and Mo-coated (Mo thickness of 750 nm) soda lime glass (SLG) were used for
CuGaSe
2
growth. The conditions were adjusted for the preparation of Ga-rich absorbers with a
[Cu]/[Ga] ratio of 0.95.

Fig. 4.5.1 Schematic drawings of the CCSVT apparatus.

Ge ions were implanted into the thin films in one- and three-stage processes [4.6]. In the
one-stage implantation, an acceleration energy of 150 keV and a fluence of 10
16
ions/cm
2
was used.
In three-stage processes, three sequential steps were used as follows: 1
st
stage: acceleration energy
50 keV, dose 3x10
15
cm
-2
, 2
nd
stage: acceleration energy 150 keV, dose 7x10
15
cm
-2
, 3
rd
stage:
acceleration energy 200 keV, dose 10
16
cm
-2
. The ion implantation processes were followed by
thermal annealing of the implanted samples at 400
o
C, in an effort to reduce the damage caused by
the implantation.

50
4.6 ZnSe/CuGaSe
2
/Mo/glass heterostructrures

Even though, the best efficiency of 19.5% for CIGS solar cells has been achieved for CdS as
a buffer layer prepared by CBD, concerns with small amounts of cadmium have lead towards the
investigation of Cd-free buffer layers [4.4], [4.7]. ZnSe is one of the materials used alternately as a
buffer layer ZnSe is deposited by the e-beam evaporation (EBE) technique on PVD grown Ga-rich
CuGaSe
2
polycrystalline films. The absorber films were deposited on molybdenum coated soda lime
glass substrates. The ZnSe deposition takes place in a Veeco VE-770 Chamber (Fig. 4.6.1) equipped
with a quartz crystal monitor-detector for controlling the deposition rate. The substrate can be heated
up to 1200

o
C, while the temperature is electronically controlled with an accuracy of 0.1
o
C. In our
case, the substrate temperature was 400
o
C, while the e-beam power was 11 KW. The deposition
process is followed by annealing at 250
o
C for

30 min. The quartz crystal frequency deviation during
the growth process was 1 KHz, corresponding to a layer thickness in the order of 100 nm. The actual
layer thickness was determined by the Rutherford Back Scattering (RBS) method and found to be 84
nm.

Fig. 4.6.1 The e-beam evaporation (EBE) chamber.

51
4.7 PVD grown CuIn
1-x
Ga
x
Se
2
polycrystalline films and solar cells

CuIn
1-x
Ga
x
Se
2
(CIGS) polycrystalline films suitable for solar cell device development were
deposited using a three-stage coevaporation process on Mo/glass(SLG) and Titanium foil substrates
[4.8]. An in-situ growth process was used, which was controlled by using laser light scattering
(LLS). The three phases of the deposition were identified by a sequence of metal selenides that were
deposited onto the different substrates, as shown in Fig. 4.7.1.
First, an (In,Ga)
2
Se
3
precursor layer is grown at a substrate temperature T
1
. The end of stage
1 is indicated by the marker e
(1)
. During phase 2, the In and Ga flux is turned off and only Cu and Se
are offered to the substrate surface at an elevated substrate temperature T
2
. It is apparent from the
scattered laser light intensity that the once transparent (In,Ga)
2
Se
3
layer, of which the growth could
be observed via interference fringes, with increasing process time, becomes opaque to the laser light.
Although the thickness of the deposited film increases, no more interference fringes are visible.
Once the stoichiometric point s
(1)
is passed, i.e., [Cu]/([In]+[Ga])>1, the roughness of the CIGS
layer increases to an extend that the scattered laser light intensity is enhanced significantly. By
turning down the Cu flux and taking back up the In and Ga evaporation rate, the deposition process
enters stage 3 (see marker e
(2)
), where the composition of the deposited layer is taken back into the
Cu-poor regime. The layer deposition is complete at e
(3)
[4.8].
The deposition conditions were adjusted to give Ga-rich CIGS absorbers. XRF
measurements show x=[Ga]/([Ga]+[In])=0.34, [Cu]/([In]+[Ga])=0.88 for the CIGS layer on the
Mo/glass substrate and [Ga]/([Ga]+[In])=0.36, [Cu]/([In]+[Ga])=0.92 for the absorber layer on the
Ti foil (flexible) substrate, in accordance with the record-efficiency CIGS-based solar cells reported
up to now [4.9]. XRF data show an absorber layer thickness of 1.71 m for the rigid and 1.78m for
the flexible solar cells. A molybdenum layer was sputtered directly on the substrate as back contact,
followed by the CIGS deposition, the chemical bath deposition of the CdS buffer layer, and a RF
sputtered i-ZnO/ZnO:Al transparent front contact as the cell window; on top, a Ni/Al grid as front
contact was evaporated to facilitate current collection. The buffer layer has a thickness of 60 nm
while the window layer consists of a 120 nm-thick ZnO and a 200 nm-thick doped ZnO (ZnO:Al).
In case that the cell was fabricated on flexible Ti-foil substrate, a NaF film was, generally, deposited
by physical vapor deposition onto the Mo back contact prior to the CIGS deposition (see 1.4, p. 14)
[4.9]. CIGS solar cells on Mo/glass and Ti-foil substrates are shown in Figs. 4.7.2a) and b),
respectively.

52

Fig. 4.7.1 LLS-signal and substrate temperature profiles for a standard CIGS co-evaporation
process.

(a) (b)

Fig. 4.7.2 a) Mo/glass and b) Ti/Mo/NaF-CIGS-solar cell.

53
5. SPECTROSCOPIC ANALYSIS TECHNIQUES

5.1 Spectroscopic Ellipsometry (SE)

Ellipsometry is an experimental method, which dates back to the middle of the last century.
Since then, it has been extensively employed in semiconductor characterization and has the potential
for in-situ diagnostics of surfaces. The principle of Ellipsometry is based on the fact that the
polarization state of light is changed upon reflection from a surface: if one reflects linearly polarized
light on a solid at non normal incidence, the reflected light will, in general, be elliptically polarized
except for the normal modes of incidence: light polarized parallel or perpendicular to the plane of
incidence. It is therefore possible to determine the two optical constants at a given wavelength by
measuring the state of polarization of the reflected light i.e. the orientation and axes ratio of the
polarization ellipse. A number of schemes have been devised to perform this type of measurement
[5.1].
In the most common experimental configuration for spectroscopic Ellipsometry (SE),
linearly polarized light is incident on a surface and the polarization state of the reflected light, which
is in general elliptically polarized (Fig. 5.1.1) is analysed. From knowledge of the polarization
states, the ratio of the Fresnel coefficients -the p- (parallel) and s- (senkrecht, perpendicular)
complex reflectances
p
r and
s
r , respectively- can be derived:
tan
p i
s
r
e
r
= = , (5.1.1)
since the polarization is determined by the ratio of the components of the electric field vector. The
parameter corresponds to the ratio of the magnitude of the total reflection coefficient and is the
phase shift in p- and s- waves due to the reflection. and are known as the Ellipsometry
parameters [5.2].
Using the Fresnel equations, can be directly translated into a complex dielectric function
( ) h . Depending on the photon energy E = h of the incident light, ( ) h is the bulk dielectric
function of the material under study provided the sample is homogeneous. However, the presence of
surface layers or roughness results in inaccurate values for the bulk dielectric function and care has
to be taken in the preparation of the samples. In case of inhomogeneity in the samples, ( ) h is an
average over the region penetrated by the incident light and is then a so-called pseudodielectric
function or effective dielectric function, written as ( ) < > h . From this effective dielectric
function ( ) < > h and appropriate models, layer properties, such as thickness or layer dielectric

54
functions, can be derived. Using this analysis two experimental parameters-the real and imaginary
part of < > - (per photon energy) are determined [5.2].

Fig. 5.1.1 Principle of ellipsometric measurements. Linear polarized light is incident on the sample
under an angle
0
and the polarization state of the reflected light, which is in general
elliptically polarized, is measured [5.2].

Since Ellipsometry is measuring the ratio (or difference) of two values (rather than the
absolute value of either), according to Eq. (5.1.1), it is very robust, accurate, and reproducible. For
instance, it is relatively insensitive to scatter and fluctuations, and requires no standard sample or
reference beam.
An ellipsometer consists of a light source, a polarizer to fix the polarization of the incident
light, an analyzer to measure the polarization state of the reflected light and a detector. With these
basic components, the ellipsometer can be configured in a large number of modes: null, rotation
analyzer, rotation porarizer and polarization modulation. In Fig. 5.1.2, the basic Ellipsometry
configuration used for multiplayer thin-film structure analysis is shown.

Fig. 5.1.2 Typical Ellipsometry measurement configuration used for a thin-film stack.

55
Ellipsometry measurements can be performed as a function of wavelength (spectroscopic),
incident angle (variable-angle single-wavelength/spectroscopic) and time (real-time/dynamic,
single-wavelength/spectroscopic) depending on the requirements.
A typical thin-film Ellipsometry analysis consists of the following steps:
a) measurement of Ellipsometry parameters and ,
b) optical modeling to functionally describe the optical properties of the sample,
c) generation of data using the optical model and
d) fitting model-generated data to minimize the error.
The accuracy of the data obtained from an analysis depends primarily on the optical model. Several
classical and quantum-mechanical oscillator models have been developed to describe the optical
constants of material in a functional form. The most fundamental classical oscillator model is the
Lorentz oscillator, which is equivalent to the classical mass on a spring. A Lorentz oscillator can be
described using the relation:
2 2
( )
( )
A
h
E h iBh

=

(5.1.2)
where A is the amplitude, E is the center energy, B is the broadening of the oscillator and h is
the photon energy in eV [5.3].

5.2 Modulation spectroscopy: Photo- and Electroreflectance (PR&ER)

Modulation spectroscopy is a powerful and versatile optical technique for obtaining valuable
information about a large variety of semiconductor systems, including bulk/thin films,
surfaces/interfaces (semiconductor/air (vacuum), semiconductor/semiconductor (hetero- and
homojunctions), semiconductor/metal, semiconductor/electrolyte), micro- and nanostructures
(quantum wells, multiple quantum wells, superlattices, quantum wires, quantum dots), the effects of
growth/processing, as well as the characterization of actual device structures (heterojunction bipolar
transistors (HBTs), pseudomorphic high electron mobility transistors (PHEMTs), quantum well
lasers, etc.).
Modulation spectroscopy is an analog method for taking the derivative of the optical
spectrum (reflectance or transmittance) of a material by modifying in a periodic way the
measurement conditions. The basic idea of this optical technique is as follows: by applying a
repetitive perturbation, such as an electric field (electromodulation), heat pulse (thermomodulation),
or stress (piezomodulation), some property of the measuring system is varied in a periodic way and
the corresponding normalized change in the reflectance R is determined.

56
The periodic variation of the measurement conditions gives rise to sharp, differential-like
spectra in the region of interband (intersubband) transitions. Therefore, modulation spectroscopy
emphasizes relevant spectral features and suppresses uninteresting background effects. It is possible
to account for the line shapes to yield accurate values of important parameters such as the energies
and broadening functions of interband (intersubband) transitions. Even at 300 K the energy of a
particular feature can be obtained to within a few meV.
Modulation spectroscopy can be also employed to investigate the effects of static perturbations such
as electric and magnetic fields, hydrostatic pressure, stress/strain (external and/or internal),
temperature, composition, etc.
A particularly useful form of modulation spectroscopy is electromodulation (electric field
modulated reflectivity (transmission)) since it is sensitive to surface/interface electric fields and can
be performed in contactless modes that require no special mounting of the sample. This perturbation
can destroy the translational symmetry of the material and hence can accelerate unbound electrons
and/or holes. This is exactly the aspect of electromodulation (EM) that produces a sharp, third-
derivative line-shape in bulk materials under certain electric field conditions (Fig. 5.2.1b)).
However, for bound states such as excitons, impurities, quantized levels in quantum wells or
the uncoupled states of multiple quantum wells, the perturbing field does not accelerate electrons
and/or holes. These types of particles do not have translational symmetry and are confined in space.
In the case of such bound states, the line-shape is first-derivative.
Two of the most widely used forms of EM are photoreflectance (PR) and contactless
electroreflectance (CER). In PR, modulation of the built-in electric field is caused by photoexcited
electron-hole pairs created by a pump source, e.g. a chopped d.c. laser. The modulating frequency is
typically ~200 Hz. In CER, which requires no pump beam, an a.c. modulating voltage (~1 kV at
~200 Hz) is applied [5.4].

57

Fig. 5.2.1 a) A schematic diagram of the change in the imaginary part of the dielectric function
expected for a first-derivative modulation process where lattice periodicity is preserved.
b) Similar diagram for electric field modulation where lattice periodicity is not preserved.
The effect of the perturbation on the energy band structure and optical transition is
shown at the left in each case [5.5].

5.2.1 Modulation spectra and the dielectric function
The perturbation induced change R in the reflectance R produces a change in the intensity
reflected by the sample as R R I I / / = . The experimental modulation spectra show R R / as a
function of energy.
In a two-phase system (material-ambient), the relationship between R and the dielectric
function of the material
i r
i + = is:

a a
a
a
n n
n n
n n
R
= =
+
=
2 2
2
,
, (5.2.1)
where n is the (real part of the) refractive index of the material, n
a
and
a
are the (real parts of the)
refractive index and the dielectric function of the ambient, respectively.

58
The differential changes in reflectance are related to the perturbation of the complex
dielectric function in a simple manner, expressed as [5.6]:

( )
( ) [ ]
i r
a
a
i
n
n
R
R

+ =
=
(
=
Re
2
Re
(5.2.2)
where
r
and
i
are the modulation induced changes in the complex dielectric function
i r
i + = ; and are the Seraphin coefficients, which depend on the unperturbed dielectric
function. The quantities
r
and
i
are related by a Kramers-Kronig inversion (see Eqs. (2.2.1)
and (2.2.2), 2.2). Near the fundamental gap of bulk materials 0 , so
1
R
R
is the only
term that is important. However, in multiplayer structures interference effects are important, so both
r
and
i
may have to be considered. The functional form of
r
and
i
can be calculated for
a given perturbation provided that the dielectric function and critical points are known [5.4], [5.7].
The general expression for is:

+
+ =
2 /
2 / 0
2
3
2 2
2
' ] ) ( [
' exp
4
1 ) , (
t
t
cv
cv
BZ
t i k E E i
dt p e dt k d
E m
ie
E
h
,
, h
, (5.2.3)
where E is the photon energy, is a phenomenological broadening parameter, BZ is the
abbreviation of the Brillouin Zone, c and v denote conduction (empty) and valence (filled) bands,
respectively, e is the unit polarization vector of the photon electric field; the momentum matrix
element
cv
P
,
is independent of the wave vector k
,
. ) ( ) ( ) ( k E k E k E
v c cv
, , ,
= is the interband energy.
The physical mechanism responsible for electric field modulation is the coupling of the field
to the electrons, causing them to accelerate through the lattice. Under the application of the electric
field F
,
, the complex dielectric function ) , , ( F E
,
is usually written as a sum of the dielectric
constant ) , 0 , ( E without a field and the change of the dielectric constant ) , , ( F E
,
due to the
electric field. The dielectric function under the application of an electric field F
,
becomes [5.8]:
(
+ +
+ =
+ =

h
, ,
3 / ) (
exp 1
) , , ( ) , 0 , ( ) , , (
3
0
3
2
t i t i E E i
dt k d
E
A i
F E E F E
cv
BZ

(5.2.4)

59
where
2
2
2
4
m
p e e
A
cv
,
h
=
, ( ) ( ) 4 / 8 /
3 2 2 2 3
h h h = = F e , h is the electro-optical energy, and
is the effective mass, defined by
h e
m m
1 1 1
+ =
(m
e
and m
h
are the electron and hole mass,
respectively).
The resulting line shapes vary according to the applied electric fields. Generally, two distinct
regions of field strength exist:
2) the high-field region where the Franz-Keldysh effect is observed and
3) the low-field region where broadening effects dominate.
In the first case, the electromodulation (EM) spectrum exhibits, above the band-gap,
oscillatory features, called Franz-Keldysh oscillations (FKOs), which are a direct measure of the
relevant electric field (built-in and/or applied) [5.4]. The second case will be discussed in detail right
below.

5.2.2 Photoreflectance-spectra in the low-field regime
In the low-field regime, the homogenous broadening is large, i.e.,
3
t t >> . In this
case, we expand h h 3 / 1 ) 3 / exp(
3 3
t i t i + in Eq. (5.2.4), which results in the Aspnes low-field
limit expression [5.4]:
(
+
|
|
\
|
+
+ =

h h
,
t i E E i t i
dt k d
E
A
F E
cv
BZ
) (
exp
3
1 1 ) , , (
0
3
3
2

. (5.2.5)
Integrating the above equation yields the final form:

4
3
3
2
3
2
) (
) ( 2 1
1 ) , , (

i E E
k d
E
A i
i E E
k d
E
A i
F E
cv
BZ
cv
BZ
+
+
+
+ =

h
,
. (5.2.6)
In the low-field regime, the modulated PR lineshapes are related to the third-derivative of the
unperturbed dielectric function.
The structures observed in the PR spectra are attributed to interband critical points (CPs),
which can be analyzed in terms of standard analytic line shapes [5.7]:
( ) ( )
n
g
i n
i E E e A E

+ =

, , (5.2.7)
which depends upon 5 parameters: amplitude A, phase projection factor , threshold (bandgap)
energy E
g
, broadening parameter , and exponent n. It is useful to define the overall amplitude
n
A

rather than A, so that the coefficient A is independent of the broadening parameter. For

60
undifferentiated spectra the exponent n has the value of 1/2 for one-dimensional (1D), 0 for 2D,
and 1/2 for 3D critical points. Discrete excitons can be included if we allow n to take the value (-1).
Thus only one functional form covers everything.
In the low-field regime, the broadening parameter is larger than the electro-optical energy
h ( h >> or h >> ). In this case, only the peak at E
g
remains; all other oscillations should
be largely washed out. The PR line-shape for band-to-band transitions is related to the third
derivative of according to ( )
( )
3
2 3
3
E
E

h .
In this case, the experimental modulation spectra of R R / can be given as:
( )
( )
( )
( )
( ) [ ]
m
g
i m
a
a
a
a
i E E e A
E
E
n
n
n
n
R
R
+ =
(
(
=
(
Re
2
Re
2
Re
3
2
3
3
h , (5.2.8)
where m=2.5 for 3D critical points. This equation is the well-known Aspnes Third Derivative
Functional Form (TDFF) [5.7].

5.2.3 Temperature dependence of transition-energies
As in bulk semiconductors, the electronic energies, in heterostructures, display a temperature
dependence at constant pressure:

ln
ln
g g g
T V
dE E E
d V
dT V dT T
| | | | | |
| |
= +
| | | |

\
\ \ \
(5.2.9)
The first term results from the variation of the band gap due to thermal expansion of the crystal. The
second term represents the change of the gap arising from electron-phonon interactions (one can
regard this as the renormalization of the band-gap energy by electron-phonon interaction) and is
usually negative in sign. The effect of thermal expansion accounts for a fraction (
1
4
) of the total
shift, the remaining temperature dependence of band-gap energies arises from electron-phonon
interactions. The electron-phonon interactions, in turn, are of two types: the first-order interaction
considered in second-order perturbation theory (self-energy or Fan term) and the second-order
(quadratic) interaction taken in first-order perturbation theory Debye-Waller or Yu-Brooks term)
[5.9].

61
The temperature-induced change in the band-gap energy
g
E is usually described by
Varshnis empirical expression:

2
( ) (0)
g g
T
E T E
T
=
+
(5.2.10)
where (0)
g
E is the band-gap energy at 0 K, and are constants for a given semiconductor, the
latter being proportional to the Debye temperature [5.10]. The temperature dependence of the
interband transitions can be alternately described with an expression in which the energy thresholds
decrease proportional to the Bose-Einstein statistical factors for phonon emission plus absorption:

/
2
( ) 1
1
B
g B B T
E T E a
e
| |
= +
|
\
(5.2.11)

The parameter
B
describes a mean frequency of the phonons involved, and
B
a the strength of the
interaction [5.11], [5.12]. It has been shown from calculations of electron-phonon spectral functions
in Si and Ge that energy shifts due to the electron-phonon interaction include contributions from
both acoustic and optical phonons. Thus
B
in Eq. (5.2.11) should be viewed as the average
frequency of both acoustic and optical branches.
The temperature dependence of the linewidth of the interband transitions of semiconductors
can be expressed as:

/
( ) (0)
1
LO
ep
T
T
e
= +
(5.2.12)
(0) represents the broadening due to temperature independent mechanisms (such as impurity,
dislocation, and surface scattering) and
ep
the strength of the excitonLO-phonon coupling. Here
LO
is the average frequency of the longitudinal optical phonons. It should be noted, as reported in
Refs. [5.11], [5.12] that the optical phonons are the main contributors to the broadening of critical
points. This leads to a higher average phonon frequency
LO
from the fit of the broadening
parameters in Eq. (5.2.12) than for the electron-phonon contribution of the energy shifts with
temperature (Eq. (5.2.11)) [5.13].

5.3 Photoluminescence (PL) spectroscopy

5.3.1 Photoluminescence emission
The process of luminescence requires a non-equilibrium carrier concentration in the
electronic bands or in the electronic states of a defect structure [5.14]. Luminescence emission can

62
be excited by various ways. The photoluminescence (PL) is excited by photons,
cathodoluminescence (CL) by cathode rays, electroluminescence (EL) by electric fields and
thermoluminescence (TL) by thermal release of energy stored in previously excited solids [5.15].
Photoluminescence spectroscopy is a contactless, nondestructive method for probing the
electronic structure of materials. Light is directed onto a sample, where it is absorbed and imparts
excess energy into the material in a process called "photo-excitation". Specifically, photo-excitation
causes electrons within the material to move into permissible excited states. When these electrons
return to their equilibrium states, the emission of light will include several different processes.
In Fig. 5.3.1, several possible processes for radiative and non-radiative recombination are
illustrated. The first three radiative processes and the last non-radiative one are intrinsic, whereas for
the others at least one impurity level is required. Reactions 1 and 2 are band-to-band
recombinations, which are usually not very efficient, and reaction 3 is the exciton luminescence.
Reaction 6 gives rise to donor-acceptor pair spectra. The trapping centers, labeled Tr in the figure,
can be very efficient for luminescence since they can first capture and localize an electron or the
hole which then strongly increases the probability of capturing the other partners for the radiative
recombination. The last type of radiative recombination is particularly important for laser processes
in the visible spectral range and for chromophores in organic crystals.

Tr
A
E D
radiative
transitions
1 2 4 3 5 6 7 8

R
nonradiative
transitions

Fig. 5.3.1 Radiative and nonradiative recombination processes for excited electrons; (E: exciton, A:
acceptor, D: Donors, Tr: trapping center, R: recombination center) [5.14].

Nonradiative recombination occurs either via recombination centers or by Auger processes.
Recombination centers are usually deep impurity levels close to the center of the energy gap. In
Auger processes the energy released as a consequence of the recombination is transferred to another
electron. This electron gets excited into a higher state in the band from where it can stepwise return
to its ground state without radiation. Auger processes represent a very general phenomenon and
occur in many different configurations. For example, the radiative recombinations from the band

63
states to the impurities (4 and 5 in Fig. 5.3.1) have to compete with the corresponding Auger
processes. The dominant process for the recombination is determined by its lifetime in the excited
state. For luminescence to be efficient, the radiative recombinations must dominate over the non-
radiative ones [5.14].

5.3.2 Photoluminescence from semiconductors
Photoluminescence is related to the energy separation between the two electron states
involved in the transition, that is, between the excited state and the equilibrium state. The intensity
of the emitted PL depends on the contributing radiative processes. PL data reveal a multitude of
structure related to electronic states in a semiconductor. In the following, some important processes
are discussed.

Band-to-band transitions
In a perfect semiconductor e-h pairs will thermalize and accumulate at the conduction and
valence band extrema, there they tend to recombine. If this semiconductor has a direct bandgap and
electric dipole transitions are allowed, the e-h pairs will recombine radiatively with a high
probability. As a result, high quality direct-bandgap semiconductors, such as GaAs, are strong
emitters of bandgap radiation [5.16].
Band-to-band transitions involve the recombination of free electrons and free holes. Let us
define
r
as the radiative recombination time of one electron and one hole. If the free electron and
hole concentrations are, respectively,
e
n and
h
n , then the rate of emission of photons by their
recombination is given by /
e h r
n n assuming that
r
is the same for all possible choices of
recombining pairs. For a thermalized distribution of free electrons and holes, the radiative
recombination time depends on the electron and hole energies and therefore changes with the photon
energy. Then,
r
should be replaced by an averaged radiative recombination time
r
< > . The
averaging procedure depends also on whether wavevector is conserved in the recombination
processes. When a high density of e-h pairs is excited, wavevector is not conserved. In
electroluminescence, where it is possible to inject one extra minority carrier into a semiconductor
containing an equilibrium distribution of electrons and holes, it is usual to define a minority carrier
radiative lifetime
rad
as the time for this extra carrier to be annihilated radiatively by the majority
carriers.

64
In an intrinsic semiconductor
h
n (
e
n = ) is given by the concentration of thermally excited
holes (usually denoted by
i
p ). For large bandgap semiconductors
i
p (
i
n = ) is very small and hence
rad
tends to be large, ranging from hours in Si to microseconds in smaller bandgap semiconductors
like InSb.
rad
is always very large for indirect bandgap semiconductors, since their electic-dipole
indirect transition probabilities are smaller. In doped semiconductors the majority carrier
concentrations are often much higher than the intrinsic carrier concentrations. As a result the
minority carrier radiative lifetimes depends on the doping concentration. There is a limit, though, to
how much we can decrease
rad
by increasing the majority carrier concentration [5.16].
Band-to-band transitions tend to dominate at higher temperatures where all the shallow
impurities are ionised. A band-to-band transition can be observed mostly by electroluminescence,
while it is less present in the photoluminescence, where the observed emissions are often exciton
recombinations [5.14].
.
Exciton emissions
In PL experiments on high purity and high quality semiconductors, the photon excited
electrons and holes can attract each other by Coulomb interaction and form free excitons (FE). As a
result, the PL spectra should be dominated by the so-called free exciton peak produced by the
radiative annihilation of FE. When the sample contains a small number of donors or acceptors in
their natural state, the FE will be attracted to these impurities via van der Waals interaction. Since
this attraction lowers the FE energy, neutral impurities are very efficient in trapping FE to form
bound excitons (BE) [5.16].
In a direct-gap semiconductor, where momentum is conserved in a simple radiative
transition, the energy of the emitted photon is:

g FE
h E E = (5.3.1)
where
FE
E is the binding energy of the FE, also called dissociation-energy. The FE state is
positioned near the bottom of the conduction band.
With increasing temperature, the integrated intensity of the FE emission peak ( ) I T is
reduced as follows [5.17]:
0
/
( )
1
FE
E kT
I
I T
Ce
=
+
(5.3.2)
The above relation is deduced from Boltzmann statistics with respect to the occupation numbers of
the energy states contributing to the PL-emission.

65
Donor-acceptor pair (DAP) transitions
The existence of pairs of oppositely charged defects in semiconductors provides efficient
radiative recombination centers for excitons. While the ground state of the system is given by the
ionized donor and acceptor with interimpurity distance R , photo-excitation leads to a neutral pair in
an excited state. This state can be described as an exciton bound to the ionized donor-acceptor core
or as a neutral donor and a neutral acceptor perturbed by the interaction with each other. A simple
approach based on the effective mass theory leads to the recombination transition energy:

( )
2
g D A
e
hv E E E
R
= + + (5.3.3)

where E
g
is the bandgap energy; E
D
and E
A
is the ionisation energy of the donor and the acceptor,
respectively. The last term in Eq. (5.3.3) represents the Coulomb interaction between the donor and
acceptor for a distance R . As donors and acceptors occupy definite sites within the crystal lattice
the distribution of different pairs with distances
i
R is determined by lattice statistics [5.15].

5.4 Photoluminescence Excitation (PLE) spectroscopy

Photoluminescence excitation (PLE) spectroscopy is a powerful tool for the experimental
investigation of the electronic states of impurity atoms or defects in semiconductors. Whereas the
usual low-temperature photoluminescence (PL) provides mainly information about the ground states
in the band gap due to the presence of crystal imperfections (impurities or intrinsic defects), the PLE
is able to access their excited states, which provides important information about the structure of the
electronic levels.
PLE spectroscopy effectively combines the information provided by PL and absorption
spectroscopy to gain an additional specificity; it identifies those absorption processes, which lead to
the excitation of the selected PL band.
In the PLE technique, the spectrometer is set to the detection emission of a particular photon
energy from the sample. The intensity of this PL-emission is then recorded as a function of the
excitation photon energy [5.16]. The PLE signal is proportional to the number of photons of the
detection wavelength
0
, generated by one incident photon. The PLE signal intensity depends
primarily on the absorption coefficient and the quantum efficiency of the luminescence processes.
The method of PLE combines selectivity with respect to a particular defect with the high
sensitivity of photoluminescence.

66
PLE requires a monochromatic tunable light source. Convenient in the visible spectral region
are dye lasers up to wavelengths around 1000 nm. A dye laser pumped optical parametric oscillator
(OPO) is employed in the range 1.0-1.2 m. Various color center lasers cover the range between 0.8
m and 3.3 m. When the defect absorption and luminescence is strong enough (due to large defect
concentrations and/or high radiative quantum efficiencies) monochromized radiation from
incandescent lamps can also be employed instead of lasers.
PLE has become very popular for studying thin epilayers grown on opaque bulk substrates. It
is often assumed that the PLE spectrum is roughly equivalent to the absorption spectrum of the
sample [5.16]. The supposed equivalence between PLE and absorption signals in semiconductors
strongly relies on the assumption that the recombination times are much larger than the intraband
relaxation times, i.e., if the laser-excited electrons and holes have enough time to relax completely
into quasi-equilibrium before radiative recombination. In this case, the emission intensity at the
lowest exciton becomes independent of the relaxation rate, and the PLE spectrum can be argued
phenomenologically to mimic the absorption signal [5.16]. However, this assumption has never been
justified by microscopic quantum-kinetic studies. Furthermore, another intriguing question has
remained completely unaddressed so far in the literature: What happens if the time t between
pulse excitation and PL detection is kept shorter than the intraband thermalization times? Then, the
one-to-one correspondence between PLE and absorption signals should break down completely, and
no simple arguments can be given what the PLE signal looks like.

5.5 Raman spectroscopy

5.5.1 Theory of Raman scattering in molecules
Raman scattering is inelastic scattering of light usually by molecular vibrations [5.18]. The
classical theory of Raman scattering is based on the idea that, in a diatomic molecule, the
electromagnetic field t cos E E
L 0

, ,
= of the incident light induces a time dependent dipole moment
E P
, ,
= , where is the electronic polarizability which depends on the electric charge distribution
of the dipole. For sufficiently small displacements of nuclei from their equilibrium position,
changes linearly with the normal coordinate ( )
1 2
u u Q = ( : reduced mass,
1
u ,
2
u :
displacements of molecules) and can be expanded in Taylors series as:
+
|
|
\
|
+
|
|
\
|
+ =
2
0
2
2
0
0
2
1
Q
Q
Q
Q

. (5.5.1)

67
The first-order Raman effect is determined by the term linear in Q. If the molecule vibrates
with the frequency
S
, then t Q Q
S
cos
0
= == = . In this case, the total dipole moment has the form:
( ) t cos E t cos Q
Q
P
L 0 S 0
0
0

, ,
|
|
\
|
|
|
\
|
+ = . (5.5.2)
With the application of trigonometric sum rules, the above relation yields:
( ) ( ) ( ) [ ] t cos t cos E Q
Q 2
1
t cos E P
S L S L 0 0
0
L 0 0

+ +
|
|
\
|
+ =
, , ,
. (5.5.3)
This equation shows that the induced dipole moment P
,
vibrates not only at the frequency
L
, but
also at the frequencies
S L
.
The intensity of scattered light per unit solid angle ) (t I is given by:
( ) ( )
( ) ( ) [ ]
terms cross
t k t k t k AE
t P A t I
S L S L L
+
+ + + =
=

2 2
2
2 2
1
2 2
0
2
0
2
cos cos cos , (5.5.4)
where
4 2
0
2
0 L
k = , ( )
2
4
2 2
1 0
0
1
4
L S
k Q
Q

| |
=
|
\
, ( )
2
4
2 2
2 0
0
1
4
L S
k Q
Q

| |
= +
|
\
The first term in
Eq. (5.5.4) is known as Rayleigh scattering, the second and third terms represent Raman scattering
at the Stokes (
S L
) and anti-Stokes frequency (
S L
+ ), respectively [5.19].
The first-order Raman scattering process can be virtually decomposed into three electronic
transitions: The interaction with an incident photon (
L
h ) results in the simultaneous excitation of a
phonon (
S
h ) and the inelastic scattering of the photon (
SC
h , at frequency
S L SC
= ) as
shown in Fig. 5.5.1. The Stokes and anti-Stokes scattering can be described by Feynman graphs
indicating that in the Stokes process, a phonon is created, while in the antiStokes process, the
phonon is annihilated.
In Stokes scattering, excitation starts at the ground state, while, in antiStokes scattering, an
excited state is the starting state (Figs. 5.5.1b) and c)). For optical phonons and not too high
temperatures, the population of the ground vibrational level ( 0 ) is much greater than that of
excited vibrational levels ( 1 ).

68
0
1
2
L
h
SC
h
r
S
h
0
1
2
L
h
SC
h
r
n
s
=2
L
h
SC
h
r
S
h
n
s
=1
n
s
=0
a) Rayleigh scattering b) Stokes scattering c) antiStokes scattering
virtual
level

Fig. 5.5.1 Transitions for a) Rayleigh scatting, b) first-order Stokes scatting and c) first-order
antiStokes scatting [5.19].

5.5.2 Raman tensor in solids
In case of crystals, the susceptibility tensor
jl
is used rather than the scalar polarizability
. The susceptibility can be expanded in analogy to in Eq. (5.5.5) according to [5.18]:
( ) +
|
|
\
|

+
|
|
\
|
+ =
m q
m q m q
jl
q
q q
jl
jl jl
Q Q
Q Q
Q
Q
0
,
2
0
0

, (5.5.5)
where the sum runs over all normal coordinates.
q jl
Q / is a component of the derived
polarizability tensor, which is known as the Raman tensor and written as ( )
q
jl
, or
jlq
.or
q jl ,
.
The components of the tensor have three indices. j and l extend over the coordinates 1 to 3 and q
runs over the 3N-3 normal coordinates for the vibrations, where N is the number of atoms in the unit
cell. In other words, q runs over all optical modes with wave vector k=0. Thus, the Raman tensor
which refers to all zone-center vibrations has rank three. For an individual mode, this tensor is given
by a matrix with three rows and three columns determined from the derived susceptibilities. This
quantity is called the Raman tensor of a particular mode with its distinct symmetry.
The scattering geometry can be described by the Porto notation as: a(bc)d, where the letters
refer to Cartesian coordinates x,y,z. a and d give the directions of the incident and scattered light
wavevector, respectively, b and c give the directions of the corresponding polarizations [5.18]. In
Table 5.5.1, the Raman tensors and their symmetries A, B, E (see 2.1.4) are given for the point
group D
2d
in the orthogonal systems O: [100], [010], [001]. [5.20].

69
Table 5.5.1 Raman tensors and their symmetries for the point group D
2d
( 42m) in the orthogonal
systems O: [100], [010], [001] [5.18].

When the energy of photons used to excite Raman scattering in a medium is resonant with
some electronic transitions of the medium, one expects in general the Raman cross sections to be
enhanced. This phenomenon is known as Resonance Raman scattering (RRS) [5.21].
A
1
B
1
B
2
(z) E(y) E(x)
( (( (
( (( (
( (( (

( (( (

b 0 0
0 a 0
0 0 a

( (( (
( (( (
( (( (

( (( (

0 0 0
0 c 0
0 0 c

( (( (
( (( (
( (( (

( (( (

0 0 0
0 0 d
0 d 0

( (( (
( (( (
( (( (

( (( (

0 0 e
0 0 0
e 0 0

( (( (
( (( (
( (( (

( (( (

0 e 0
e 0 0
0 0 0

70
6. EXPERIMENTAL

6.1 Experimental set-ups

6.1.1 Photoreflectance (PR) and Electroreflectance (ER) spectrometer
The experimental set-up of the PR- (and ER-) spectrometer (Fig. 6.1.1) consists of a spectral
lamp (XBO, 100 W or Tungsten/halogen lamp 75 or 100 W), a single diffraction grating
monochromator (CVI, 1200/grate, 0.25 m), set in the path of the incident light beam, several mirrors
and lenses to guide the incident and reflected light, and a semiconductor detector (Si- or InGaAs-
diode). The modulation source is an Ar
+
- or Kr
+
-laser chopped by a mechanical chopper at a
frequency of 10 Hz. Laser light scattered on the sample is spectrally separated by a second
monochromator (SPEX 1704, 1600/grate, 1 m) set in the path of the reflected light. The detected
light is amplified by lock-in techniques. For scans in the energy region above 1.5 eV, the XBO lamp
and the Si-detector may be used. Below 1.5 eV, the halogen lamp and the InGaAs detector should be
used instead. For low temperature measurements, samples are cooled down to 20 K in a closed-cycle
He-cryostat (a chopping frequency of 30 Hz is then chosen).

71

Fig. 6.1.1 Photoreflectance spectrometer.

6.1.2 Raman spectrometer
The Raman set-up (Fig. 6.1.2) consists of a vertically polarized Kr
+
- (or Ar
+
-) laser, with a
small prism monochromator set in its path to filter out the laser plasma lines, and several mirrors to
guide the laser beam. A cylindrical and a spherical lens are used to focus the incident and scattered
light, respectively. Raman scattering is spectrally analyzed by a double grating monochromator with
a GaAs-PMT detector. The Raman spectra of chalcopyrite films are recorded in the region 50-700
cm
-1
under the excitation of the 647.1nm Kr
+
-laser line (or the 514.5 nm Ar
+
-laser line) at output
powers varying between 150 and 300 mW.

72

Fig. 6.1.2 Raman spectrometer.

6.1.3 Photoluminescence (PL) and Photoluminescence Excitation (PLE) spectrometer
The PL-PLE spectrometer is shown in Fig. 6.1.3. The PL and PLE spectra are excited by a
tungsten halogen lamp (beam power: 250 W) dispersed by a 0.27 m double-grating monochromator
as tunable light source. The excitation source is chopped by a mechanical chopper at a frequency of
80 Hz. The emission is spectrally dispersed by a 0.3 m double-grating monochromator and detected
with a cooled Ge-photodiode. The detected light is amplified by lock-in techniques. The samples are
cooled down at 7 K in a continuous-flow He cryostat.

Fig. 6.1.3 The PL-PLE spectrometer (7 K).

73

PL spectra are also excited by the 514.5 nm of an Ar
+
-laser at 2 K. Several mirrors and
spherical lenses are used for guiding and focusing the incident and the scattered beam. The emission
is spectrally analyzed by a single-grating monochromator (Jarrell Ash, Czerny-Turner, 1 m). The
plasma lines of the laser beam and the parasitic light are discarded using a combination of
interference and colour filters. For measurements acquired in the lower energy region (down to
1300nm=0.95 eV), a N
2
-cooled Ge-photodiode is used as a detector. In this case the emitted light is
amplified by a lock-in amplifier (Stanford Research Systems SR510) and the reference signal has a
chopping frequency of 85 Hz. In the higher energy region (above 900 nm =~1.4 eV), a GaAs- diode
combined with a Picoamperometer (Keithley 417) is used as a detector. The samples are cooled
down in a liquid-He-bath cryostat. The PL-set up is shown in Fig. 6.1.4.

Fig. 6.1.4 The PL-spectrometer (2 K).

6.1.4 Spectroscopic ellipsometers (SE)
The spectroscopic ellipsometer used (Fig. 6.1.5) in our experiments is a commercial SE800
Sentech Instruments GmbH ellipsometer. The light source is a xenon arc lamp. The rotating analyser
is operated in a step scan mode while the motorized polarizer is fixed at 45 with respect to the plane
of incidence during the measurements. The reflected beam is analysed by spectrometer equipped
with a fast CCD array. The spectra are recorded in the spectral range of 230-620 nm (2-5.4 eV). The
data are analyzed using SpectraRay II software.

74

Fig. 6.1.5 The SE800 Sentech Instruments GmbH spectroscopic ellipsometer.

For ellipsometric measurements at lower energies (0.75-4.2 eV), a VASE J.A. Woolam Co.
spectroscopic ellipsometer is used (Fig. 6.1.6). In the VIS-NIR range (1000-1700nm) a quartz
tungsten halogen (QTH) lamp is used as a light source combined with an InGaAs-based diode. Light
source and detector are changed to a Xe lamp and a Si-based diode, respectively, for the 400-
1000nm spectral range.

Fig. 6.1.6 The VASE Woolam spectroscopic ellipsometer.

75
7. RESULTS AND DISCUSSION
- CHALCOPYRITE SELENIDE HETEROSTRUCTURES
Epitaxial layers

Up to now, the best efficiencies of 19.5 % for chalcopyrite-based solar cells have been
achieved using CuIn
1-x
Ga
x
Se
2
(CIGS) absorbers with a Ga content of x=0.25 and a band gap of
E
g
=1.15 eV [7.1]. However, solar cells based on quaternary absorbers have not reached their
theoretical conversion efficiencies: 33 % for an absorber band gap of E
g
=1.15 eV, as expressed
by the black body efficiency limit of solar cells. The efficiencies of real CIGS solar cells are
limited by two parameters: spatial fluctuations due to variations of alloy composition, stress and
stoichiometry of the absorber layer and electrostatic potential fluctuations due to charged states
either within the grains, at grain boundaries, at interfaces or at surfaces of CIGS films. The latter
fluctuations are the most significant, but both ones influence the measured electronic and optical
properties of the absorber layers and thus the performance of the corresponding solar cells [7.2].
CIGS epitaxial layers with six different Ga-fractions constitute a representative system for
studying the material properties of quaternary chalcopyrites with the aim to optimise the
performance of CIGS photovoltaic devices. In this work, the effects of Ga addition in the optical
properties of the quaternary selenides are investigated using a variety of methods, as described in
the following:
1) in 7.1, the fundamental band gaps of CIGS layers are directly determined using
Photoreflectance (PR) spectroscopy which measures the derivative of the dielectric
function, at room and low temperatures (20 K). The higher band gaps of the CIGS
compounds are calculated from the second derivative of the dielectric function in 7.4,
using the complementary method of Spectroscopic Ellipsometry (SE) at room
temperature (RT).
2) the phonon mode frequencies of the quaternary CIGS compounds, interacting with the
electronic transitions are calculated in 7.2 by RT Raman scattering and are discussed
together with the RT PR-results.
3) in 7.3, the role of defects in the fundamental band gaps of the CIGS alloys is studied by
Photoluminescence (PL) spectroscopy at temperatures down to 2 K and
Photoluminescence Excitation (PLE) spectroscopy at 7 K. By combining the PR-, PL-
and PLE-results, an excitation schema in agreement with structural XRD analysis is
introduced. The donor and acceptor binding energies of the CIGS chalcopyrite
compounds are determined.

76
7.1 (RT&LT) Study of CuIn
1-x
Ga
x
Se
2
epitaxial layers by Photoreflectance (PR) spectroscopy

a) RT PR-spectra
In Fig. 7.1.1, the room temperature PR spectra of CuIn
1-x
Ga
x
Se
2
(CIGS) epitaxial layers
with different Ga fractions (x=0.08-0.82) are presented. The chalcopyrite band structure of the
upper-most valence-band has been already described in detail in 2.3. In the PR-spectra of the
CIGS layers, with x<0.80, only the E
a
-band of the quaternary compound is observed. The PR-
signal of the GaAs-substrate is not observed, since the incident light beam, at energies in the
range of the band-gap energy of GaAs (1.42 eV at 300 K), is completely absorbed in the
chalcopyrite layers (for x<0.80, (CIGS)=1.4-4.7x10
4
cm
-1
[7.3].
With increasing the x ratio, the E
a
-band energy shifts to higher values, varying from the
CuInSe
2
band energy (E
a
=1.02eV) to that of CuGaSe
2
(E
a
=1.68 eV). According to Ref. [7.4],
Ga-addition to CuInSe
2
(CIS), to form the CIGS alloy, increases the band gap energy which is
given by: E
g
(x)=E
a
=1.010+0.626x-0.167x(1-x), with a bowing factor of b=0.167.
For x<0.30, the PR-bands are sharp and intensive, even at 300 K. With the increase of the
Ga-fraction between 0.30<x<0.80, the PR-bands are broadened and less intensive. For x>0.80,
the PR spectra exhibit a more complicated band-shape, evident of the different structure of the
epilayers with very high Ga-content, which is in agreement with the results referred in Refs.
[7.5], [7.6].
In fact, the PR-bands observed confirm the presence of a quaternary CIGS and a ternary
CuGaSe
2
(CGS) phase, as shown by SEM and XRD analysis [7.6]. The high-resolution XRD
(HR-XRD) diffractograms of the CIGS layers are given in Figs. 7.2.1c) and 7.3.1c) [7.6], [7.7].
The HR-XRD diffractograms of the films with x0.30, grown at 570 C, indicate the presence of
a heavily-strained CGS layer at the CIGS/GaAs interface. Diffusion of Ga from GaAs into the
CIGS films has been observed in Ref. [7.10] as well. The three valence split-bands of the ternary
compound, E
a
, E
b
and E
c
, are detected at energies 1.68 eV (Fig. 7.1.1).
The fundamental transition energies of the CIGS layers were obtained by line-shape
analysis of the PR-spectra using a Third Derivative Functional Form (TDFF). A representative
fitting of a PR-spectrum using one Aspnes function (denoted as DT in the fitting program
DATLAB used) (Eq. 5.1.8, 5.1.2) is shown in Fig. 7.1.2 for the film with x=0.08. The
parameters derived from the fitting, for 3D critical points (m=2.5), are: the band-gap energy E
g
,
the amplitude A, the broadening and the phase . The E
a
-transiton energies of the CIGS layers
at RT are listed in Table 7.1.1.

77
1.0 1.2 1.4 1.6 1.8 2.0 2.2
E
c
E
b
E
b
E
a
E
a
E
a
E
a
E
a
E
a
E
a
R
/
R

(
x
1
0
-
3
)
CuIn
1-x
Ga
x
Se
2
300 K

0.82
x0.5
x0.5
0.60
0.50
0.33
0.19
x=0.08
Energy (eV)

Fig. 7.1.1 Compositional dependence of the PR-spectra of CIGS epitaxial layers at 300 K (for
x=0.82, solid arrows designate the PR-bands of the CIGS phase, dotted arrows those
of the CuGaSe
2
phase).

Table 7.1.1 E
a
-, E
b
- and E
c
-transition energies of CIGS compounds in dependence of
composition at 300 and 20 K.

[Ga]/([Ga]+[In]) 300 K 20 K
E
a

(eV)
E
b

(eV)
E
c

(eV)
E
a

(eV)
E
b

(eV)
E
c

(eV)
0.08 1.083 - - 1.080 1.101 1.312
0.19 1.141 - - 1.146 1.156 -
0.33 1.152 - - 1.175 1.254 -
0.50 1.301 - - 1.318 1.340 -
0.60 1.369 - - 1.371 1.407 -
0.82 1.514 1.568 - 1.554 1.610 -
1.00 1.676 1.789 1.994 1.704 1.824 2.034

78
1.00 1.05 1.10 1.15 1.20
-0.15
-0.10
-0.05
0.00
0.05
0.10
0.15
E
g

E
g
:1.08280.0005
A:1.56551x10
-4
6.52x10
-6

:1.4504x10
-2
5.47x10
-4
:5.450.07
m: 2.5
CuIn
0.92
Ga
0.08
Se
2
, PR 20 K
R
/
R

(
x
1
0
-
3
)
Energy (eV)

Fig. 7.1.2 Fitting of the PR-spectrum of a CIGS layer with x=0.08 (Evaluation example of a PR-
spectrum). The function used is: MB+DT. MB corresponds to a manual linear
background used as a baseline and DT to one Aspnes function. The fitting parameters
are: band-gap energy E
g
, amplitude A, broadening , phase . m=2.5 corresponds to
the dimension of the critical point.

The value of the ternary at x=1 was obtained from the PR-spectrum of the quaternary
with x=0.82. The fitted values in dependence of composition are presented in Fig. 7.1.3 and are
in good agreement with those known from the literature [7.3], [7.4] for quaternary chalcopyrites
with the same Ga fraction as the ones measured here. This dependence can be described by a
quadratic polynomial as:
E
a
=1.054 + 0.313 x + 0.310 x
2
eV (7.1.1)

For x=0.82, the E
b
-transition energy of the quaternary compound and the E
a
- E
b
- and E
c
-
transition energies of the ternary (Fig. 7.1.3) could be also calculated: E
b
(CuIn
0.18
Ga
0.82
Se
2
)=
(1.5680.001)eV, and E
a
(CuGaSe
2
)= (1.6760.001)eV, E
b
(CuGaSe
2
)= (1.7890.002)eV and
E
c
(CuGaSe
2
)= (1.9940.008)eV. The fitted value of the E
a
-transition of the ternary, E
a
=1.676
eV, is in agreement with the value, E
a
=1.677 eV, calculated with Eq. (7.1.1) by extrapolation to
x=1.

79
0.0 0.2 0.4 0.6 0.8 1.0
1.0
1.2
1.4
1.6
Experimental data
quadratic fit of exp. data
Ref. [7.4]
Ref. [7.3]

B
a
n
d

g
a
p

e
n
e
r
g
y
,

E
a

(
e
V
)
[Ga]/([Ga]+[In])
CuIn
1-x
Ga
x
Se
2
300 K

Fig. 7.1.3 Compositional dependence of the E
a
-transition energy of CIGS epitaxial layers at 300
K (comparison with values known from spectroscopic ellipsometry measurements
[7.3], [7.4]).

b) LT PR spectra (20 K)
In Fig. 7.1.4, the low temperature (LT) PR spectra of CIGS epitaxial layers with different
Ga fractions (x=0.08-0.82) are presented.
In the PR-spectra of quaternary layers recorded at 20 K, both the E
a
-and E
b
-bands are
present. Though they lie energetically close to each other, they are clearly resolved. The energy
separation of the E
a
- and E
b
-bands increases with the increase of Ga fraction at maximum
amounts to 40 meV, except for the layer with x=0.33, where it is twice as much. Evidently, the
energy separation of the two upper valence split bands of quaternary CIGS chalcopyrites is
relatively small indicating small distortion of cubic symmetry. With the increase of the x ratio,
the band energies shift to higher values in accordance with the observations of this work (Table
7.1.1, Fig. 7.1.1) and the literature reports [7.3], [7.4] on the compositional dependence of band
energies at room temperature. For x0.50, the three valence split-bands of the ternary CuGaSe
2
-
phase, E
a
, E
b
and E
c
, formed at the CIGS/GaAs interface are additionally observed.
The transition energies at 20 K were calculated using TDFF (see Evaluation example of a
PR-spectrum, Fig. 7.1.2) and are listed in Table 7.1.1 together with the values at 300 K. As
expected, the low temperature transition energies are higher than the ones at room temperature.

80
For the quaternary layers studied in this work, a quadratic dependence on composition was found
at 20 K for both, the E
a
- (Eq. (7.1.2)) and the E
b
-transition energies (Eq. (7.1.3)), which is
depicted in Fig. 7.1.5. The E
a
- and E
b
-transition energies of the ternary intermediate layer,
obtained from the PR-spectrum of the quaternary compound with x=0.82, have been also
included in order to derive Eqs. (7.1.2) and (7.1.3).

E
a
=1.051 + 0.359 x + 0.299 x
2
eV (7.1.2)
E
b
=1.084 + 0.298 x + 0.433 x
2
eV (7.1.3)

For the intermediate CuGaSe
2
layer with x=0.82, the fitted values of the E
a
- E
b
- and E
c
-
bands (Fig. 7.1.3) are: E
a
=(1.7040.001)eV, E
b
=(1.8240.001)eV and E
c
=(2.0340.002)eV. The
fitted value of the E
a
-transition of the ternary, E
a
= 1.704 eV, is almost equal to the value,
E
a
=1.709 eV, obtained from Eq. (7.1.2) by extrapolation to x=1. However, the E
a
-transition
energy is considerable lower than previously reported [7.9], [7.10].
In particular, it is lower than the respective energy measured in Ref. [7.10] with PR
spectroscopy at 20 K on a CuGaSe
2
single crystal grown by Chemical Vapor Transport (CVT)
(E
a
=1.726 eV) and slightly lower than that measured on a CuGaSe
2
layer grown by MOVPE on
GaAs (001) substrate (E
a
=1.714 eV) in the same work. Reciprocal space mappings of the films
studied have shown that the CuGaSe
2
layer is highly tensile strained. This leads to a reduction of
the band gap as it has been observed in Ref. [7.11]. The strain increases with decreasing
temperature due to the lattice contraction. In Ref. [7.10], the thermal strain for CuGaSe
2
was
calculated to 6.9x10
-3
at room temperature and 8.7x10
-3
at 20 K.
According to the results of the present work, small variations of composition, in the order
of x=10%, lead to an increase of the transition energies that is well resolved in the PR-spectra at
300 K (Fig. 7.1.1) and 20 K (Fig. 7.1.4). In fact, this is the first measurement on the
compositional dependence of the E
a
- and E
b
-transition energies of CIGS at low temperatures.

81
1.0 1.2 1.4 1.6 1.8 2.0 2.2
CuIn
1-x
Ga
x
Se
2
20 K
R
/
R

(
x
1
0
-
3
)
x0.4
x0.4
x0.4
x0.1
E
b
E
a
E
b
E
b
E
b
E
a
E
a
E
a
E
b
E
a
E
b
E
a
E
c
E
b
E
a
0.82
0.60
0.50

0.33
0.19
x=0.08
Energy (eV)

Fig. 7.1.4 Compositional dependence of PR-spectra of CIGS epitaxial layers at 20 K (for
x0.50, solid arrows designate the PR-bands of the CIGS phase, dotted arrows those
of the CuGaSe
2
phase).

It should be noted that at low temperatures (20 K), the band-edge is screened by the
exciton having a thermal energy of kT =2 meV. Therefore, in the LT PR spectra the E
a
, E
b
and E
c
transitions represent the A-, B- and C-exctions, respectively. On the other hand, at room
temperature the corresponding kT value is calculated to 25 meV, and the excitons with binding
energies up to 25 meV are ionised. It is thus suggested that, the LT PR-bands represent the
exciton states, while the RT PR-bands the band-gap energies. Bearing that in mind, the exciton
binding energies of the CIGS alloys are calculated at 7 K, in 7.3f) and g).

82
0.0 0.2 0.4 0.6 0.8 1.0
1.0
1.2
1.4
1.6
1.8
2.0
CuIn
1-x
Ga
x
Se
2
20 K

T
r
a
n
s
i
t
i
o
n

e
n
e
r
g
y

(
e
V
)
[Ga]/([Ga]+[In])
E
a
E
b

Fig. 7.1.5 Compositional dependence of the E
a
- and E
b
-bands of the CIGS epitaxial layers at 20
K.

Data on the gap energies of chalcopyrites known from the literature are constrained to
room temperature. Moreover, in order to obtain transition energies from spectroscopic
ellipsometry measurements, the second derivative of the ellipsometry spectra has to be calculated
(see Fig. 7.4.2, 7.4.2) [7.3], [7.4]. A quadratic dependence of the E
a
- E
b
- and E
c
-band energies
has been also found in Refs. [7.3] and [7.4]. However, the bowing parameter b, that is, the
coefficient of the quadratic term, was rather small and decreased from E
a
to E
c
.

1-x
Ga
x
Se
2
epitaxial layers by Raman spectroscopy

The Raman spectra of CuIn
1-x
Ga
x
Se
2
(CIGS) epitaxial layers are excited at room
temperature (RT) by (Figs. 7.2.1a) and b)): a) the 647.1 nm-line of a Kr
+
-laser and b) the 514.5
nm-line of an Ar
+
-laser. The results derived by excitation with the two different excitation
wavelengths are compared in 7.2c) and combined with the RT PR-spectra of the same films
already discussed in 7.1a).

83

Fig. 7.2.1 Compositional dependence of Raman spectra of CIGS epitaxial layers at 300 K under
excitation by: a) 647.1 nm and b) 514.5 nm. c) High resolution (HR)-XRD data on
the same layers [7.6], [7.7].

The optical properties (extinction coefficients k , absorption coefficients ( 4 / k = )
and penetration depths
1
) of the 514.5 nm- and the 647.1 nm-laser wavelengths in the CIGS
compounds are shown in Table 7.2.1 [7.3].
63 64 65 66 67 68 69
100
1000
10000
100000
(c)
HR-XRD
G
G
I
=
0
.
6
0
G
G
I
=
0
.
3
3
G
G
I
=
0
.
1
9
G
G
I
=
0
.
0
8
C
u
I
n
S
e
2
(
0
0
8
)
G
G
I
=
0
.
5
0
G
a
A
s
(
0
0
4
)
G
G
I
=
0
.
8
2
C
u
G
a
S
e
2
(
0
0
8
)

I
n
t
e
n
s
i
t
y

(
c
p
s
)
2-Theta ()
0 100 200 300 400 500 600 700
116
128
248
262
230
248
514.5nm Ar
+
- laser, 300mW
183
242
236
268
x2
x2
x0.5
175
CuIn
1-x
Ga
x
Se
2
x=0.08
0.19
0.33
0.50
0.60
0.82

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Raman-shift (cm
-1
)
(b)
0 100 200 300 400 500 600 700
(a)
231
93
(p.l.)
181
647.1nm Kr
+
- laser_300mW
2*267
267 231
(p.l.)
172
x=0.08
0.33
0.19
0.50
0.60
x0.5
0.82
CuIn
1-x
Ga
x
Se
2
x0.5

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Raman shift (cm
-1
)

84
a) 647.1 nm Kr
+
-laser
The RT-Raman spectra of CIGS epitaxial layers excited by the 647.1 nm-line of a Kr
+
-
laser are presented in Fig. 7.2.1a). According to the selection rules of Raman scattering, by
excitation with a vertically polarized laser beam, only the A
1
, B
1
, and B
2
modes are observed
[7.12]. The spectra consist of several peaks, assigned to phonon-modes of the quaternary CIGS
compound and modes due to the ternary CGS formed at the interface of the CIGS layer to the
GaAs substrate. Raman-frequency, width (Full Width at Half Maximum, FWHM) and intensity
are obtained by fitting the Raman-spectra with Lorentzians (see Evaluation example of a Raman-
spectrum (1) in Fig. 7.2.2).
The mode-frequency values of the CIGS layers under the excitation of the 647.1 nm-line
are shown in Table 7.2.2. The A
1
-mode of the CIGS absorber dominates the spectra and shifts,
with the increase of the [Ga]/([In]+[Ga]) content, from 172 cm
-1
to 181 cm
-1
, thus between the
A
1
-mode frequency of the CuInSe
2
(CIS) and the one of CuGaSe
2
(CGS) ternary compounds,
respectively [7.13]. This behaviour agrees with the one-mode model, according to which one
Raman peak is observed in the alloys and its frequency varies continuously between those of the
end-members [7.14].
For low Ga-fractions, x<0.30, a weak band at 231cm
-1
is additionally observed, assigned
to the B
2
(LO)-mode of the CIGS absorber, in accordance with the B
2
(LO)-mode frequency
reported for the ternary CIS compound [7.13]. The sharp peak at the same frequency as well as
the peak at 93 cm
-1
, observed for the higher Ga-contents CIGS, with x=0.50 and 0.82, are
intensive plasma lines (p.l.) of the exciting Kr
+
-laser beam [7.15]. In the Raman spectrum of the
film with the highest Ga-content (x=0.82), the B
2
(LO)-

mode of CGS

at 267 cm
-1
and its second
order at 2x267 cm
-1
are also observed. Assignment of the peak at 267 cm
-1
to the ternary rather
than to the quaternary CIGS compound is explained as follows: the penetration depth
1
of the
excitation light (647.1 nm) is calculated to be 170 nm (Table 7.2.1). At the interface of the
absorber layer near the substrate, a ~50 nm-thick CGS film is formed [7.6]; therefore, in the
Raman spectrum of the 250 nm-thick CIGS layer (x=0.82), the peak at 267 cm
-1
is more likely to
belong to the ternary compound. This result is in agreement with the high resolution (HR)-XRD
data on the same film, shown in Fig. 7.2.1c) [7.6], [7.7]. In fact, the presence of CGS-B
2
-modes,
also by excitation with the more-surface-sensitive-514.5nm-laser beam (see 7.2b)), implies the
dispersion of the ternary phase over the whole CIGS layer and the presence of CGS in a much
higher concentration near the interface to the GaAs substrate.

85
Table 7.2.1 Extinction coefficients k , absorption coefficients ( 4 / k = ) and penetration
depths
1
of the 514.5 nm-line Ar

+
-laser, the 647.1 nm-line Kr
+
-laser and the 750
nm-Tungsten lamp (7.3) wavelengths in the CIGS compounds [7.3].

[Ga]/([Ga]+[In]) Thickness
(nm)
Excitation
light
( E in eV)
k 4 / k =
2
4
10
1239.84
kE
x
=
(x10
5
cm
-1
)
1

(nm)
2.4
(514.5 nm)
0.583 1.418 71
1.9
(647.1 nm)
0.433 0.834 120
0.08

440

1.65
(750 nm)
0.38 0.636 157
2.4 0.586 1.425 70
1.9 0.436 0.840 119
0.19 440

1.65 0.38 0.636 157
2.4 0.58 1.411 71
1.9 0.433 0.834 120
0.33 360
1.65 0.373 0.625 160
2.4 0.515 1.253 80
1.9 0.385 0.741 135
0.50 390

1.65 0.318 0.533 188
2.4 0.506 1.231 81
1.9 0.376 0.724 138
0.60 290

1.65 0.294 0.492 203
2.4 0.46 1.119 89
1.9 0.31 0.600 168
0.82 250
1.65 0.186 0.311 321

b) 514.5 nm Ar
+
-laser
The RT Raman spectra of CIGS epitaxial layers excited by the 514.5 nm-line of an Ar
+
-
laser are presented in Fig. 7.2.1b). These spectra show a better signal-to-noise ratio, compared to
those excited by the 647.1 nm-line of a Kr
+
-laser. Raman spectra are recorded, in either of these
cases, using similar integration times. This is not thus expected according to resonant Raman
scattering: the 647.1 nm(1.9 eV)-laser wavelength is more resonant to the band gap energy (1.0-
1.7 eV) of the quaternary chalcopyrite selenides. In the wavelength-dependent-Raman study of
PVD-grown CuGaSe
2
thin films, reported in Ref. [7.10], lower signal-to-noise ratio spectra are
recorded by excitation with the 514.5 nm(2.4 eV)-line, compared to the spectra excited by the
676.4 nm(1.8 eV)-line and the 727.5nm(1.7 eV)-line. The enhanced Raman-signals, excited by
the 514.5 nm-laser beam, can be explained here considering the different penetration depth of the
excitation wavelengths (see Table 7.2.1) and the Ga-incorporation within the CIGS layers [7.6]
as follows: the 647.1 nm-wavelength has a twice as much penetration depth in the CIGS films,
compared to that of the 514.5 nm-wavelength (see Table 7.2.1), and thus the latter gives

86
information on a region of the CIGS layer which is closer to the surface. The Ga-gradient within
the CIGS layers [7.5] can resemble an internal step-like concentration gradient giving rise to
spatial potential fluctuations [7.2]. The higher intensity-to-noise-ratio spectra recorded using the
514.5 nm-line can be thus explained as originating by the interaction of the beam with the upper-
most, more homogeneous, region of the layer resulting in more intensive Raman peaks.
By excitation with a vertically polarized laser beam, peaks assigned to A
1
-, B
1
- and B
2
-
modes are expected, according to the selection rules of Raman scattering [7.12]. Modes assigned
to the CIGS quaternary phase and the ternary CGS phase formed at the CIGS/GaAs interface are
observed. The Raman-band frequencies are determined by fitting the Raman spectra with
Lorentzians (Evaluation example of a Raman-spectrum (1)). In Fig. 7.2.2, a representative fitting
of the Raman spectrum of the film with x=0.19 is illustrated. The background is subtracted using
a polynomial. In the fitting program DATLAB we use: a manual linear (MB) background as a
baseline and three Lorentzian (LO) functions.
As in case of the Raman-spectra excited by the 647.1 nm-line, discussed above in 7.2a),
the A
1
-mode of the CIGS compound dominates the spectra and shifts from 175 cm
-1
to 183 cm
-1

with the increase of the [Ga]/([In]+[Ga]) content. However, by excitation with the 514.5 nm-line,
more peaks assigned to the B
1
- and B
2
-modes of the CIGS phase are present, in comparison with
the spectra excited by the 647.1 nm-line (Table 7.2.2). In particular, for the film with the lower
Ga-fraction, x=0.08, two well-resolved peaks are observed at 230 and at 242 cm
-1
assigned to the
B
2
(LO)- and B
2
(TO)-modes of the quaternary compound in accordance with the mode-
assignment of the CIS and CGS ternaries, respectively [7.13]. With the increase of the Ga-
content, these two peaks become wider and shift slightly to higher frequencies. In particular, the
first peak, attributed to a CIS-like-B
2
-mode, shifts at 236 cm
-1
for the film with x=0.60 and is not
present in the spectrum of the film with the higher Ga-content. The peak at 242 cm
-1
, attributed
to a CGS-like-B
2
-mode,

is located at 248 cm
-1
in the spectrum of CIGS with x=0.33, disappears
in the ones of the films with Ga-contents in the intermediate range and appears again in the
spectrum of the film with x=0.82 at 248 cm
-1
. The films with Ga-contents, x0.33, show peaks at
105, 116 and 128 cm
-1
, assigned to the B
1
-modes of the CIGS absorber. These modes are CGS-
like modes [7.13].

87
0 100 200 300 400 500
0
10
20
30
40
CuIn
0.81
Ga
0.19
Se
2
, Raman 300 K
LO
3
LO
2
LO
1
LO
1
:1
st
Lorentzian
Pos
1
: 176.465.46x10
-2

Amp
1
: 28.45.9x10
-1

Wid
1
: 5.21.6x10
-1

LO
2
:2
nd
Lorentzian
Pos
2
: 227.621.09
Amp
2
: 2.414.08x10
-1

Wid
2
: 11.943.68
LO
3
:3
rd
Lorentzian
Pos
3
: 247.571.67
Amp
3
: 2.03.35x10
-1

Wid
3
: 17.315.41

I
n
t
e
n
s
i
t
y

(
c
p
s
)
Raman-shift (cm
-1
)

Fig. 7.2.2 Fitting of the Raman-spectrum of a CIGS layer with x=0.19 (Evaluation example of a
Raman-spectrum (1)). The function used is: MB+LO+LO+LO. MB corresponds to a
manual linear background used as a baseline and LO to one Lorentzian function. The
fitting parameters are: Pos the Raman-mode frequency, Amp the Raman-intensity and
Wid the width (FWHM).

In the Raman spectra of the films with relatively high Ga-contents, x0.50, a peak
assigned to the B
2
-mode of the ternary CGS film. This peak is more pronounced in the spectrum
of the film with the higher Ga-content (x=0.82) at a frequency of 168 cm
-1
, in accordance with
the HR-XRD data on this film, shown in Fig. 7.2.1c), revealing a sharp CGS-(008) peak.
However, a signal due to the CGS compound is not expected with respect to the penetration
depth of the 514.5 nm-wavelength calculated to 90 nm (see Table 7.2.1). This contradiction can
be surpassed by assuming that the CGS phase is dispersed over the whole CIGS layer and is
present, in a much higher concentration, near the interface to the GaAs substrate. The calculated
mode-frequencies of the CIGS and CGS chalcopyrite compounds by excitation with a 514.5 nm-
line are given in Table 7.2.2.

88
c) Comparison of Raman spectra excited by two different wavelengths
(Comparison with the CIGS PR)
The compositional dependence of the A
1
-mode frequency of the CIGS layers under
excitation with the 647.1-line Kr
+
-laser and the 514.5 nm-line Ar
+
-laser, is presented in Fig.
7.2.3. With the increase of the Ga-fraction from x=0.08 to x=0.82, the A
1
-phonon mode is, in
both cases, linearly shifted. However, by excitation with the 514.5 nm-line, the A
1
-mode-
frequencies are shifted to higher frequencies by an amount of 1-3 cm
-1
, compared to those by
excitation with the 647.1 nm-line. This can be explained with respect to the Ga-incorporation
within the CIGS layers: the interaction of the excitation laser beam with regions of different Ga-
content may shift the A
1
-mode-frequency of CIGS between the mode frequencies of the CIS and
CGS ternaries.
The present work is a first detailed investigation on the compositional dependence of the
Raman spectra of quaternary chalcopyrite compounds; there are just a few publications on the
Raman scattering from CIGS films [7.16] and [7.17].

0.0 0.2 0.4 0.6 0.8 1.0
170
172
174
176
178
180
182
184
647.1 nm-line Kr
+
-laser
514.5 nm-line Ar
+
-laser
Raman spectra, 300 K
R
a
m
a
n
-
s
h
i
f
t

(
c
m
-
1
)

[Ga]/([Ga]+[In])

Fig. 7.2.3 Compositional dependence of the A
1
-mode frequency of the CIGS epitaxial layers at
300 K excited by the 647.1-line Kr
+
-laser and the 514.5 nm-line Ar
+
-laser

According to the results of the present study, both the band-energy shift of the PR-spectra
and the phonon-frequency shift of the Raman spectra can be used to calibrate the Ga-fraction in
quaternary chalcopyrites of unknown stoichiometry.
Apart from this, the Raman and PR results (7.1) obtained at each composition
[Ga]/([In]+[Ga]) can be combined to give the energy band gap of a CIGS absorber in case that its

89
Raman spectrum is known. The combination of Raman and PR-results is illustrated in Figs.
7.2.4a) and 7.2.4b) under the excitation of the 647.1nm-line and the 514.5 nm-line, respectively.
A band-energy versus Raman-shift relationship is derived (Eqs. (7.2.1) and (7.2.2)) that can be
used for calibration purposes.

a) Excitation line: 647.1 nm: E
g
(
phonon
) =103.436-1.208 +0.004
2
(7.2.1)
b) Excitation line: 514.5 nm: E
g
(
phonon
) =98.716-1.149 +0.004
2
(7.2.2)

where is the A
1
-phonon shift of CIGS.
It is concluded that the energy band gap shifts with the A
1
-phonon frequency with a
bowing of 0.004, for both excitation wavelengths.

Fig. 7.2.4 Band-energy versus Raman-shift calibration curve for two excitation lines: a) 647.1
nm and b) 514.5 nm.

172 174 176 178 180
1.1
1.2
1.3
1.4
1.5
(a)
[Ga]/([In]+[Ga]
0.08 0.230.25 0.52 0.62 0.81
b
a
n
d
-
g
a
p

e
n
e
r
g
y

(
e
V
)
E
a
= 103.436-1.208 +0.004
2
Raman-shift (cm
-1
)
176 178 180 182
1.1
1.2
1.3
1.4
1.5
(b)
E
a
= 98.716-1.149 +0.004
2
[Ga]/([In]+[Ga]
0.81 0.62 0.52 0.25 0.23 0.08
Raman-shift (cm
-1
)
b
a
n
d
-
g
a
p

e
n
e
r
g
y

(
e
V
)

90
Table 7.2.2 Raman mode-frequencies of CIGS layers at 300 K.

1-x
Ga
x
Se
2
epitaxial layers by Photoluminescence (PL) and
Photoluminescence Excitation (PLE) spectroscopy

a) PL at 7 K
The PL emission of the CIGS layers was excited by the 750 nm-wavelength of a tungsten
lamp at 7K. In Fig. 7.3.1a), the PL-spectra of the CuIn
1-x
Ga
x
Se
2
(CIGS) epitaxial layers in
dependence of composition (x=[Ga]/([Ga]+[In])) at 7 K are presented.
The PL spectra consist of two main bands: the PL bands on the lower energy side are
assigned to the quaternary compound, while the narrower band at 1.47 eV is assigned to the
GaAs substrate. For the film with x=0.19, only one band is recorded, while for the one with
x=0.82, the PL band of the CIGS absorber is overlapped by the relatively sharper and more
intensive PL band arising from the GaAs substrate. Though the penetration depth of the
excitation wavelength (750 nm) in the CIGS layers, given in Table 7.2.1, is smaller than the
[Ga]/([Ga]+[In]) B
3
1
-
mode
(cm
-1
)
B
1
2

-
mode
(cm
-1
)
B
1
1
-
mode
(cm
-1
)
A
1
-
mode
(cm
-1
)
B
2 LO
-
mode
(cm
-1
)

B
2 TO
-
mode
(cm
-1
)

B
2

TO or
LO
-mode
CuGaSe
2

(cm
-1
)
1) excitation line: 647.1 nm
0.08 172.4
0.3
223.6
9.1

0.19 174.1
0.2
230.8
1.1

0.33 174.6
0.2

0.50 92.6
0.1
177.6
0.8

0.60 179.2
0.7

0.82 92.9
0.1
180.7
0.3
266.6
1.2
2) excitation line: 514.5 nm
0.08 175.3
0.1
230.4
1.2
242.0
0.9

0.19 176.5
0.1
228.3
1.0
247.2
1.4

0.33 128.4
0.3
177.3
0.1
226.6
1.5
247.9
2.0

0.50 116.2
0.3
128.1
0.4
180.0
0.1
224.4
1.8
262.4
3.2
0.60 180.2
0.04
236.0
1.7
260.7
0.6
0.82 105.5
0.2
115.8
0.3
182.6
0.1
248.2
5.5
268.2
0.4

91
layer thickness, the GaAs PL emission is excited. This is probably due to an increasing reduction
of the CIGS absorption coefficient, with the increase of the Ga-content and thus, an increasing
transparency of the layer with the temperature increase. Three well-resolved PL bands are
recorded for the alloys with x=0.33 and 0.60. Excluding the band originating from the substrate,
the origin of the two PL-bands of the CIGS absorbers with 33 and 60% Ga is discussed in the
following, together with the results of structural XRD-analysis: The high resolution (HR)-XRD
diffractograms of both CIGS layers (Fig. 7.3.1c), [7.6], [7.7]) show, apart from the expected
CIGS-(008) peak and the CGS-(008) peak, the latter being present in the films with x0.30,
several reflection maxima due to the inhomogeneous Ga-distribution within the films. Therefore,
the two PL bands can be explained as originating from two different regions of the films having
different Ga content and thus different band gaps. The LT PR spectra (see Fig. 7.1.4) recorded
on these films do not reveal two-phase systems. However, these spectra are relatively broad and
have a low signal-to-noise ratio, indicative of the increased disorder within these films. In fact,
the widths (FWHM) calculated for the PL emissions of the CIGS films with 8 and 19% Ga are
40 meV, while the corresponding values for the layers with 33% and 60% are twice as much,
which is found to 100 and 80 meV, respectively. Additionally, the SEM graph [7.6] of the film
with x=0.33, shows large voids within the film, revealing the large disorder and low quality of
this film, compared to the CIGS films with different Ga-contents.
A quaternary absorber layer with a similar Ga-content (x~30%), has given, up to now, in
its polycrystalline form, a CIGS solar cell of optimum efficiency (19.5 %) [7.1]. In an effort to
improve the quality of the CIGS epitaxial layer with x=0.33, grown at 570
o
C, different growth
conditions have been tried: several films with the same x ratio were grown at different
temperatures: lower (500
o
C) and intermediate (550
o
C) temperatures. However, all films with
x~0.30 appear to be extremely inhomogeneous, as shown by EDX measurements, while the PL-
signals are very sensitive to the [Cu]/[III] and [Ga]/([Ga]+[In]) ratios of the CIGS layers, already
discussed in [7.10]. Conclusively, it seems that the film with x~0.30 is not easy to be epitaxially
grown.

92

Fig. 7.3.1 PL spectra of the CIGS layers excited by a) a Tungsten lamp at 7 K and b) the 514.5
nm Ar
+
-laser at 2 K. c) High resolution (HR)-XRD data on the same layers [7.6],
[7.7].
0.8 1.0 1.2 1.4 1.6 1.8
750 nm
GaAs
x0.5
(a)
x2
x2
CuIn
1-x
Ga
x
Se
2
, PL 7 K
Tungsten lamp

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
0.19
0.08
0.50
0.33
x=0.82
0.60
0.8 1.0 1.2 1.4 1.6 1.8
x=0.82
x0.2

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
0.60
0.50
0.33
0.19
0.08
CuIn
1-x
Ga
x
Se
2
, PL 2K
514.5 nm Ar
+
-laser_200 mW
x0.2
(b)
GaAs
63 64 65 66 67 68 69
100
1000
10000
100000
(c)
HR-XRD
G
G
I
=
0
.
6
0
G
G
I
=
0
.
3
3
G
G
I
=
0
.
1
9
G
G
I
=
0
.
0
8
C
u
I
n
S
e
2
(
0
0
8
)
G
G
I
=
0
.
5
0
G
a
A
s
(
0
0
4
)
G
G
I
=
0
.
8
2
C
u
G
a
S
e
2
(
0
0
8
)

I
n
t
e
n
s
i
t
y

(
c
p
s
)
2-Theta ()

93
b) PL at 2 K
PL spectra of the CIGS epitaxial layers have been also excited by the 514.5 nm line of an
Ar
+
-laser at 2K and are shown in Fig. 7.3.1b). A laser output power of 200 mW is used. As in
case of the CIGS PL excited by the tungsten lamp, described in 7.3a), the spectra consist of
emissions assigned to the CIGS chalcopyrite layer and the GaAs substrate. In particular, the PL
bands on the lower energy side are due to the quaternary compound, while the one at 1.47 eV,
shown only in the spectra of the CIGS films with x0.50, is due to the substrate. Though the
penetration depth of the excitation wavelength (514.5 nm) in the CIGS layers, given in Table
7.2.1, is smaller than the layer thickness, an emission due to the substrate is excited, in case of
the high Ga-content (x0.50) layers. This is probably due to an increasing reduction of the CIGS
absorption coefficient, with the increase of the Ga-content and thus, an increasing transparency
of the layer with the temperature increase. CIGS PL consists of one or two bands; For the films
with x=0.19, 0.33 and 0.60, two emissions are observed. In fact, the spectrum of the film with
0.19 (Fig. 7.3.1b)) exhibits a low signal-to-noise ratio and thus the second PL peak will not be
further discussed. By comparing, therefore, the PL spectra recorded using two different
excitation sources (the Tungsten lamp at 7 K (Fig. 7.3.1a) in 7.3a) and the 514.5 nm-line Ar
+
-
laser at 2 K), the following are observed: In both cases, the films with x=0.33 and 0.60 give two
PL emissions which have been assigned to two different phases in these films (7.3a). The PL
bands of the film with x=0.33 are well resolved under excitation of either the 750 nm-Tungsten
lamp or the laser beam; on the contrary, the second band of the film with x=0.60 at 2 K is
overlapping with the GaAs PL at 1.47 eV. The PL intensity ratio of the two emissions, defined as
the first (main) PL peak-intensity over the second PL peak-intensity, is different in each of the
two-phase films (x=0.33 and 0.60): in the former case (x=0.33), the intensity-ratio is unity at 2 K
and larger than unity at 7 K. On the other hand, the intensity-ratio is smaller than unity for the
film with x=0.60 using both excitation sources (Figs. 7.3.1a) and b)).
The evaluation of the PL spectra is different in each case: at 7 K, the PL peak-energy,
peak-width (FWHM) and intensity are read or graphically estimated by the spectra, due to the
asymmetry of the emissions. On the other hand, the spectra at 2 K are fitted using Gaussians
(GA). A representative fitting of a PL spectrum is shown in Fig. 7.3.2 for the film with x=0.50.
In the fitting program DATLAB, a constant background (CB) as a baseline and two Gaussian
(GA) functions are used.

94
1.0 1.2 1.4 1.6 1.8
0
1
2
3
GA
2
GA
1
CuIn
0.5
Ga
0.5
Se
2
, PL 2 K
GA
1
:1
st
Gaussian
Pos
1
: 1.26182.89x10
-4

Amp
1
: 2.462.71x10
-2

Wid
1
: 5.8410x10
-2
7.06x10
-4

GA
2
:2
nd
Gaussian
Pos
2
: 1.46717.58x10
-3

Amp
2
: 9.72x10
-2
3.37x10
-2

Wid
2
: 4.52x10
-2
1.79x10
-2

I
n
t
e
n
s
i
t
y
Energy (eV)

Fig. 7.3.2 Fitting of the PL spectrum of a CIGS layer with x=0.50 (Evaluation example of a PL-
spectrum). The function used is: CB+GA+GA. CB corresponds to a constant
background used as a baseline and GA to one Gaussian function (GA). The fitting
parameters are: Pos the PL peak- energy, Amp the peak-intensity and Wid the width
(FWHM).

In Figs. 7.3.3a) and b), the PL peak-energies and -widths (FWHM) of the CIGS layers at
2 K and 7 K, in dependence of composition, are presented. In case that, two CIGS-emissions are
present, only the first one is studied here. The peaks excited by the laser beam (2 K) are located
at slightly lower energies than the ones excited by the 750 nm-Tungsten lamp (7 K) (Fig.
7.3.3a)). In fact, at lowest excitation densities- as in the case of the Tungsten lamp -only a few
donors are occupied by electrons. In this case, fast relaxation of electrons into energetically
lowest-lying donor states will occur before DAP recombination, giving rise to emissions at lower
energies. The dependence of the CIGS PL peak-width (Fig. 7.3.3b)) on composition is discussed
as follows: with the increase of the Ga-fraction, the PL peak-width increases, reaching a
maximum for the film with x=0.60 and decreases again for the higher-Ga content film (x=0.82)
[7.6]. The data points referring to the layer with x=0.33 are beyond the other points, due to the
large disorder of this layer, destructing the succession in the CIGS alloys (in Fig. 7.3.3b), line is
guide to the eye).

95
0.0 0.2 0.4 0.6 0.8
1.0
1.2
1.4
0.03
0.06
0.09
0.12 1
st
PL band (7 K)
1
st
PL band (2 K)
(a)
x=[Ga]/([Ga]+[In])

P
L

p
e
a
k
-
e
n
e
r
g
y

(
e
V
)
(b)
CuIn
1-x
Ga
x
Se
2
, PL 2K&7K
F
W
H
M

(
e
V
)

Fig. 7.3.3 a) PL peak-energies and b) FWHM of CIGS layers at 2K and 7K (line is guide to the
eye).

The origin of the PL emission of the CIGS quaternary alloys is discussed in the following
together with the results of PR measured on the same samples (7.1).

c) On the origin of the CIGS PL
(Comparison with the CIGS PR)

In Fig. 7.3.4, the E
a
- and E
b
-transition energies of the CIGS layers, calculated by PR (20
K), discussed in detail in 7.1 (Fig. 7.1.4, Table 7.1.1), are plotted together with the PL peak-
energy (7 K). As expected, the PL emission of the quaternary compounds shifts with the band
gap to higher energies with the increase of the Ga-content. In accordance with the compositional
dependence of the E
a
-transition, the PL peak-energy varies quadratically with the
[Ga]/([Ga]+[In]) ratio, with a bowing of 0.343, according to the equation:

2
0.968 0.303 0.343 PL peak energy x x eV = + + (7.3.1)

96
The energy difference between the PL maximum and the E
a
-band varies between 80 and
110 meV. An assumption of an excitonic PL would imply a free exciton binding energy of 100
meV, which is an extremely high value. Therefore, a luminescence mechanism due to excitons is
not possible.
0.0 0.2 0.4 0.6 0.8 1.0
1.0
1.2
1.4
1.6
1.8
2.0
PR (20 K) & PL (7 K)
E
a
-transition (PR 20 K)
E
b
-transition (PR 20 K)
1
st
PL-peak (PL 7 K)
2
nd
PL-peak (PL 7 K)

E
n
e
r
g
y

(
e
V
)
[Ga]/([Ga]+[In])

Fig. 7.3.4 E
a
- and E
b
-transition and PL peak-energies of CIGS layers at 20 K and 7 K,
respectively.

Excitation power dependent PL experiments applied on Cu-rich CuGaSe
2
films [7.18]
have shown that the dominant emission lines at low temperature (10 K) are due to the
recombination between donor and acceptor states (DAP). In the case of the quaternary system,
the PL emission of slightly Cu-rich CIGS samples has been also attributed to a DAP
recombination mechanism. A shallow acceptor state is dominant in CIGS films with a ratio of
[Cu]/([In]+[Ga])1.01.1, according to the two acceptor- and one donor-recombination model
proposed for Cu(In,Ga)Se
2
in Ref. [7.5]. In the following, the origin of the PL emissions of the
CIGS layers is studied by power dependent PL measurements:
Power dependent PL measurements are performed on the film with the higher Ga content
(x=0.82) at 2 K (Fig. 7.3.5). The PL spectra are excited by the 514.5 nm line of an Ar
+
-laser,
with an output power varying between 5 and 200 mW. At low excitation power the PL spectrum
exhibits a broad band, and the two components assigned to the quaternary compound and the
GaAs are not resolved. With increasing the excitation power, the peak at the lower energy
region, due to GaAs, is saturated and the emission spectrum of the chalcopyrite film is enhanced.
At higher excitation powers (>100 mW) the two emissions are spatially separated at 2 K. It

97
should be noted that in the PL spectra excited by the lower excitation power source of a tungsten
lamp (Fig. 7.3.1b)), the GaAs-emission is located on the high-energy side of the emission of the
film with x=0.82. The situation is reversed by excitation with the higher excitation power laser
beam (Figs. 7.3.1a) and 7.3.5).
The PL spectra with variable excitation power can measure the limit for impurity
saturation in the films and, therefore, explain the PL spectrum of the film with x=0.82 at 7 K.
The origin of the PL emission can be studied using the variation of the PL peak-energy with the
excitation power as described by the relationship:

0
( ) log( / )
peak exc exc
E P P P = i (7.3.2)

where is the energy shift/decade,
exc
P is the excitation power and
0
P is a reference excitation;
Here,
0
P =200 mW has been utilized [7.19]. For the CIGS film with x=0.82, the PL peak-energy
in dependence of excitation power is plotted in Fig. 7.3.6. By using Eq. (7.3.2), a blue shift of
11meV/decade is found for the film with x=0.82. As described by Shklovskji and Efros [7.20], a
blue shift of 1-7 meV/decade is expected for DAP transitions due to the Coulomb interaction
of the charged defects in the final state. Higher blue shifts indicate fluctuating potentials due to
high compensation of the semiconductor. Thus, the =11meV/decade, determined for the
chalcopyrite compound with x=0.82, can be related to fluctuating potentials due to the high
compensation of this semiconductor [7.5].
1.3 1.4 1.5 1.6 1.7
0.0
0.4
0.8
1.2
1.6
2.0
CIGS
GaAs
CuIn
0.18
Ga
0.82
Se
2
PL 2 K, 514.5 nm Ar
+
-laser

P
L
-
i
n
t
e
n
s
i
t
y
200 mW
100 mW
50 mW
40 mW
30 mW
20 mW
15 mW
10 mW
5 mW
Energy (eV)

Fig. 7.3.5 Power-dependent PL spectrum of the CIGS film with x=0.82 at 2 K.

98

-2.0 -1.6 -1.2 -0.8 -0.4 0.0 0.4
1.50
1.51
1.52
1.53
CuIn
0.18
Ga
0.82
Se
2
=11meV/decade
PL 2 K, 514.5 nm Ar
+
-laser

log (P
exc
/P
o
)
P
L

p
e
a
k
-
e
n
e
r
g
y

(
e
V
)

Fig. 7.3.6 PL peak-energy in dependence of excitation power for the CIGS film with x=0.82 at
2 K.

The dependence of emission intensity on excitation power
exc
P , can give an additional
information on the origin of the luminescence mechanism. According to ref. [7.19], an intensity
versus excitation-power law has been derived:

I
k
exc
P , (7.3.3)

where the exponent k describes the increase of PL intensity with the excitation power. 1 k < is
expected for defect-related recombination, like donor-acceptor-pair (DAP) or free-to-bound (FB)
transitions. Values below 1 have been also found for excitonic transitions. For the CIGS layer
with x=0.82, a value of k =0.94 is calculated.
Combining the PL- and the PR-results, a donor-acceptor recombination mechanism
(DAP) of the PL emission of the CIGS layers is concluded.

d) PLE at 7 K
The incorporation of the defects in the quaternary alloy is further investigated by
Photoluminescence Excitation (PLE) spectroscopy. PLE spectra are recorded at 7 K with the
detection energies fixed at the PL maximum or maxima -in case of the films with x=0.33 and
0.60- and energies corresponding to the left and right flank of the PL emissions. The flanks

99
correspond to positions located at the full width at half-maximum (FWHM) of the main PL
emission. The PLE spectra of CIGS with various Ga-contents are shown in Figs. 7.3.7a)-f),
together with their PL emission already given in Fig. 7.3.1a). For the film with x=0.82, PLE is
also recorded with the wavelength fixed to the PL maximum of the GaAs substrate (denoted as
GaAs PL-max in Fig. 7.3.7f)).
The spectra of the films with x=0.08 and 0.33, representative for low and high Ga-
content, respectively, will be discussed below in detail.
0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
1.062
CuIn
0.92
Ga
0.08
Se
2
, PL/PLE 7K
1.336 1240 nm
1258 nm (PL-max1)
1284 nm
1.107

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
(a)
(III)
(II)
(I)

0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
(b)
CuIn
0.81
Ga
0.19
Se
2
, PL/PLE 7K
1.131
1.40
1200 nm
1166 nm (PL-max1)
1152 nm

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
1.179

100
0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
(IV)
1.14
1.52
(II)
(III)
(I)
CuIn
0.67
Ga
0.33
Se
2
, PL/PLE 7 K
1.232
1.305
1.266
1.43

1202nm
1164nm (PL-max1)
1120nm
1000 nm (PL-max2)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
(c)

0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
CuIn
0.5
Ga
0.5
Se
2
, PL/PLE 7K
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)

1.362
1.373
1.403
1038nm
1010nm (PL-max1)
990nm
Energy (eV)

(d)
1.308

101
1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8
1.359
1.445
1.46
1.48
1.521
CuIn
0.4
Ga
0.6
Se
2
, PL/PLE 7K

1011nm
982nm (PL-max1)
960nm
880nm (PLmax2)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
(e)

1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
CuIn
0.18
Ga
0.82
Se
2
, PL/PLE 7K
CIGS
GaAs
1.612
1.521
892nm
865nm (PL-max1)
843nm (GaAs PL-max)
834nm

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
(f)

Fig. 7.3.7 PL- and PLE-spectra of CIGS layers at 7 K (PL-max1 and PL-max2 designate the
first and second PL peak-energy of the CIGS layers, respectively).

In case of the film with the lower Ga-content (x=0.08), the three PLE spectra, denoted as
line (I), (II) or (III) in Fig. 7.3.7a), show identical results. The corresponding PLE spectra
recorded on the film with x=0.19 (Fig. 7.3.7b)) are also similar to each other. Only line (I)

102
recorded with the detection at the maximum of 0.987 eV will be further discussed. There is a
sharp rise in the spectrum above 1.062 eV, known as onset, and a well-pronounced peak at 1.107
eV. An additional structure at 1.336 eV is observed at higher energies than the main peak (I).
The PLE-results can be interpreted as follows:
The E
a
-, E
b
- and E
c
- transition energies reported for the layer with x=0.08, at 20 K, are:
1.080, 1.101 eV and 1.312 eV, respectively (see Table 7.1.1). By combining the PR- and the
PLE-results, an energy difference of approximately 25 meV is obtained between the PLE maxima
at 1.107 and 1.336 eV and the E
a
(1.080 eV) and E
c
(1.312 eV) transition energies, respectively.
Bearing in mind, that at low temperatures the band-edge is screened by excitons, the
PLE-shift to higher energies, with respect to the PR-band energies, can be interpreted in the
frame of i) band-to-band transitions and ii) a phonon-assisted transition-mechanism.
Case (i) will be discussed in detail in 7.3f).
In case (ii), phonon-energies of 21.4 and 21.6 meV are determined for the most
pronounced A
1
-mode of the films with x=0.08 and 0.19, respectively, by taking into account the
Raman analysis of the same CIGS layers under excitation with 647.1 nm Kr
+
-laser at RT, as
discussed in 7.2. With respect to the E
a
- and E
c
-gap energies, extracted from the PLE maxima,
the red-shift of the PR-band energies can be thus attributed to an interaction of the edge exciton
with the A
1
-phonon mode in the quaternary alloy system.
The PLE spectra obtained for the films with higher Ga-content, x0.30, are more
complicated. For the CIGS layers with x=0.33 and 0.60 (Figs. 7.3.7c) and e), respectively), it is
reminded that the corresponding PL spectra (Fig. 7.3.1a) excitation by 750 nm tungsten lamp)
consist of two bands. Excitation spectra were successively recorded with the detection energy
fixed first at the lower, and then at the higher PL maximum, denoted as PL-max1 and PL-max2,
respectively, in Fig. 7.3.7c). For the film with x=0.33 (Fig. 7.3.7c)), for example, the spectra
obtained with the detection set to 1.071 eV (I) and 1.252 eV (IV), are significantly different: the
lower energy recombination at 1.071 eV is excited at 1.14 eV, while the recombination at 1.252
eV is excited at 1.34 eV. Excitation spectra have been also recorded with the detection at the left
(II) and the right (III) flank of the first PL band. No features due to the first emission (at 1.071
eV) are shown in line (IV). The PLE spectra give no indication, thus, of the two phases of this
film, clearly observed on the corresponding PL spectra (Fig. 7.3.1a)). This may be due to the fact
that the energy difference (1.34-1.18) eV =160 meV between the onsets of the lines recorded at
the two PL maxima is smaller than the one needed for resolving the two different emissions (180
eV) by PLE, and therefore the two different phases in these films. It should be noted, that the
onset gives the energy needed for the excitation of the corresponding recombination. Structures
observed at 1.43 eV on lines (II) and (III), and at 1.52 eV, on lines (I) and (III), arise from the

103
GaAs substrate and overlap with the PLE signal of the chalcopyrite layers. As shown in Fig.
7.3.7c), the PLE spectra of the film with x=0.33 exhibit a significant dispersion of the maximum
energies and the onsets in dependence of the detection energy. This is observed on the PLE
spectra of all layers with Ga-content in the intermediate range 0.30<x<0.60. The PLE spectrum
of the film with x=0.82 is not easy to evaluate due to the overlap of the CIGS absorption bands
with the bands of the GaAs substrate. In particular, the maxima obtained with the detection
energy fixed at the maxima and the right and left flanks of the PL emissions shift to higher
energies with the increase of the detection energy: from 1.232 eV (in line-II) to 1.305 eV (in
line-III). For the right flank-PLE-line, in particular, the onset and the slope of the absorption
differ significantly from those of lines (I) and (II): an onset energy difference of 40 meV is
extracted.
It is found, that the energy difference between the PLE maximum and the onset, known
as Stokes shift (SS), varies with respect to the variation of the detection energy. In general, the
Stokes-shift (SS) is the energy difference between the spectral positions of the band maxima of
the absorption and the luminescence arising from the same electronic transition [7.21]. Larger SS
values are obtained from the excitation spectra fixed at the PL maximum, smaller are derived
from the detection at the right PL flank and the smallest from that at the left PL flank.
In the films with Ga-content in the intermediate range, 0.30<x<0.60, there is a large
dispersion of the calculated SS values dependent on the detection energy. This effect may be
attributed to the fluctuating potentials, which seem to play an important role in the optical
transitions of the films. The variation of PLE maximum and onset with the detection energy is, in
fact, indicative of Ga-incorporation in the intermediate range. Potential fluctuations are thus
raised in this compositional range, which significantly affect the optical properties of
compensated and heavily doped semiconductors. After excitation of PL, the excess carriers are
first captured by potential wells and then by an impurity and recombine with extended lifetimes.
Such optical transitions have similar features to DAP-type transitions [7.22].

e) Temperature dependent measurements
The temperature dependence of the CIGS band-gap and defects playing an important role
in electronic transitions is discussed in the following.
Temperature dependent PR-, PL-, and PLE-measurements have been performed on a
CIGS absorber with x=0.19, since it lies within the compositional region for solar-cell device
development and, in addition, it exhibits just one intensive PL band, which simplifies
comparative studies. The temperature dependence of the PR-spectra resembles the temperature
dependence of the material band-gap.

104
e1) temperature dependence of PL-measurements
In Fig. 7.3.8, temperature dependent PL spectra in the temperature range of 10-80 K are
shown. In this range, the PL spectra consist of one asymmetric band, while at 80 K an increased
background arising in the low energy region is superimposed to the main PL band. The
background may be luminescence related to defects being activated at this temperature. Above
80 K, the PL signal disappears.
The PL peak-energies of the CIGS film with x=0.19 at different temperatures obtained by
evaluation of these spectra are plotted in the inset of Fig. 7.3.8. With the decrease of temperature
below 80 K, the main PL band is shifted to lower energies (red-shift). It is known from the
literature [7.23], that in lightly compensated materials the DAP-emission in the low temperature
regime may exhibit blue-shift (shift to higher energies) with the temperature increase due to
thermal release of electrons from donors of distant short-living electron-hole pairs.
0.8 1.0 1.2 1.4 1.6

P
L
-
i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
30 K
x10
CuIn
0.81
Ga
0.19
Se
2
PL spectra
70 K
40 K
60 K
50 K
20 K
10 K
x10
x2
0 20 40 60 80
1.064
1.068
1.072
1.076
1.080

P
L
-
m
a
x

(
e
V
)
T (K)
80 K

Fig. 7.3.8 Temperature dependent PL spectra of the CIGS layer with x=0.19. In the inset, the PL
peak-energy in dependence of temperature is shown.

105
e2) temperature dependence of PLE-measurements
It is reminded, that the compositional dependence of the PLE spectra recorded at 7 K
with the detection energy at the maximum and also at the left and right flanks of the PL emission
has been already discussed in 7.3d) for compositions in the range x=0.08-0.82. In this section,
only CIGS with x=0.19 in the temperature range 10-70 K is involved in the discussion. The PLE
spectra of CIGS with 19% Ga-content exhibit two PLE maxima assigned there to the E
a
- and E
c
-
transitions.
In Fig. 7.3.9, the temperature dependent PLE spectra recorded with the detection energy
at the PL maximum, between 10 and 70 K, are shown. As in the PLE spectra at 7 K (Fig.
7.3.7b)), two PLE maxima are observed. For the first PLE maximum located at 1.18 eV at 10 K,
a red-shift of 10 meV is observed with the decrease of temperature, while the second PLE
maximum at 1.40 eV seems to be temperature independent. The red energy-shift of the first PLE
maximum with the decrease of temperature below 70 K is experimental evidence of the so called
anomalous temperature dependence of the fundamental energy-gap [7.24] in chalcopyrite
semiconductors; the red-shift of the PL peak-energy, as discussed in the previous section
7.3e1), seems to coincide with that of the first PLE maximum. Moreover, the differences
observed in the temperature dependence of the first and second PLE maxima are indicative of a
different temperature dependence of the E
a
- and E
c
-transition energies, which is further
supported by the temperature dependence of the PR spectra in Fig. 7.3.10.
1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
20 K
CuIn
0.81
Ga
0.19
Se
2
PLE spectra
1.18 eV
1.40 eV

60 K
70 K
40 K
50 K
30 K
10 K
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Energy (eV)
x10
x4
0 10 20 30 40 50 60 70 80
1.176
1.178
1.180
1.182
1.184
1.186

P
L
E
-
m
a
x

(
e
V
)
T (K)

Fig. 7.3.9 Temperature dependent PLE spectra of the CIGS layer with x=0.19. In the inset, the
temperature dependence of the first PL maximum is given.

106
e3) temperature dependence of PR-measurements
In Fig. 7.3.10, temperature dependent PR spectra recorded on the CIGS absorber with
x=0.19 are shown. Transitions assigned to the three split valence bands of chalcopyrite
semiconductors are designated E
a
, E
b
, and E
c
(see Fig. 2.3.1, 2.3). Transition energies derived
by fitting the PR spectra with three TDFFs (see Eq. (5.1.8), 5.1.2 and Evaluation example of a
PR-spectrum, Fig. 7.1.2) are presented in Table 7.3.1 and are plotted in dependence of
temperature in Fig. 7.3.11. The non-cubic crystal field
cf
and spin-orbit interaction
so
energies
calculated by using Eqs. (2.3.2) and (2.3.3), are also given in Table 7.3.1.

0.9 1.0 1.1 1.2 1.3 1.4 1.5
CuIn
0.81
Ga
0.19
Se
2
PR spectra
50 K
20 K

R
/
R

(
x
1
0
-
3
)
Energy (eV)
100 K
300 K
200 K
E
c
E
b
E
a
x2

Fig. 7.3.10 Temperature dependent PR spectra of the CIGS layer with x=0.19.

107
Table 7.3.1 Temperature dependence of E
a
-, E
b
- and E
c
-transition energies,
cf
and
so

parameters of the CIGS layer with x=0.19.

T (K) E
a

(eV)
E
b

(eV)
E
c

(eV)
cf

(meV)
so

(meV)
20 1.142 1.167 1.376 -36 220
50 1.147 1.178 1.370 -43 205
100 1.147 1.172 1.363 -35 201
200 1.139 1.157 - - -
300 1.128 1.141 - - -

0 50 100 150 200 250 300
1,14
1,17
1,35
1,38
CuIn
0.81
Ga
0.19
Se
2

t
r
a
n
s
i
t
i
o
n

e
n
e
r
g
y

(
e
V
)
T (K)
E
a
E
b
E
c

Fig. 7.3.11 E
a
-, E
b
- and E
c
-transition energies of the CIGS layer with x=0.19 in dependence of
temperature.

A red-shift is found for the E
a
- and E
b
-transition energies with the decrease of
temperature below 70 K. This red energy-shift is an effect known from the literature as
anomalous temperature dependence of the material band-gap. This phenomenon was first
observed in lead chalcogenides (PbS, PbSe, PbTe) [7.25] and cuprous halides (CuCl, CuBr, CuI)
[7.24], [7.26]; in PbTe, the decrease of the lowest direct gap with decreasing temperature has
been attributed to a combination of anomalous thermal-expansion with electron-phonon (Debye-
Waller) interaction. The anomalous temperature dependence has been already observed on
chalcopyrite semiconductor materials, as discussed below.

108
In Fig. 7.3.11, in particular, starting from 20 K and up to 100 K, the E
a
- and E
b
-bands
shift to higher energies with the temperature reaching a maximum at approximately 100 K. The
temperature dependence is reversed above 100 K; both bands shift to lower energies, as expected
according to the Varshni formula (Eq. (5.2.10), 5.2.3), and are both present even at room
temperature. The E
c
-band exhibits a different temperature behavior than the lower energy E
a
- and
E
b
-bands. The E
c
-band diminishes above 100 K and cannot be detected at room temperature.
Differences in the temperature dependence of the E
c
- compared to the E
a
- and E
b
-bands have
been also found in the PLE temperature dependence (Fig. 7.3.9, 7.3e2). In general, the PR- are
in very good agreement with the PLE-results.
An anomalous temperature dependence of the energy-gap is commonly observed on
chalcopyrites of type I-III-VI
2
. In particular, chalcopyrites containing Ag exhibit a red-shift in
g
E at T<150 K found not only in PL, but also in reflectivity and absorption measurements
[7.27], [7.28]. Similar red-shifts of the LT PL have been observed on CuInSe
2
[7.29] and CuInS
2

single crystals [7.30], and on InGaN alloys [7.31]. Low-field surface-barrier electroreflectance
measurements on CuInS
2
single crystals have also shown anomalous behaviour of the lower
energy- gaps with temperature variation [7.32]. In the case of InGaN alloys, this behaviour has
been attributed to the inhomogeneous broadening of excitons resulting from alloy fluctuations
[7.31], whereas in AgGaS
2
,

it has been assigned to a low energy phonon mode detected in the LT
Raman spectra of the Ag chalcopyrite [7.33].
Generally, the anomalous temperature dependence of the E
a
- and E
b
-transitions has been
explained as follows [7.34]: for bulk materials the temperature dependence of the energy gap
derives partly from lattice thermal expansion and partly from the renormalization of band
energies by electron-phonon interactions (see Eq. (5.2.9)). In principle, the first term can be
calculated if the coefficient of thermal expansion, the band gap pressure dependence and the bulk
modulus of the sample are known [7.33]. The electron-phonon interaction is usually the larger
contribution and the most difficult to evaluate. There are two types of electron-phonon
contributions, the self energy term and the Debye-Waller term. A perturbative calculation of
the electron self-energy to second order in atomic displacement u yields both terms, but only the
second is commonly named as self-energy, the first being independent of frequency. Both are
necessary to preserve translational invariance [7.35], [7.36]. The self-energy due to electron-
phonon coupling has been calculated for a bulk semiconductor by Fan [7.37] and several
refinements of this calculation have followed.
Because of the anomalous temperature dependence of E
a
-

and E
b
-band energies, it was
not possible, by fitting energy-position and -width of the respective bands according to Eqs.

109
(5.2.10), (5.2.11), and (5.2.12), 5.2.3, to obtain the phonon frequencies (energies) assisting the
transitions in the low temperature regime.
Energy shifts due to electron-phonon interaction include contributions from both acoustic
and optical branches (see Eq. (5.2.11) in 5.2.3). A possible explanation of the PR-results
obtained for the E
a
- and E
b
-transitions in dependence of temperature could be that the
deformation-potential coupling to phonon modes is different for acoustic and optical modes at
low and high temperatures, based on the temperature dependence on cuprous halides, reported in
Ref. [7.25]. At low temperatures up to 100 K, coupling to acoustic seems to dominate over the
coupling to optical modes. This is related to the dominance of the intraband contributions in the
self-energy over the corresponding interband ones. The former electron-phonon terms are
usually negligible. The situation is reversed at temperatures above 100 K. A typical Varshni
behaviour is observed in the temperature dependence of the excitonic peaks. This is
characteristic of the take over of the interband electron-phonon terms in the self-energy of the
quaternary system in this temperature range.

f) Determination of exciton binding energy
By fitting the E
a
- and E
b
-band intensities according to Eq. (5.3.2), 5.3.2, an attempt is
made to determine the exciton binding energies. It is reminded, that at low temperatures, exciton
states direct below the lower conduction band are involved in electronic transitions. Therefore,
the E
a
-, E
b
- and E
c
-transitions are attributed to A-, B- and C-excitons, respectively. The exciton
states do not contribute at room and elevated temperatures because thermal energies are usually
higher than exciton ionization energies.
In Fig. 7.3.11, the E
a
- and E
b
-band intensities are plotted as a function of the reversed
temperature (1/T) and fitted with an exponential decay law as described in Eq. (5.3.2), 5.3.2.
The calculated binding energies of the A- and B-excitons contributing to the E
a
- and E
b
-
transitions are 56 and 110 meV, respectively. Under the assumption, that the energy of 33 eV
resulting from the subtraction of the E
a
-transition energy of the low temperature PR (1.146 eV at
20 K) from the low temperature PLE maximum (1.179 eV at 7 K) can be ascribed to the A-
exciton, its binding energy obtained by fitting the low temperature PR-spectra is larger. It is also
much larger than the exciton energy of 12 meV obtained in Ref. [7.5]. Possible reasons for this
discrepancy may be, in the first case, inaccuracy of the fitted values because of insufficient data
points (the number of measurements was limited to 5 (see Fig. 7.3.11), and in the second case,
the different composition of the samples or the different experimental techniques applied in this
work and in Ref. [7.5]. In Ref. [7.5], the energy of the A-exciton has been obtained from the
temperature dependence of the excitonic PL emission of a Cu-rich ([Cu]/{[In]+[Ga])=1.1) CIGS

110
sample with x=([Ga]/([In]+[Ga]))=0.19, while in the present work, both exciton energies have
been obtained by fitting the PR temperature dependence of a stoichiometric CIGS sample with
Ga-content (x=0.19) equal to that of Ref. [7.5]. According to theoretical predictions, exciton
binding energies of ternary chalcopyrites, such as CuInSe
2
, should be even lower: From a simple
hydrogen atom model for the free exciton, a dielectric constant 13.6
r
= for CuInSe
2
and a
reduced electron and hole mass 0.08
r e
m m = a free exciton binding energy of 6 meV is
determined [7.38], [7.39].
0.00 0.01 0.02 0.03 0.04 0.05
1E-4
1E-3
0.01

I
n
t
e
n
s
i
t
y
1/T
E
a
E
b

Fig. 7.3.11 E
a
- and E
b
-band intensities of the CIGS layer with x=0.19 in dependence of
reversed temperature.

On the other hand, the energy shift of PLE- compared to PR-spectra (33 meV) in
combination with the presence of both, E
a
- and E
b
-bands, at room temperature suggests that the
transitions observed on the PR spectra correspond rather to the A- and B-excitons than to the E
a
-
and E
b
-gaps.
The band-to-band transitions are thus represented by the PLE maxima; an excitonic
binding energy as high as 33 meV can be concluded for the CIGS film with x=0.19. The
exciton binding energy of the CIGS quaternary compounds is determined in 7.3g2).
Similar conclusions can be drawn for the C-exciton by taking in account the PR- and
PLE-measurements; the binding energy of the C-exciton has been estimated to 24 meV from the
LT PR (1.376 eV at 20 K) and the LT PLE max (1.400 eV at 7 K).

111
g) Determination of donor and acceptor binding energies
Assuming a DAP mechanism for the CIGS luminescence emission, both donor and
acceptor binding energies can be calculated according to the following equation [7.40] (Eq.
(5.3.3)):
( )
DAP g D A C
E E E E E = + + (7.3.4)
where E
g
is the energy band-gap,
D
E and
A
E are the energies of the participating donor and
acceptor defect states, and
2
0
/ 4
C
E e R = describes the Coulomb attraction between the final
charged donor and acceptor states.
C
E depends on the distance R within the donor-acceptor pairs. For the Coulomb
attraction, the maximum value,
max C
E , is obtained by assuming 2
B
R = , where
B
is the Bohr
radius of spatially more extended defects. The shallow donors in CuInSe
2
have a Bohr radius of
approximately 80 , an electron effective mass of
*
0
0.09
e
m m = and a static dielectric constant of
13.6 = . A value of
max
7
C
E meV = is thus determined [7.41].
In samples with one CIGS phase, E
g
is obtained from the first PLE maximum, whereas,
in sample with two phases revealed by combination of the XRD- and PL-results, first the Ga-
fraction is calibrated, and then E
g
is determined for the corrected (x
corr
) Ga-content.
It should be noted, that in the PR-, PL- and the PLE-analysis of the CIGS epitaxial layers
in 7.1, 7.3a)-f), the Ga-content (x=[Ga]/([Ga]+[In])) measured by EDX has been considered
(Table 4.1.1). However, evaluation of the PL spectra (Fig. 7.3.1a) and b)), revealed the presence
of two phases in the films with x=0.33 and 0.60. This observation has been supported by the
high-resolution (HR)-XRD data of the same films, already discussed in 7.3a).
Based on the XRD- and PL-results, an attempt was made to calibrate the composition of
the films with x=0.33 and 0.60 and extract a corrected Ga-fraction (details will be given in
section g
1
)). By using the corrected x-values (x
cor
) of these films, a defect analysis has been
possible that will be discussed later in section g
2
); this allows the donor and acceptor state
energies to be calculated.

g
1
) Correction of the Ga-content of the films with x=0.33 and 0.60
XRD data
The high resolution (HR)-XRD diffractograms, given in Fig. 7.3.1c) in 7.3a), show,
apart from the main (008) peak, several reflection maxima assigned to the inhomogeneous Ga-
incorporation within these films. Such maxima are more pronounced in the films with x=0.33
and 0.60. For each of these films, two reflections are thus considered: the main (008) peak and a
second, less intensive, peak. The calibration curve Bragg-angle versus Ga-content is derived as

112
follows: In Fig. 7.3.12, the XRD-data of the quaternary CIGS layers with a single (008) Bragg-
reflection peak has been given in dependence of composition. Experimental data of ternary CIS
and CGS epitaxial layers, corresponding to x=0 and 1, respectively, have been also included. For
the film with x=0.82, though a shoulder is superimposed on the high-energy side of the (008)
reflection (Fig. 7.3.1c) in 7.3a)), only the Bragg-angle of the main (008) peak is shown (Fig.
7.3.12). In addition, theoretically calculated Bragg-angles of the (008) peak of the ternary CIS
and CGS compounds, at 64.138
o
and 67.979
o
,
respectively, are designated with open squares
[7.6]. A linear fit of the experimental data gave following equation:
0
Bragg-angle( )= 63.969 + 4.087 x (7.3.5)
In order to obtain the correct Ga-fraction of films with nominally x=0.33 and 0.60
[Ga]/([Ga]+[In]), the Bragg angles of the main and secondary peak have been inserted in Eq.
(7.3.5) and two x
cor
values have been calculated for each film:

1
st
peak of CIGS with x=0.33:
0
1
64.888 Bragg angle = 0.22
A
x =
2
nd
0
2
B
x =
(7.3.6)
1
st
0
1
A
x =
2
nd
0
2
B
x =

0.0 0.2 0.4 0.6 0.8 1.0
63
64
65
66
67
68
69
Bragg angle(
0
)=63.969 + 4.087 x
HR-XRD 300 K

B
r
a
g
g

a
n
g
l
e

(
o
)
[Ga]/([Ga]+[In])
theoretical
experimental

Fig. 7.3.12 Calibration curve (1): Bragg reflection versus Ga-content (by EDX).

113
PL data
Based on the PL peak-energy of the CIGS layers (Fig. 7.3.1a), 7.3a)), a second
calibration curve has been obtained as follows: excluding the data points corresponding to the
films with x=0.33 and 0.60, a PL peak-energy versus Ga-content at 7 K diagram (Fig. 7.3.13)
has been drawn for the films with a single PL emission peak. Fitting the peak-position with a
polynomial has led to following equation:

2
0.953 0.502 0.118 PL peak energy x x eV = + + (7.3.7)

By inserting the PL peak-energies of the films with x=0.33 and 0.60 in Eq. (7.3.7), the
corrected values x
cor
have been obtained:

1
st
peak of CIGS with x=0.33: max1 1.071 PL eV = 0.22
A
x =
2
nd
peak of CIGS with x=0.33: max 2 1.252 PL eV = 0.53
B
x =
(7.3.8)
1
st
peak of CIGS with x=0.60: max1 1.268 PL eV = 0.56
A
x =
2
nd
peak of CIGS with x=0.60: max 2 1.42 PL eV = 0.79
B
x =
0.0 0.2 0.4 0.6 0.8 1.0
0.9
1.0
1.1
1.2
1.3
1.4
1.5
PL 7 K
PL peak-energy =0.953+0.502 x+0.118 x
2

P
L

p
e
a
k
-
e
n
e
r
g
y

(
e
V
)
[Ga]/([Ga]+[In])
PL-max1

Fig. 7.3.13 Calibration curve (2): PL peak-energy versus Ga-content (by EDX).

By comparison of the x-values, calculated for the two-phase CIGS films using the XRD
and PL data, following conclusive remarks can be made:

114
a) The more intensive PL peak, in Fig. 7.3.1a), corresponds to the predominant phase in
the CIGS layers with x=0.33 and 0.60. b) the results of the corrected x-values, calculated
according to Eqs. (7.3.6) and (7.3.8), e.g. the
A
x -value of the film with x=0.33 and the
B
x -value
of the film with x=0.60 are consistent in both calculations(Figs. 7.3.12 and 7.3.13). However,
the
B
x -value of the film with x=0.33, in the 1st calculation (Fig. 7.3.12), uses a low-intensity
XRD-maximum and has, therefore, a relatively big computational error. In case of the film with
x=0.60, the
A
x -value of the 1st calculation (Fig. 7.3.12) uses a XRD-peak that overlaps with the
GaAs (004) peak (see Fig. 7.3.1c)). It can, therefore, be expected that the most reliable x-values
(x
cor
), calculated for the two-phase CIGS films arise from the PL data and are given in Table
7.3.2; these x
cor
-values are used for the defect analysis described in the following section g2),
instead of the x=0.33 and 0.60, which have been initially used (7.1-7.3.f).

g2) Defect analysis based on the corrected x-values of the films with x=0.33 and 0.60
The donor
D
E and the acceptor
A
E state energies are calculated using Eq. (7.3.4), where:

Table 7.3.2 [Ga]/([Ga]+[In])=x ratios (EDX- and x
cor
-values (see 7.3g1))), PL peak-energies,
PLE-onsets, energy band gaps
g
E , donor
D
E and acceptor
A
E
binding energies of
CIGS layers at 7 K.

x
(EDX)
x
cor

DAP
E
PL peak-
energy
(eV)
PLE-
onset
(eV)
g
E
(eV)
D
E
(meV)
A
E
(meV)
0.08 0.08 0.987 1.062 1.107 38 75
0.19 0.19 1.064 1.131 1.179 41 67
0.22 1.071 1.14 1.188 41 69 0.33
0.53 1.252 1.337 1.388 44 85
0.50 0.50 1.228 1.308 1.362 47 80
0.55 1.268 1.359 1.402 36 91 0.60
0.75 1.42 1.499 1.555 49 79
0.82 0.82 1.522
*
1.575 1.614 32 53

*the PL peak-energy is derived from the data at 2 K (Fig. 7.3.1b), 7.3b)).

DAP
E = PL peak-energy (Table 7.3.2)
g
E = first PLE-max (Fig. 7.3.7, 7.3d))
A
E =(PLE-onset) (PL peak-energy) (Table 7.3.2)
max C C
E E = =7 meV [7.40]

115
In case of the films with x=0.08, 0.19, 0.50 and 0.82, the energy band gaps
g
E are
obtained from the first PLE-max, which, as already stated in 7.3f), corresponds to a band-to-
band transition (see in Table 7.3.2 in bold). Taking into account the PLE data on these films
(Figs. 7.3.7a), b),d) and f)), another calibration curve (3) has been derived and is plotted in Fig.
7.3.14. In case of the film with x=0.50, which exhibits three different PLE-maxima, at 1.362 eV,
at 1.373 eV and at 1.403 eV (Fig. 7.3.7d)), the lower energy-maximum (at 1.362 eV) has been
considered in Fig. 7.3.14. By fitting the E
g
=PLE-max with a polynomial, another calibration
curve has been calculated:

2
max
1.073+0.475 x +0.224 x
g
PLE E = = (7.3.9)

Setting in Eq. (7.3.9) x=x
cor
(7.3g
1
), the band gap energies of the two-phase films, with x=0.33
and 0.60, have been calculated. The calculated band gap energies
g
E of all CIGS layers are
given in Table 7.3.2.
0.0 0.2 0.4 0.6 0.8
1.1
1.2
1.3
1.4
1.5
1.6
1.7
PLE 7 K
1
st
PLE-max

E
g
=1.073+0.475 x +0.224 x
2
E
n
e
r
g
y

b
a
n
d

g
a
p
,

E
g

(
e
V
)
[Ga]/([Ga]+[In])

Fig. 7.3.14 Calibration curve (3): first PLE-max energy versus Ga-content (by EDX).

The energy difference between the PLE-onset and the PL peak, assigned to a DAP
transition (see 7.3c)), gives the acceptor binding energy (
A
E
) in the CIGS films (Table 7.3.2).
The calculated values are between 70 and 90 meV.

116
In case of the layer with the higher Ga-content, the PL band at 7 K overlaps with the
GaAs-emission (Fig. 7.3.1a)). Therefore, for the film with x=0.82, the PL peak-energy derived
from the PL spectrum at 2 K (Fig. 7.3.1b)) has been considered. The donor binding energy (
D
E
)
has been determined from Eq. (7.3.4) assuming a Coulomb interaction of 7 meV [7.41]. The
DAP-emission energies
DAP
E , the energy band gaps
g
E , the PLE-onsets, and the donor
D
E and
acceptor
A
E state energies of the CIGS layers are accumulatively given in Table 7.3.2. For the
CIGS chalcopyrite absorbers, a donor state lying at 30-50 meV below the conduction band and
an acceptor state at 70-90 meV above the valence band have been found. The donor state has
lower binding energy than the acceptor, in accordance with the hydrogen model [7.5].
For the film with x=0.82, the acceptor binding energy is calculated to 52 meV, and is thus
lower than the binding energy of the acceptor state in the other CIGS layers. This may be due to
the different excitation source, a 514.5 nm-laser beam (Figs. 7.3.1b) and 7.3.3), that may have
excited a different defect state than the Tungsten lamp.
According to Ref. [7.5], the PL emission of slightly Cu-rich CIGS layers, having a ratio
of [Cu]/([In]+[Ga])1.01.1, has been attributed to the DA
1
-recombination, as presented in Fig.
7.3.15, where D is the donor and A
1
the swallow acceptor (A
1
=40 meV in CIS and A
1
=60 meV
in CGS). In the CIGS alloys, the donor and acceptor defect states are positioned between the
corresponding states of the ternary CIS and CGS end-points. As shown in Fig. 7.3.15, the CIGS
alloys with x=0.25 and 0.50, have an acceptor state at energies 46 and 55 meV, respectively,
above the valence band.

Fig. 7.3.15 Defect model for Cu(In,Ga)Se
2
[7.5].

117
The CIGS films (Table 4.1.1) studied in this work have a ratio of
[Cu]/([In]+[Ga])1.01.1, similar to those measured by PL in Ref. [7.5]. However, the
calculated acceptor and donor binding energies (Table 7.3.2), are larger than the ones reported in
Ref. [7.5]. According to the model described in Ref. [7.5], acceptor energies in the range of 70-
90 meV (Table 7.3.2) would imply a DAP emission where the
2
, -not the A
1
, acceptor state,
following the notation used in Fig. 7.3.15, would participate in DAP transitions. Also, the donor
binding energies of 30-50 meV are significantly larger than those calculated in Ref. [7.5].
Possible reasons for this discrepancy might be the assumption of a short range Coulomb-
interaction
max C
E =7 meV in Eq. (7.3.4). In Ref. [7.41],
max C
E =14 meV has been calculated,
which is twice as much compared to the value used here. The evaluation of the PLE- and PL-
spectra may be another reason for the determination of larger
D
E and
A
E energies than those
expected considering the state energies in the ternary CIS and CGS end-members (Fig. 7.3.15):
due to the asymmetry of the PLE- and the PL-bands, the PLE-onsets, PLE-max, and PL peak-
energies in CIGS could not be fitted; the respective values have a high degree of uncertainty.
. By combining the PL- PLE- and PR-results, an excitation schema has been evolved for
the determination of the donor and acceptor state energies in CIGS quaternary chalcopyrite
compounds, and is demonstrated in Fig. 7.3.16. In the frame of this schema, a PL-, a PLE-, and a
PR-spectrum recorded at low temperatures are representatively shown.
This schema is based on the presence of one donor (D) and one acceptor (A) state and
uses Eq. (7.3.4). In Fig. 7.3.16, PLE-max corresponds to the lower energy band-gap (E
g
), which
in case of the chalcopyrites is the E
a
-gap, E
DAP
is the PL peak- energy, E
A
is derived by
subtracting E
DAP
from PLE-onset energy (Table 7.3.2) and E
D
by inserting the above calculated
values in Eq. (7.3.4).
In Fig. 7.3.16, a LT PR spectrum is also shown. Three PR bands assigned to the A- B-
and C-excitons, from lower to higher energy, are present, as discussed in detail in 7.1b) and
7.3f). In Fig. 7.3.16, only the A-exciton is marked with an arrow for simplicity. The energy
difference between the PLE-max(=E
g
) and the first PR band (Aexc) corresponds to the exciton
binding energy of the A-exciton. In 7.3f) an exciton binding energy of 33 meV has been
calculated for the A-exciton in the CIGS film with x=0.19. The binding energy (
exc
E
) of the A-
exciton in CIGS films is given in Table 7.3.3. It should be noted that the corrected Ga-fractions
(x
cor
) derived in 7.3g1) are considered. By excluding the two-phase films, the exciton binding
energies calculated are in the range of 27-60 meV, which are rather large for a free exciton. This
result suggests that the first PLE-max assigned to the band-gap energy E
g
(band-to-band
transition), as discussed in detail in 7.3d)-f) may be further blue-shifted due to electron-A
1
-

118
phonon interaction. The A
1
-phonon mode-energy of CIGS is slightly dependent on the Ga-
content ranging between 21.4 meV, for the film with x=0.08, and 22.4 meV, for the film with
x=0.82, under excitation with the 647.1 nm Kr
+
-laser (see Table 7.2.2).

0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
E
D
=PLE-max(=E
g
)-E
A
-E
C
E
A
=PLE-onset-E
DAP
Aexc
onset
PLE-max
I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Energy (eV)
E
DAP
PL
PR
PLE

Fig. 7.3.16 Excitation schema for Cu(In,Ga)Se
2
. Combination of PL- PLE- and PR-results.

In the case of the two-phase films, the binding energy derived for the second phase is
extremely large. This can be explained as follows: the PR signals, that were recorded on these
films (Fig. 7.1.4) and provide the A-exciton (Aexc) energy of the CIGS films, are very broad and
bands assigned to the two different phases are not resolved. Additionally, the light of a Tungsten
lamp, used as an excitation source in the PLE spectra, penetrates the CIGS films up to the
substrate (see Fig. 7.3.7 and Table 7.2.1), which is much deeper compared to the penetration
depth of the laser-beam (488 nm or 457.9 nm Ar
+
-laser) used as a modulating source in the
corresponding PR spectra. Therefore, considering the Ga-incorporation in the CIGS films, Aexc
determined by PR is more indicative of the Ga-poor-phase near the film surface (x
corr
=0.22
instead of 0.33 and x
cor
=0.55 instead of 0.60).

119
Table 7.3.3 [Ga]/([Ga]+[In])=x ratios (by EDX and x
cor
(see 7.3g1))), energy band gaps
g
E , A-
exciton ( Aexc ) (PR 20 K) and exciton binding energies
exc
E of CIGS layers at 7 K.

x
(EDX)
x
cor

max g
E PLE =
(eV)
Aexc
(PR 20 K)
(eV)
for A-exciton:

max
exc
E PLE Aexc =
(meV)
0.08 0.08 1.107 1.080 27
0.19 0.19 1.179 1.146 33
0.22 1.188 1.175 13 0.33
0.53 1.388 1.175 213
0.50 0.50 1.362 1.318 44
0.55 1.402 1.371 31 0.60
0.75 1.555 1.371 184
0.82 0.82 1.614 1.554 60

1-x
Ga
x
Se
2
epitaxial layers by spectroscopic Ellipsometry (SE)

Absorbance and reflectance of solar-energy modules in the spectral range of solar-
energies (0.5-2.5 eV, max. 1 eV) are most important macroscopic functions for solar-energy
conversion. Spectroscopic Ellipsometry (SE) has been, therefore, applied to determine the
dielectric function, thus the optical constants and the higher band gaps of the CIGS epitaxial
layers at RT (7.4.1). The fundamental band gap energies of the CIGS films have been already
determined, in 7.1, by the complementary experimental technique of Photoreflectance (PR),
which measures directly the derivatives of the dielectric function. Though fundamental energy-
gaps can be also studied by SE (7.4.2), the SE-measurements of the E
a
-gap energies of CIGS
absorbers could not be evaluated because of very strong thickness interferences at energies in the
range of the E
a
-gap energy. PR has proven to be a powerful and most reliable tool for the
determination of the fundamental gap-energies of CIGS absorber layers. Moreover, for
technological applications, proper installation of solar-cell modules plays also an important role.
Orientation effects have been investigated by angle dependent ellipsometric measurements.

7.4.1 Determination of optical constants and higher band-gap energies by SE
The optical properties of CIGS epitaxial layers with different Ga fractions (x=0.08-0.82)
were measured by SE at room temperature (RT). In Fig. 7.4.1, the RT real and imaginary part of
the effective dielectric function,
1
< > and
2
< > are presented. The spectra were recorded at
an incident angle of 65
o
.

120
The second derivative of the imaginary part of the dielectric function
2 2
2
/ d d E is used
to evaluate the higher band gaps of the quaternary CIGS alloys. The
2 2
2
/ d d E spectra of the
CIGS films in dependence of composition are illustrated in Fig. 7.4.2.
The assignment of the observed minima, is based on a previous study of CIGS
polycrystalline films [7.4]. More intensive signals are recorded in case of films with low and
intermediate Ga-contents, up to x=0.50. Above 2.7 eV, three main transitions, labeled as
1
(),
() and
1
() in Fig. 7.4.2, are found. These transitions are assigned to critical points at the
Brillouin-zone centre () and edge N- point. In some cases, a peak assigned to the E(X)
transition is also observed. In particular, E
1
(A) and E
1
(B) are assigned to E
1
-like transitions at the
N point of the Brillouin zone, while () is assigned to those at the -point. E(X)
corresponds to an electronic transition at T-point. Among them, the E
1
(A) dominates the
ellipsometric spectra of CIGS. Similar is observed on both, CIS and CGS materials [7.4]. The
peaks at energies below 2.7 eV, will be discussed in 7.4.2.

Fig. 7.4.1 RT dielectric functions
1
< > and
2
< > of the CIGS films.

1.5 2.0 2.5 3.0 3.5 4.0 4.5
0.82
0.60
0.50
0.33
0.19
x=0.08
<
1
>
1
of CuIn
1-x
Ga
x
Se
2
layers

Energy (eV)
1.5 2.0 2.5 3.0 3.5 4.0 4.5
0.82
0.60
0.50
0.33
0.19
x=0.08
<
2
>
2
of CuIn
1-x
Ga
x
Se
2
layers
Energy (eV)

121
The second derivative of both, the real and imaginary part of the dielectric tensor are
calculated; the final spectra are, additionally, smoothed. Both spectra are shown, as evaluation
example of a SE-spectrum, in Fig. 7.4.3. The minima of the
2 2
2
/ d d E spectrum correspond to
the higher
1
(), () and
1
() gap energies. For the films with x=0.33 and 0.60, the
2 2
2
/ d d E spectra are more complicated exhibiting a number of minima, mainly due to the
presence of two different phases in these films. Additionally, the films with x0.33 show a
transition due to the ternary CuGaSe
2
compound formed at the interface of the CIGS layer and
the GaAs substrate.

1.5 2.0 2.5 3.0 3.5 4.0 4.5
CuIn
1-x
Ga
x
Se
2
E(X)
x0.5
x0.5
x0.5
E
1
(B)
E
1
(A)
0.82
0.60
0.50
0.33
0.19

x=0.08
d
2
2
/
d
2
E
Energy (eV)

Fig. 7.4.2
2 2
2
/ d d E spectra of the CIGS films in dependence of composition.

122
2.0 2.5 3.0 3.5 4.0 4.5
-40
-20
0
20
40
E()
E
1
(B)
E
1
(A)

3.685
3.212
2.925
CuIn
0.81
Ga
0.19
Se
2
d
2
/
d
2
E
Energy (eV)
d
2
1
/d
2
E
d
2
2
/d
2
E

Fig. 7.4.3 Second derivatives of both dielectric tensors of the CIGS film with x=0.19
(Evaluation example of a SE-spectrum).

The calculated transition energies of the CIGS layers with different compositions are
listed in Table 7.4.1 and are plotted as a function of the corrected Ga-fraction x
cor

(={[Ga]/([Ga]+[In]}
cor
) in Fig. 7.4.4. For comparison, the data known from the literature for the
ternary CIS and CGS compounds are also shown with open symbols [7.3]. {[Ga]/([Ga]+[In]}
cor

represents, in case of the two-phase CIGS films with x=0.33 and 0.60, the corrected Ga-fraction
(x
cor
), as it has been determined in 7.3g1). It is reminded, that the calculation of the corrected
Ga-content of these films is based on a combination of PL-, PLE- and XRD-results (see Figs.
7.3.1a) and b), 7.3.7, 7.2.1c) and 7.3.1c)). In these films, two phases at least exist and an
<effective> dielectric function is measured. The <effective> dielectric function of the CIGS film
with x=0.33 seems to have its origin mainly in the phase with the lower Ga-content of x
cor
=0.22,
since the calculated gap-energies are closer to those of the CIGS film with x=0.19 than to those
of the film with x=0.50.

123
0.0 0.2 0.4 0.6 0.8 1.0
3.0
3.3
3.6
3.9
4.2
4.5 E
1
(A) =2.939-0.322 x+0.499 x
2
E() =3.205-0.105 x+0.422 x
2
E
1
()=3.611+0.211 x+0.140 x
2
E()

E(X)
E
1
(B)
E
1
(A)
T
r
a
n
s
i
t
i
o
n

e
n
e
r
g
y

(
e
V
)
{[Ga]/([Ga]+[In])}
cor

Fig. 7.4.4 Transition energies of CIGS films in dependence of composition (solid symbols). The
data for the ternary CIS and CGS compounds are shown with open symbols [7.3].

With the increase of the Ga fraction, the higher gap energies of the quaternary films
increase slightly; still they lie between the gap energies of the ternary end-members of the series,
CIS and CGS. The variations of gap-energies with the composition have been fitted with
polynomials and are shown in Fig. 7.4.4. The energy difference between E
1
(A) and E
1
(B)
corresponds to the crystal-field splitting of the valence band at the N-point. It is increased from
0.73 eV in CIGS with x=x
cor
=0.08 to 0.85 eV in CIGS with x=x
cor
=0.82, in agreement with the
values found in CIS (0.75 eV) and CGS (0.95 eV) [7.4].

Table 7.4.1 Thickness d and higher transition energies of CIGS films.

x x
cor
d
(nm)
E
1
(A)
(eV)
E()

(eV)
E()
CuGaSe
2
(eV)
E
1
(B)
(eV)
E()

(eV)
0.08 0.08 440 2.88 3.182 3.609
0.19 0.19 440 2.925 3.212 3.685
0.22 0.33
0.53

360

2.921

3.212

3.436

3.666

3.929
0.50 0.50 390 2.909 3.273 3.517 3.759
0.55 2.876 3.263 3.511 3.745 0.60
0.75
290
2.963
0.82 0.82 250 3.033 3.38 3.634 3.885 4.115

124
The optical properties, e.g. refractive index and extinction coefficient of CIGS films,
were calculated in the energy region 2.0 - 4.5eV, as illustrated in Figs. 7.4.5a) and b).
Chalcopyrites are actually uniaxial crystals and their optical properties are represented by an
ordinary and an extraordinary component of the dielectric tensor. However, due to the (001)
orientation of the films grown following the orientation of the substrate, the measured effective
indices, refractive index <n> and extinction coefficient <k>, are represented almost by the
ordinary with only a very small admixture of the extraordinary component of the dielectric
tensor [7.4]. For the films with x0.50, refractive indices between 2 and 3 are obtained, in
agreement with the values published in Ref. [7.4]. The lower refractive index, calculated for the
films with higher Ga-contents (x0.60), are indicative of the presence of surface over-layers
[7.43]. Additionally, the small size of the sample with x=0.60 does not allow acquirement of a
very accurate spectrum.
The penetration depth (alpha
-1
) of the excitation light in the CIGS films is shown as a
function of composition in Fig. 7.4.5c). The maximum penetration depth was calculated to 70
nm. Therefore, the light reaches only the uppermost part of the layer. Comparing the CIGS layer
thickness d , given in Table 7.4.1, with the calculated penetration depth (Fig. 7.4.5c)), the
presence of peaks assigned to the CGS layer, which is formed at the CIGS/GaAs interface, is not
expected in the
2
or the
2 2
2
/ d d E spectra. Still, CGS-peaks are detected which is also in
agreement with the results of Raman- ( 7.2), XRD-, and PL-analysis (7.3a) and b)). This
contradiction can be surpassed by assuming that the CGS phase is dispersed over the whole
CIGS layer and is present, in a much higher concentration, near the interface to the GaAs
substrate. It is evident that absorption is favored by increasing the Ga content; absorption
coefficients at optical energies, depicted in Fig. 7.4.5d), become as high as 6 x 10
5
cm
-1
.

125

Fig. 7.4.5 a) Refractive index n b) extinction coefficient k c) penetration depth
1
alpha
and, d)
absorption coefficient alpha values of CIGS films.

7.4.2 Complementary Study of fundamental gap-energies by SE
Ellipsomertic measurements of CIGS films have been also performed in the spectral
range 0.75-4.2 eV at room temperature (RT) to verify the fundamental gap-energies obtained by
PR techniques (7.1). The angle of incidence was set to 55
o
in most samples, except from the
one with x=0.60; an angle of 40
o
has been chosen there because of the small size of the sample.
The real
1
< > and imaginary
2
< > part of the dielectric tensor of the CIGS films are depicted
in Fig. 7.4.8.

1.5
2.0
2.5
3.0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
0.8
1.2
1.6
(a)
Energy (eV)
k

n
x=0.08
x=0.19
x=0.33
x=0.50
x=0.60
x=0.82

(b)

15
30
45
60
75
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
2
4
6
(c)

a
l
p
h
a
-
1
(
n
m
)
x=0.08
x=0.19
x=0.33
x=0.50
x=0.60
x=0.82

Energy (eV)
(d)
a
l
p
h
a

(
x
1
0
5
)

(
c
m
-
1
)

126

Fig. 7.4.8 RT dielectric functions
1
< > and
2
< > of the CIGS films.

In the low energy region, the spectra exhibit very intensive asymmetric peaks within and
below the fundamental gap-energy previously determined by PR techniques (7.1). An attempt
to evaluate these spectra by calculating the second derivative of the effective real
1
< > and
imaginary
2
< > part of the complex dielectric function reveals the presence of interferences in
the low energy region. These interferences can be explained in the following: The Ga-gradient
within the CIGS layers [7.5] resembles an internal step-like concentration gradient giving rise to
an internal pseudo-interface. Therefore, the interferences are due to the interaction of incident
light with the front surface and this pseudo-interface in the absorber. Since the interference
fringes overlap with the fundamental gap, a determination of the fundamental gap-energy by SE
is not possible. Generally, for band-gap studies by Spectroscopic Ellipsometry (SE), detailed
information on the precise film structure is required. Excluding from the evaluation the energy
region where very intensive interferences are present, the higher gap-energies, E
1
(A) and E(),
could be derived and are given in Table 7.4.2. These values are in good agreement with the
values calculated from the high-energy Ellipsometry-spectra (7.4.1). Only in case of the film
with x=0.60, no signal could be detected. The angle of incidence chosen to 40
o
, because of the
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

<
1
>
Energy (eV)
CuIn
1-x
Ga
x
Se
2
x0.5
0.60
0.82
0.50
0.33
0.19
x=0.08

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
CuIn
1-x
Ga
x
Se
2

<
2
>
Energy (eV)
x0.5
x0.5
x0.5
0.60
0.82
0.50
0.33
0.19
x=0.08

127
small size of the sample studied, is much smaller than the Brewster angle in semiconductors,
being in the range 55-75
o
.

Table 7.4.2 Higher transition energies of CIGS films.

x x
cor
E
1
(A)
(eV)
E()

(eV)
0.08 0.08 2.79 3.14
0.19 0.19 2.9 3.21
0.22 0.33
0.53
2.87 3.21
0.50 0.50 2.94 3.29
0.55 0.60
0.75
0.82 0.82 - 3.39

7.4.3 Angle-dependent SE measurements
The presence of optical anisotropy in the CIGS samples has been studied by angle
dependent ellipsometric measurements. The real <
1
> and the imaginary <
2
> parts of the
complex dielectric function have been recorded by varying the angle of incidence from 55
o
to
75
o
. In Figs. 7.4.6 and 7.4.7, data obtained on CIGS films with low- and high Ga-fraction,
x=0.08 and 0.60, respectively, are shown as representative.
The spectra were fitted using an anisotropic layer model. There is good agreement
between the measured spectra and the model calculations over the entire spectral range for both
samples. However, the fitting results confirm the very small contribution of the extraordinary
component to the measured effective dielectric function. Thus, in chalcopyrite alloys, the
extraordinary component cannot be separated by altering the angle of incidence [7.4].

128
2.0 2.5 3.0 3.5 4.0 4.5
2
4
6
8
4
5
6
7
<
2
>
<
1
>
55
o
60
o
65
o
70
o
75
o
CuIn
0.92
Ga
0.08
Se
2

Energy (eV)

Fig. 7.4.6 Angle dependent measurements for the film with x=0.08.

2.0 2.5 3.0 3.5 4.0 4.5
0
2
4
6
2
4
6
CuIn
0.40
Ga
0.60
Se
2
<
2
>
55
o
60
o
65
o
70
o
75
o

<
1
>
Energy (eV)

Fig. 7.4.7 Angle dependent measurements for the film with x=0.60.

129
1-x
Ga
x
Se
2
polycrystalline films and solar cells by Photoreflectance and
Electroreflectance spectroscopy

Up to now, the best efficiencies for chalcopyrite-based solar cells have been achieved
using Ga-rich (0.88<[Cu]/([In]+[Ga])<0.95) CuIn
1-x
Ga
x
Se
2
(CIGS) absorbers with Ga content
~30 %, corresponding to an absorber band gap energy of 1.14 eV [7.1]. PVD-grown CIGS
polycrystalline films deposited on Mo/glass substrates have been mostly used for solar cell
device applications. However, the last few years, CIGS solar cells on flexible substrates with
potential space applications have attracted a significant amount of interest. Flexible solar cells
are also of interest wherever mobile generation of electrical power is required and weight is an
issue [7.44], [7.45]. The optical properties of CIGS films on rigid (Mo/glass) and flexible (Ti
foil) substrates and those of the corresponding solar cells are studied here using Photoreflectance
(PR) and Electroreflectance (ER) spectroscopy.

a) PR spectra of CIGS absorbers on glass and Ti-substrates
PR spectra of CIGS polycrystalline films on both, glass and Ti-foil substrates have been
measured at room temperature (RT) and are presented in Fig. 7.5.1. The 457.9 nm-line of Ar
+
-
laser was used as a modulation source. The PR spectra recorded have a relatively low intensity to
noise ratio, due to the polycrystallinity of the films and, in addition, they exhibit thickness
interferences. The evaluation of these spectra is relatively difficult because of the low quality
signals. Fitting with one TDFF (see Evaluation example of a PR-spectrum, Fig. 7.1.2) gives
band-gap energies at 1.212 and 1.214 eV for the CIGS film on the rigid and the flexible
substrates, respectively. The PR results on the CIGS absorbers are not sufficient and further
analysis of the PR spectra of the corresponding solar cells would help to investigate the optical
properties of the polycrystalline quaternary compounds. CIGS solar cells on rigid and flexible
substrates are thus studied by PR in the following section.

130
0.9 1.0 1.1 1.2 1.3 1.4
-0.02
0.00
0.02
-0.02
0.00
0.02
0.04
0.06
1.212
(a)
glass/Mo

R
/
R
(
x
1
0
-
3
)
Energy (eV)
1.214
CIGS films
PR spectra, 300 K
(b)
Ti/Mo/NaF

Fig. 7.5.1 PR spectra of the CIGS absorber on a) Mo/glass and b) Ti/Mo/NaF substrates.

b) PR spectra of CIGS solar cells on glass and Ti-substrates
In Figs. 7.5.2a) and 7.5.3a), the RT PR spectra of CIGS-based solar cells fabricated on
both, glass and Ti-foil substrates are shown. The 457.9 nm-line of Ar
+
-laser was also in this case
used as a modulation source. Evaluation of these spectra gives the absorber band gap of the cell.
As in the case of the PR spectra of the CIGS absorbers, discussed in section 7.5a), the spectra
exhibit a number of interference fringes at energies below the band gap energy. The origin of
these fringes is discussed in the following: The penetration depth
1
of the 457.9 nm Ar
+
-laser
line in the CIGS cell is given in Table 7.5.1. In the same table, the absorption coefficients
derived from Eq. (2.2.8), using the extinction coefficients k of CIGS [7.3] and CdS [7.46] are
also given. Since for the higher band gap ZnO window layer (E
g
ZnO
=3.37 eV [7.47]) there is
practically no absorbance, the ZnO and
1
-values are not given in Table 7.5.1. The 457.9

nm Ar
+
-laser beam, used as a modulating source, reaches only the upper region of the CIGS
layer, just the ~50nm of the absorber (Table 7.5.1). The inhomogeneous Ga-incorporation into
the CIGS films can be a possible reason of the fringes observed in the PR spectra of the CIGS
cells (Figs. 7.5.2a) and 7.5.3a)); this can possibly lead to the interference of light beams reflected

131
at the front surface and the interface formed due to the step-like concentration gradient of the
absorber. It should be noted, that the increased background on the high-energy side of the spectra
is due to the modulating laser beam.
In the PR spectra of CIGS cells on glass and Ti-foil, two bands are present that can be
assigned to the E
a
- and E
b
-energy bands of the quaternary absorbers. The absorber band energies
were determined by fitting these bands with two TDFFs (see Evaluation example of a PR-
spectrum, Fig. 7.1.2). Band energies obtained for CIGS polycrystalline films are listed in Table
7.5.2. The fitting results for glass and Ti foil substrate solar cells are depicted in Figs. 7.5.2b) and
7.5.3b), respectively.

Table 7.5.1 Optical properties of CIGS solar cells at different wavelengths.

Modulating source Material Optical properties
457.9nm
(2.7 eV)
514.5nm
(2.4 eV)
632.8nm
(1.96 eV)
Absorption coefficient
( , 10
5
cm
-1
)
absorber: 2.1
CdS: 1.1
absorber: 1.4
CdS: 0.4
absorber: 0.9
CdS: wihout
CIGS
solar cell
on glass
x=0.34
Penetration depth
(
1
, nm)
absorber: 47
CdS: 91
absorber: 71
CdS: 246
Absorber: 114
CdS: without
Absorption coefficient
( , 10
5
cm
-1
)
absorber: 2.1
CdS: 1.1
absorber: 1.4
CdS: 0.4
absorber: 0.9
CdS: without
CIGS
solar cell
on Ti
x=0.36
Penetration depth
(
1
, nm)
absorber: 48
CdS: 91
absorber: 72
CdS: 246
absorber: 117
CdS: without

In the RT PR spectra of the CIGS epitaxial layers on GaAs substrate, already discussed in
7.1a), the E
a
- and E
b
-bands could not be resolved at room temperature. The PR signals of the
CIGS polycrystalline films show an energy separation of the E
a
- and E
b
-bands of approximately
60 and 70 meV for the rigid and the flexible substrate solar cell, respectively. The splitting of the
A-B excitons at 300 K is 0 meV for CuInSe
2
and 85 meV for CuGaSe
2
, as reported for single
crystals in Refs. [7.48], [7.49], [7.50]. This splitting is due to the combined effect of the non-
cubic crystal field and the spin-orbit interaction. The increased energy separation
ab
=E
a
-E
b
in
our case, as calculated from the PR spectra, is tentatively attributed to two additional sources of
distortion, e.g. polycrystallinity and Ga-incorporation into the absorber layer. The energy
separation may be additionally increased in the presence of elastic strain.

132
0.9 1.0 1.1 1.2 1.3 1.4 1.5
-0.04
-0.02
0.00
0.02
0.04
-0.04
-0.02
0.00
0.02
0.04
PR spectrum, 300 K
(a)

Energy (eV)
R
/
R

(
x
1
0
-
3
)
E
b
E
a (b)

Fig. 7.5.2 PR spectrum a) and fitting b) for the CIGS-absorber-on-glass solar cell (cell:1.5).

For the flexible solar cell, shown in Fig. 7.5.3a), the lattice mismatch between the
absorber layer and the NaF layer deposited on Mo, prior to the absorber deposition, can lead to
compressively strained CIGS layer: The lattice constant of NaF is 4.60 [7.51], that of CIGS
with x=0.36 is 5.723 and has been obtained by linear extrapolation of the lattice constants of
the ternary compounds, CIS and CGS, known from X-ray Fluorescence (XRF) data (
CIS
=5.784
and
CGS
= 5.614 [7.52]. Conclusively, the compressive strain in a CIGS on Ti-foil solar cell
leads to an increased energy separation of E
a
- and E
b
-bands in agreement with Ref. [7.10].

133
0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
-0.02
0.00
0.02
0.04
-0.02
0.00
0.02
0.04
CIGS solar cell on Ti substrate
PR spectrum, 300 K

(a)

Energy (eV)
R
/
R

(
x
1
0
-
3
)
E
b
E
a (b)

Fig. 7.5.3 PR spectrum a) and fitting b) for the CIGS-absorber-on-Ti-foil solar cell (cell:1.2).

Inserting the E
a
-gap energies determined by fitting the PR spectra of CIGS solar-cell
absorbers in Eq. (7.1.1), the Ga-content (x=[Ga]/([Ga]+[In])) of the CIGS absorbers was
calculated to x=0.31 and x=0.23 for the rigid and flexible substrate solar cell, respectively. For
the CIGS-absorber-on-glass solar cell, the calculated value is consistent with the value obtained
from XRF measurements. For the CIGS-absorber-on-Ti-foil solar cell, the respective value is
much smaller than the one known from XRF data. A possible explanation could be the strong
concentration gradient of this absorber: Usually, the gallium concentration is higher close to the
back contact, leading to an inevitable grading of the Ga-content throughout the absorber active
layer. However, by comparison with the CIGS-absorber-on-glass, the CIGS-absorber-on-Ti-foil
exhibits a higher Ga segregation close to the substrate due to the lower growth temperature of
this absorber; this results in an enhanced Ga diffusion towards the Mo back contact and, thus, in
a smaller amount of Ga close to the surface, compared to the CIGS-absorber-on-glass. It should
be noted, that, in this case, the PR spectra give information on the band gap of the upper region
of the CIGS layer because of the small penetration depth of the modulating laser beam (~50nm
for the 457.9 nm-line of an Ar
+
-laser, see Table 7.5.1), whereas XRF-analysis refers to the whole

134
1.78 m thick layer. Optical modulation can, therefore, be used to extract the local concentration
of the absorber layer by selection of the proper modulation wavelength. Considering that, RT PR
spectra of CIGS solar cells were recorded with different wavelengths as a modulating source and
are discussed in the following section.

c) Wavelength-dependent PR spectra of CIGS solar cells
In Figs. 7.5.2a) and 7.5.3a), the PR spectra of CIGS cells on glass and Ti-substrate,
respectively, excited by the 457.9 nm Ar
+
-laser are shown. PR spectra were also recorded using
the 514.5 nm Ar
+
-laser and the 632.8 nm He-Ne laser as a modulating source. The wavelength-
dependent-PR spectra of CIGS solar cells on both substrates are presented in Figs. 7.5.4 and
7.5.5.
CIGS cells consist of 21 different cells (see Figs. 7.5.4 and 7.5.5). By using the I-V
curves (an example is depicted in Fig. 1.2.4) acquired for these CIGS cells at HMI-Berlin, the
efficiency (see Eq. (1.2.7)) of each cell has been determined. In an effort to study a possible
correlation between the PR spectrum and the cell efficiency on both substrates, PR spectra are
recorded on different cells. In each case, the cell studied is denoted as cell:i.j, where i=1-3
designates the column number and j=1-7 the row number (see Figs. 7.5.4 and 7.5.5). In Figs.
7.5.4 and 7.5.5, PR spectra recorded using three different laser-wavelengths as modulating
source on the glass-substrate-cell:1.5 and on the Ti-substrate-cells:1.2 and 1.4 are shown. Among
the two flexible cells, cell:1.2 exhibits a very low efficiency, =0.04 % and is thus characterized
as a bad cell, while cell:1.4 has a quite satisfactory efficiency of =12.49 %.
Evaluation of the PR spectra (see Evaluation example of a PR-spectrum, Fig. 7.1.2) gives
the absorber band gap of both cells for different modulating sources, listed in Table 7.5.2. The
variation of the modulating source and thus of the laser-wavelength-penetration depth
1

(Table 7.5.1) in the CIGS cell aims to the study of the energy band gaps of the non-homogeneous
absorber-cells. The strong compositional gradient within the CIGS absorbers is analyzed in
7.5b). The following are observed:
1) the spectra obtained using the Ar
+
-laser as modulating source (457.9 nm and 488 nm)
consist of two peaks, assigned to the E
a
- and E
b
-transitions, already discussed in 7.5b).
Additionally, the PR spectra exhibit a number of interference fringes at energies below the band
gap energy.
2) the most penetrating modulating laser beam (the 632.8 nm-line He-Ne laser) used (see
Table 7.5.1), reaches only the upper region of the absorber layer, the ~100nm of the 1.78 m-
thick CIGS absorber layer. This PR spectrum is very noisy and only one peak, assigned to the
E
b
-peak, can be evaluated by fitting using TDFFs. No fringes are present.

135
3) in general, the E
a
- and E
b
-transition energies obtained for the absorber in the Ti-foil-
substrate-solar cell are smaller than the ones for the absorber in the rigid solar cell.
4) with increasing penetration depth (increasing wavelength) of the modulating source,
the values of the E
a
- and E
b
-transition energies are slightly decreased. In particular, comparing
the E
b
-energy values obtained by the modulation field of 457.9 nm (more surface-sensitive) and
632.8 nm (more penetrating)-laser wavelengths that provide information on the upper 50 and 100
nm of the absorber layer, respectively, a red-shift of 30 meV (shift to lower energies) is found in
both cells (see Table 7.5.1). This shift can be explained with respect to the XRF data on the
CIGS films revealing a slight increase of the Ga-content towards the CIGS/CdS interface.

Fig. 7.5.4 PR spectra of the CIGS-absorber-on-glass cell:1.5 (= 15.64 %).

0.9 1.0 1.1 1.2 1.3 1.4 1.5
R
/
R

(
x
1
0
-
3
)
457.9 nm
514.5 nm
632.8 nm

Energy (eV)
PR spectra, 300 K
cell:1.5

136

Fig. 7.5.5 PR spectra of the CIGS-absorber-on-Ti-foil-solar cell: a) cell:1.2 (=0.04 %bad
cell) and b) cell:1.4 (=12.49 %).

cell:1.2
cell:1.4

0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
R
/
R

(
x
1
0
-
3
)
632.8 nm
514.5 nm
457.9 nm

Energy (eV)

(a) cell:1.2
PR spectra, 300 K

0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
632.8 nm
457.9 nm
514.5 nm

R
/
R

(
x
1
0
-
3
)
Energy (eV)

(b) cell:1.4
PR spectra, 300 K

137
Table 7.5.2 PR spectra. E
a
- and E
b
-transition energies of CIGS absorbers on rigid and flexible
substrate solar cells.

Modulating wavelength in PR spectra
457.9 nm 514.5 nm 632.8 nm
Substrate [Ga]/([Ga]+[In])
E
a

(eV)
E
b

(eV)
E
a

(eV)
E
b

(eV)
E
a

(eV)
E
b

(eV)
glass 0.34 (cell:1.5) 1.181 1.242 1.155 1.220 1.209
Ti 0.36 (cell:1.4)

0.36 (cell:1.2bad cell)
1.119

1.144
1.199
1.222
1.214
1.125

1.133
1.243

1.219
1.201

1.205

d) Correlation between PR spectra and efficiencies in CIGS-on-Ti-foil solar cells
By using the most surface-sensitive laser wavelength of 457.9 nm as modulating source,
different Ti-substrate-solar cells have been studied by PR. PR spectra are recorded on cells in the
x-direction, cells:1.4, 2.4, 3.4 and in the y-direction, cells:1.5, 1.4, 1.2, as depicted in Fig. 7.5.6.
In addition, electrical measurements of the efficiencies of these cells have been conducted
(Table 7.5.3), in an effort to correlate the PR signals to the corresponding efficiencies of the
cells. The E
a
- and E
b
-transition energies calculated by fitting with two TDFFs (see Evaluation
example of a PR-spectrum, Fig. 7.1.2) are given in Table 7.5.3. It is found that, the maximum
energy difference between the E
a
- and E
b
-transitions in different cells is 60 meV, as in the case
of the E
b
-transition in cell:1.4, compared to the one in cell:1.5. The energy of the E
a
- and E
b
-
transitions are dependent on the Ga-content of the CIGS absorber: By moving in the x-direction
(from cell:1.4 to cell: 3.4) a slight shift of the PR bands to higher energies is observed. It can be
thus assumed that there is an increase in the Ga-content of the CIGS absorber by moving from
the left to the right (x-direction) side in the same cell, as shown in Fig. 7.5.6. The same tendency
is observed by moving in the y-direction (from cell:1.5 to cell:1.2) in the CIGS cell. The degree
of compositional gradient (degree of inhomogeneity) within the cell of size 10x10cm
2
needs to
be further studied with structural analysis techniques (XRF).
In addition, by comparison of the PR spectra of the cell:1.2 (low efficiency cell) with
those of the cell:1.5 (high efficiency cell), no significant difference in the signal-to-noise ratio of
these spectra is observed. The signal-to-noise-ratio of a PR spectrum is indicative of the degree
of disorder of the sample studied and decreases when the sample has an increased disorder.
Therefore, the low efficiency of the cell:1.2, for which a PR spectrum of similar signal-to-noise-
ratio with that of the cell:1.5 (high efficiency cell) is recorded, should be attributed to parameters
of the upper layers (CdS, ZnO) constituting the cell and/or the CIGS/CdS, CdS/ZnO interfaces
and not to the presence of disorder in the absorber.

138

Fig. 7.5.6 PR spectra of the CIGS-absorber-on-Ti-foil solar cell measured at different cells. The
modulating source used is the 457.9 nm Ar
+
-laser.

0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

R
/
R

(
x
1
0
-
3
)
Energy (eV)
x3
PR spectra, 457.9 nm Ar
+
-laser
cell:1.5
cell:1.4
cell:1.2

0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
R
/
R

(
x
1
0
-
3
)

Energy (eV)
PR spectra, 457.9 nm Ar
+
-laser
cell:2.4
cell:1.4
cell:3.4

cell:1.2
cell:1.4
cell:1.5
x
y
cell:2.4 cell:3.4

139
Table 7.5.3 PR spectra. Transition energies of different Ti foil-substrate solar cells
(modulating source: 457.9 nm Ar
+
-laser).

Cell Efficiency
(%)
E
a
(eV) E
b
(eV)
y -direction
1.2 0.04 1.144 1.214
1.4 12.49 1.119 1.199
1.5 14.76 1.130 1.259
x-direction
1.4 12.49 1.119 1.199
2.4 14.24 1.137 1.251
3.4 8.04 1.150 1.261

e) ER spectra of CIGS cells
RT ER spectra were recorded on CIGS-based solar cells fabricated on both, glass and Ti-
foil, substrates at room temperature and are shown in Fig. 7.5.7. Two bands were observed
assigned, as in the case of the PR spectra (7.5b)), to the E
a
- and E
b
-transition energies of the
chalcopyrite layer used as absorber. The ER spectra are fitted using two TDFFs (see Evaluation
example of a PR-spectrum, Fig. 7.1.2); the fitting results are given in Table 7.5.4. The band gap
energies of the quaternary absorbers obtained from the ER spectra are, in principal, mean values
averaged over the whole absorber layer. In the case of the Ti-substrate-solar cell, the absorber
band-gap energies found are smaller than the ones calculated by the evaluation of the PR spectra
(7.5b)). The opposite is observed on the glass-substrate-solar cell.
As discussed in detail in 7.1, in the CIGS quaternary alloy system, the band gap-energy
depends on the Ga-content of the absorber, as described by Eq. (7.1.1). By inserting in Eq.
(7.1.1) the E
a
-gap energy of the absorber (Table 7.5.4), as determined by fitting the ER spectra of
the corresponding CIGS cells, the Ga-content (x=[Ga]/([Ga]+[In])) of the absorber is calculated
to x=0.32 and x=0.18 for the rigid and flexible substrate solar cell, respectively. Therefore, the
Ga-fraction incorporated in the absorber of the flexible solar cell is much smaller than that
calculated by EDX to x=0.36. In accordance with the PR results (7.5b), the calculated value of
the CIGS-absorber-on-glass solar cell is consistent with the value obtained from XRF
measurements. On the other hand, the values found for the CIGS-absorber-on-Ti-foil solar cell,
is even smaller than the one calculated by PR.
It is concluded that ER spectroscopy is a powerful tool for the determination of the
absorber band-gap energy in solar cell devices.

140
0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
-0.8
0.0
0.8
-3
-2
-1
0
1
2
1.189
1.226
glass/Mo (a)

R
/
R

(
x
1
0
-
3
)
Energy (eV)
1.123
1.200
Ti/Mo/NaF
CIGS solar cells
ER spectra, 300 K
(b)

Fig. 7.5.7 ER spectra of the CIGS-absorbers on a) Mo/glass solar cell (cell:1.5 with = 15.64 %)
and b) Ti-foil solar cell (cell:1.4 with = 12.49 %).

Table 7.5.4 ER spectra. E
a
- and E
b
-transition energies of CIGS absorbers on rigid and flexible
substrate solar cells.

ER, 300 K
CIGS solar cells
Substrate [Ga]/([Ga]+[In]) E
a
(eV) E
b
(eV)
glass 0.34 1.189 1.226
Ti 0.36 1.123 1.200

7.6 (RT) Study of ZnSe/CuGaSe
2
/Mo/glass heterostructrures by Photoreflectance spectroscopy

In the last decade, serious efforts to substitute the CdS buffer layer by other nontoxic
low-absorbing materials have been made [7.45], [7.53]. ZnSe is one of the materials used
alternately as a buffer layer.
A RT PR spectrum of the ZnSe films deposited on CuGaSe
2
/Mo/glass substrates by E-
Beam Evaporation (EBE) is shown in Fig. 7.6.1. The 351 nm-line of a Kr
+
-laser has been used as
a modulation source. The spectrum was fitted with one TDFF function (see Evaluation example

141
of a PR-spectrum, Fig. 7.1.2). According to the fitting results, a mean value of the (fundamental)
energy band gap of E
g
= 2.69 eV has been determined. It should be noted that, in the case of
polycrystalline films, PR spectra are usually obtained only at low temperatures. Thus, the good
signal-to-noise ratio of the PR spectrum of the ZnSe film even at room temperature underlines
the very good crystal quality of the deposited films. This result is supported by the results of
XRD, SEM, AFM, and Raman studies [7.54].

1.5 2.0 2.5 3.0 3.5
-0.6
0.0
0.6
1.2
1.8
PR 300 K, 350.7 nm Kr
+
- laser
ZnSe on CuGaSe
2

R
/
R

(
x
1
0
-
3
)
Energy (eV)
2.7 eV
laser

Fig. 7.6.1 PR spectrum of ZnSe on CuGaSe
2
.

- CHALCOPYRITE SELENIDE HOMOSTRUCTURES
7.7 Raman (RT) and PL-study (RT&LT) of as- grown and Ge-doped CuGaSe
2
films

In the case of CuGaSe
2
-heterojunction cells, one of the major problems that need to be
encountered is related to the absorbers dopability. Efficient heterojunction solar cells can be
achieved by inversion of the heterointerface i.e. the surface of the p-type absorber layer should
be converted into n-type. However, CuGaSe
2
thin films exhibit only p-type conductivity, for all
compositions, which is in accordance with the doping pining rule, introduced by Zhang et al.
[7.55]. The experimentally observed maximal p-type doping limit of CuGaSe
2
has been found to
be 1.4x10
20
cm
-3
, while the corresponding n-type is negligible. Several efforts have been made
on extrinsic donor doping of CuGaSe
2
single crystals, using Ge in principal, B or Ag, as dopants.
In this work, the effect of donor doping on the structural properties of CuGaSe
2

polycrystalline films is studied by Raman and Photoluminescence (PL) spectroscopy. The

142
investigation of the mechanism of extrinsic doping is a step towards the preparation of
homojunction-photovoltaic devices based on large band-gap chalcopyrites with improved solar
cell performance.

a) RT Raman spectra
In Figs. 7.7.1a), b), and c), the Raman spectra of as grown CuGaSe
2
and Ge doped
CuGaSe
2
absorbers prepared using three-and one-stage-implantation processes are presented.
According to the polarization selection rules of the point group D
2d
12
of chalcopyrites, by using a
vertically polarized laser beam for the excitation of Raman scattering, as in our case, only the
A
1
-, B
1
-, and B
2
- modes are allowed [7.12]. The spectra of the as grown and Ge doped films
consist of three main peaks assigned to the A
1
- and B
2
-modes of CuGaSe
2
[7.12]. The narrow
peak at 234 cm
-1
is an intensive plasma line (p.l.) of the exciting Kr
+
-laser beam. [7.15].
The Raman spectra of as grown films (Fig. 7.7.1a)) exhibit spectral line-shapes of
unperturbed bulk material and could be fitted with Lorentzians (see Evaluation example of a
Raman-spectrum (1), Fig. 7.2.2). The most intense Raman mode is the A
1
-mode of the CuGaSe
2
absorber at 184 cm
-1
, which results from the motion of Se relative to Cu and Ga at rest (breathing
mode) [7.13]
.
The A
1
-mode corresponds to the
1
representation of the folded chalcopyrite zone-
schema; it appears independently of the experimental configuration and dominates the Raman-
spectrum [7.56], [7.57]. The peaks at 249 cm
-1
and 273 cm
-1

are assigned to the B
2
(TO)- and B
2
(LO)-modes of CuGaSe
2
, respectively [7.13]. These two vibrations arise from the opposite
motion of Cu and Ga atoms along an axis perpendicular to the plane of motion of the Se atoms.
The B
2
- longitudinal and transverse modes are associated with the high-energy
4
[
15
]
component, which originates from the
15
optical mode of the equivalent cubic material [7.57].
In the Raman spectra of the Ge doped films (Figs. 7.7.1b) and c)), the two bands
observed at 184 and 273 cm
-1
and attributed to the A
1
- and B
2
(LO)-modes of the CuGaSe
2
absorber, respectively, exhibit asymmetric broadening, representative of a Fano-line-shape
[7.58]. The increased Raman-linewidths are accompanied by an increased background. The
Fanos theoretical formula [7.59],
background
1
) q (
I I
2
2
0
+
(
+
+
=
(7.7.1)

where =(-
0
)/,
0
: phonon frequency, : phonon linewidth, q: asymmetry factor, describes
the interference of a discrete autoionized state with a continuum giving rise to characteristic
asymmetric peaks in the excitation spectra. In the Raman spectra of heavily doped
semiconductors, the Fanos expression is used to describe the interaction of a discrete scattering

143
state (phonon) with a continuous background (electronic excitations between valence bands)
[7.59].

150 200 250 300
100
200
(a)

as grown
Raman-shit (cm
-1
)
R
a
m
a
n
-
i
n
t
e
n
s
i
t
y

(
c
p
s
)
100
(b)
B
2
(LO)
273 cm
-1
B
2
(TO)
249 cm
-1
A
1
184 cm
-1

100
(c)
(p.l.)

Fig. 7.7.1 Raman spectra of a) as grown CuGaSe
2
films, and Ge doped CuGaSe
2
films in b)
three-stage process, and c) one-stage process excited by 647.1nm/250mW Kr
+
-laser at
300 K.

The Raman-spectra of doped CuGaSe
2
films were fitted using one Lorentzian and two
Fano line-shapes. The fitting results are demonstrated, in the case of CuGaSe
2
absorbers doped
in one stage, in Fig. 7.7.2. The background was subtracted using a polynomial. The 184 cm
-1

(A
1
) mode was fitted with a pure Fano line-shape. The 249 cm
-1
(B
2
, TO) mode appeared
relatively weak in all spectra and also located on the wings of the dominant feature at 273 cm
-1

(B
2
, LO). The frequencies, widths and intensities of these two phonons were obtained by fitting
the corresponding Raman bands with a combination of a Lorentzian, for the 249 cm
-1
, and a
Fano line-shape, for the 273 cm
-1
band. The combined Lorentz-Fano line-shape has been also
used in Ref. [7.60].

144
150 200 250 300 350 400
-20
0
20
40
60
LO
FA
2
FA
1
(p.l.) FA
1
: 1
st
Fano
Pos
1
: 184.0020.412
Amp
1
: 39.772.16
Wid
1
: 9.3200.825
q
1
: 0.20360.0392
LO: Lorentzian
Pos : 246.304 1.39
Amp : 6.40878 2.47
Wid : 7.254.82
FA
2
: 2
nd
Fano
Pos
2
: 273.67 0.62
Amp
2
: 24.02 2.56
Wid
2
: 6.89 1.17
q
2
: -0.1750.082
CuGaSe
2
doped in one-stage, Raman 300 K

R
a
m
a
n
-
i
n
t
e
n
s
i
t
y

(
c
p
s
)
Raman-shift (cm
-1
)

Fig. 7.7.2 Fitting results of the Raman spectrum of a CuGaSe
2
absorber doped in one stage. The
narrow peak at 234 cm
-1
is an intensive plasma line (p.l.) of the exciting Kr
+
-laser
beam (Evaluation example of a Raman-spectrum (2)). The function used is:
MB+FA+LO+FA. MB corresponds to a manual linear background used as a baseline,
FA to one Fano function and LO to one Lorentzian function. The fitting parameters
are: Pos the Raman-mode frequency, Amp the Raman-intensity, Wid the width
(FWHM) and q the asymmetry parameter of the Fano function (see Eq. (7.7.1)).

In the case of a CuGaSe
2
absorber doped in one stage, the A
1
-peak shows an asymmetric
broadening towards larger wave numbers (positive q in Eq. (7.7.1)). The q factor represents the
Fano asymmetry parameter, which, for the A
1
-mode, was calculated to q=0.20. On the other
hand, the B
2
(LO)-mode situated at 273 cm
-1

is broadened towards smaller wave numbers
(negative q, in our case q=-0.17). Left (right) asymmetry, represented by a negative (positive) q
factor can be found in materials with n-type (p-type) doping. The fitting of the Raman spectra of
heavily doped polycrystalline silicon thin films, for example, gives a relatively small positive q
for the LO-TO peak of B-doped films (p-type) and a negative q for the same peak of P-doped
films (n-type) [7.61]. It can be, though, assumed, that there is a relationship between the sign of
the q parameter and the symmetry of Raman phonon modes. In fact, a study of the Raman modes
in YBa
2
Cu
3
O
y
has given a positive value of q for the B
1g
-mode and a negative one for the A
g
-
mode [7.60] that has been then explained as originating from the coupling of different symmetry
Raman modes to different sets of electrons. Following this, the right-left asymmetry of the A
1

(184 cm
-1
) and the B
2
(273 cm
-1
) modes in Ge doped CuGaSe
2
absorbers is tentatively
interpreted as a result of the interaction of the A
1
- and the B
2
-phonons with different sets of

145
electrons. It is noted, that the fitting of the Raman-spectrum of the CuGaSe
2
absorber doped in
three stages gives smaller asymmetry parameters (q=0.15 for the A
1
-mode and q=-0.12 for the B
2

(LO)-mode) than in the case of the absorber doped in one stage.
The fitting results of Raman band-intensities and -widths of as grown and Ge doped
CuGaSe
2
films are depicted in Figs. 7.7.3a) and b), respectively. In Fig. 7.7.3a), the intensities of
the A
1
-, B
2
(TO)-, and B
2
(LO)-modes of as grown and Ge doped films normalized to the intensity
of the A
1
-mode are compared. Since the thickness of the implanted region was 200 and 150 nm
for films implanted in a three- and an one-stage process, respectively, and the penetration depth
of the incident laser light (647nm/1.9 eV Kr
+
-laser) was 200 nm ((CuGaSe
2
) at 1.9 eV
=4.89x10
4
cm
-1
[7.43]), Raman scattering intensities were generated mainly in the implanted
sample region. The normalized mode intensities in Fig. 7.7.3a) show that, in the Raman spectra
of as grown films, the A
1
-mode dominates. On the contrary, in the spectra of Ge doped films, the
A
1
mode is damped and the B
2
(LO) modes are favored. In particular, in the spectra of as grown
films, the intensity ratio I(B
2
(LO))/I(A
1
) is 0.3, while in the spectra of films doped in one- and
three-stages it is, respectively, two and three times larger. It is assumed, that bond-breaking and
bond reorientation effects, generated by the implantation process, favor excitation of asymmetric
lattice vibrations (B
2
) instead of the symmetric ones (A
1
).
In Fig. 7.7.3b), the band-widths of as grown and Ge doped films are compared. Possible
reasons for Raman band broadening are considered to be: sample off-stoichiometry, disorder
induced by minor secondary phases [7.62], and implantation damage. However, grazing
incidence X-Ray Diffraction (GI-XRD) data of films prepared by the same growth process as the
films studied here showed no secondary phase formation [7.63], which rules out the possibility
of secondary phase induced disorder. Non-stoichiometry may be, therefore, responsible for the
Raman band-widths of the as grown samples. On the other hand, band broadening was more
pronounced in Ge doped films, which implies that implantation damage is, in this case, the most
probable broadening mechanism. In addition, the band-widths of the most intense Raman modes,
A
1
and B
2
(LO), indicate that films doped in one-stage suffer more from implantation damage
than those doped in three-stages.

146
180 200 220 240 260 280
0.0
0.5
1.0
0
10
20
Raman-shift (cm
-1
)
F
W
H
M

(
c
m
-
1
)
(a)
B
2
(LO) B
2
(TO) A
1

I
n
t
e
n
s
i
t
y

r
a
t
i
o

I
/
I
(
A
1
)
as grown
doped in 3-stages
doped in 1-stage
(b)

Fig. 7.7.3 Raman a) band-intensities of the A
1
- (184 cm
-1
), B
2
(TO)- (249 cm
-1
), and B
2
(LO)-
(273 cm
-1
) modes normalized to the intensity of the A
1
-mode, and b) band-widths of
as grown (), doped in three-stages (), and doped in one-stage () CuGaSe
2
films.

b) Photoluminescence spectra
PL spectra at 300 K
Figs. 7.7.4a), b), and c) show the photoluminescence (PL) spectra of as grown (Fig.
7.7.4a)) and Ge doped (Figs. 7.7.4b) and c)) CuGaSe
2
([Cu]/[Ga]=0.95)

absorbers at room
temperature. The PL-spectra illustrated in Figs. 7.7.4a)-c) were fitted with a combination of
Gaussians (see Evaluation example of a PL-spectrum, Fig. 7.3.2). The PL-emission of as grown
CuGaSe
2
films at 300 K (Fig. 7.7.4a)) consists of a rather symmetric band situated at 1.67 eV.
This is in agreement with the results of a similar study on polycrystalline PVD grown Ga-rich
CuGaSe
2
films ([Cu]/[Ga]=0.92) [7.64]. The room temperature PL-emission has been assigned
there to band-to-band transitions [7.64]. One-stage implantation with Ge-ions (Fig. 7.7.4c))
retains the band-to-band emission at 1.67 eV and, at the same time, it gives rise to a new more
intensive and very broad PL-emission centered at 2.10 eV. This emission at energies higher than
the band-gap energy is probably related to the PL-emission of ion activated secondary phases

147
(CuSe, Cu
2
Se, Ga
2
Se
3
) on and near the film surface. Three-stage implantation (Fig. 7.7.4b))
seems to quench the PL-emission in the energy range 1.6-2.3 eV.
1.4 1.6 1.8 2.0 2.2 2.4
0
100
200
300
0
100
200
300
200
400
600
(a) as grown

P
L
-
i
n
t
e
n
s
i
t
y

(
c
p
s
)
PL-energy (eV)
(b)
2.1 eV

(c)
laser
1.67 eV

Fig. 7.7.4 PL-spectra of a) as grown CuGaSe
2
2
films in b) three-
stage process, and c) one-stage process excited by 514.5nm/200mW Ar
+
-laser at 300
K.

PL spectra at 2 K
The PL spectra of as grown and Ge doped CuGaSe
2
films at 2 K are presented in Figs.
7.7.5a), b), and c). At low temperatures, the PL emission of as grown films (Fig. 7.7.5a)) consists
of two components at least: an intense, high- and a weak, low-energy component at 1.66 and
1.63-1.60 eV, respectively. It should be noted, that the broad-band emission at energies above
the absorber gap energy, that was observed on the room temperature PL-spectra, does not
contribute to the low temperature spectra. PL-emission at energies below the band-gap energy, in
chalcopyrites, has been studied extensively and has been assigned to donor-acceptor pair
recombination (DAP). Low temperature (10 K) PL studies on CCSVT grown Ga-rich CuGaSe
2

films ([Cu]/[Ga]=0.93) have been reported in [7.63]. The PL emission consisted of an
asymmetric DAP-band at 1.58 eV. The low temperature PL spectra of Ga-rich Cu
x
Ga
y
Se
2

epitaxial layers on GaAs(001) substrates reported in [7.64], [7.18] depended strongly on the

148
[Cu]/[Ga] ratio. Ga-rich material has more defects and its PL-emission was referred to as defect
related PL. With increasing the Ga fraction, the emission maxima were shifted to lower energies
and the respective bands were broadened. Also in the case of the samples studied in this work,
Ge implantation results in both, one- (Fig. 7.7.5c)) and three-stage (Fig. 7.7.5b)) processes, in a
shift of the overall PL-band to lower energies, band-width increase, and intensity decrease. The
intensities and widths of the PL sub-bands are changed because the contribution of the respective
sub-components is changed due to generation and/or activation of defects by the implantation
process. By comparison of Figs. 7.7.5b) and c) (Ge doped films) with Fig. 7.7.5a) (as grown
films), it can be seen, that the low energy sub-band in the range 1.63-1.60 eV is enhanced.
Considering both, the Raman and PL results, these strongly indicate an increase in
structural disorder and defect concentration, particularly, in CuGaSe
2
films doped in one-stage.
The intensity increase of the low-energy PL-component, in this case, may be associated with the
increase in defect concentration due to implantation damage.
1.4 1.6 1.8 2.0 2.2
0
2
4
6
0
1
0
1
(a)
as grown

P
L
-
I
n
t
e
n
s
i
t
y

(
n
A
)
PL-energy (eV)
1.63 eV
1.60 eV
(b)

1.62 eV
1.66 eV
1.63 eV
(c)
1.66 eV

Fig. 7.7.5 PL-spectra of a) as grown CuGaSe
2
2
films in b) three-
stage process, and c) one-stage process excited by 514.5nm/200mW Ar
+
-laser at 2 K.

149
- CHALCOPYRITE SULFIDE HETEROSTRUCTURES

The optical and structural properties of CuIn
1-x
Ga
x
S
2
(CIGS) films and CIGS/CdS and
CIGS/CdS/ZnO heterostructures are studied by Photoreflectance (PR) and Raman spectroscopy,
at low (20 K) and room temperatures, respectively. Then, the corresponding CIGS-based solar
cells are measured by Electroreflectance spectroscopy. Two different x=[Ga]/([In]+[Ga]) ratios,
0.04 and 0.12, have been utilized. The absorber with x=0.12 is already at the upper limit of the
quaternary that can lead, up to now, to good quality CIGS solar cells with maximum widened
energy gap, while the one with x=0.04 is expected to give results very close to the ternary
CuInS
2
(CIS) chalcopyrite.

1-x
Ga
x
S
2
1-x
Ga
x
S
2
/CdS and
CuIn
1-x
Ga
x
S
2
/CdS/ZnO heterostructures by Photoreflectance spectroscopy

7.8.1 CuIn
1-x
Ga
x
S
2
polycrystalline films

a) Determination of LT transition energies
In Fig. 7.8.1, the PR spectra of the CuIn
1-x
Ga
x
S
2
(CIGS) samples (x=0, 0.04, and 0.12) at
20 K are shown. The room temperature PR spectra could not be evaluated due to their low
intensity to noise ratio and they will not be further discussed.
In CuInS
2
(CIS), with a small distortion from the cubic symmetry, the A and B peaks are
so close that they are never resolved at room temperature (
cf
>0) [7.4]. However, Tell et al.
[7.65], by comparing the electro- (ER) and photoreflectance (PR) spectra with reflectance
spectra, concluded that the dominating mechanism for CIS at 2 K is the change in the dielectric
functions of two excitonic transitions. Low-temperature studies of exciton reflectivity and
photoreflectance have failed to locate a third valence band in any of the studied sulphides, CIS
included [7.66]. The PR spectra of CIS single crystals below 200 K consist of two well-resolved
peaks related to the fundamental transition E
0
and the transition involving spin-orbit splitting
E
0
+
0
[7.67]. In general, in the low temperature PR spectra, only E
a
- and E
b
-transitions are
expected to appear [7.66]. The two bands observed in the PR spectra of the absorbers in Fig.
7.8.1 are, thereafter, attributed to the E
a
- and E
b
-excitonic transitions.
The fitting of the PR spectra using a Third Derivative Functional Form (TDFF) gives the
positions of the fundamental band gap energies of the ternary and two quaternary polycrystalline
absorbers (see Evaluation example of a PR-spectrum, Fig. 7.1.2). The fitted values are shown in
Table 7.8.1.

150
1.3 1.4 1.5 1.6 1.7 1.8 1.9
-0.2
0.0
0.2
0.4
-0.1
0.0
0.1
-0.1
0.0
0.1
0.2
(c)
(b)
(a)
Energy (eV)
CuIn
1-x
Ga
x
S
2
absorbers
PR spectra, 20 K
E
b
E
b
E
b
E
a
E
a
E
a
x=0.12
x=0.04
x=0.00

R
/
R

(
x
1
0
-
3
)

Fig. 7.8.1 PR spectra of CIGS (x=0, 0.04, and 0.12) absorbers at 20 K modulated by a)-b) 488
nm Ar
+
-laser and c) 457.9 nm Ar
+
-laser.

Table 7.8.1 E
a
- and E
b
-transition energies of CIGS absorbers at 20 K.

PR 20 K Absorber
a
(eV)
b
(eV)
CuInS
2
1.5330.001 1.5520.001
CuIn
1-x
Ga
x
S
2
with x=0.04 1.5320.001 1.5800.002
CuIn
1-x
Ga
x
S
2
with x=0.12 1.6510.002 1.6720.002

b) Determination of thickness
The reflectance spectra of the CISG absorbers, demonstrated in Fig. 7.8.2, exhibit a
number of interference fringes at energies below the band gap energy. The fringes are originating
from the interference of light beams reflected on the front and back face of the absorber layer.
These fringes can be used to calculate the absorber thickness using a relationship derived in Ref.
[7.68]:

1 2
2 2 1/ 2
1 2
2( )( sin )
N
t
n

=

(7.8.1)

151
where t is the layer thickness, n is the refractive index of the layer, is the angle of incidence,
1
,
2
are the start and end wavelength (
1 2
> ), respectively, and is the number of fringes
between
1

and
2
.
1.0 1.2 1.4 1.6 1.8 2.0 2.2
x5
N=7
N=5
CuIn
1-x
Ga
x
S
2
1008.9 nm
762.5 nm
1002.3 nm
813 nm
Reflectance spectra, 20K

x=0.12
x=0.04 R
e
f
l
e
c
t
a
n
c
e
Energy (eV)

Fig. 7.8.2 Reflectance spectra of CIGS (x= 0.04 and 0.12).

For the calculation of the absorber thickness, the refractive index of the ternary CIS is
used [7.43], since the refractive index of the quaternary CIGS

is not known. In Ref. [7.69], two
different values of n corresponding to the start- and end-wavelength of the scanned region were
chosen. In the present work, the wavelength dispersion of n has been taken into account by
choosing a value in the middle of the scanned spectral region: n =2.87 at 1.4 eV for both CIGS
films with x=0.04 and 0.12. By adding Ga into CIS, the refractive index of the quaternary
compound is lowered. The refractive index of pure CuGaS
2
(CGS) is n =2.58 at 1.4 eV [7.43].
However, addition of 4%-12% Ga does not significantly changes the refractive index of the
ternary. In fact, the refractive indices of the quaternary films studied are almost the same as the
refractive index of CIS due to the small gallium content of the films (12%).
For the thickness calculation, =45
o
was used as an angle of incidence
.
Inserting in Eq.
(7.8.1), =5,
1
=1002.3 nm,
2
=813 nm, in the case of CIGS with x=0.04 and, =7,
1

=1008.9 nm,
2
=762.5 nm, in the case of CIGS with x=0.12, it is found t =3.9 m for both non-
etched films. According to the scanning electron micrographs (SEM), the films appear to be
compact with grain sizes in the order of one m. Prior to etching, the film is covered
homogenously with CuS (4.2), which has not been taken into account in the thickness
determination [7.70]. The SEM micrographs of the etched absorbers indicate a film thickness of

152
about 3 m for both Ga fractions, which is in agreement with the optical thickness calculated by
using Eq. (7.8.1).

c) Determination of carrier concentration
The number of holes N or density of states can be calculated using the relation [7.71]:

* 3/ 2
3
0
8 2 2
3
E
VC
N dn m E
h
= =
(7.8.2)
where n is the number of free electrons in cm
-3
,
* *
*
* *
h e
VC
h e
m m
m
m m
=
+
is the reduced effective mass of
an electron with effective mass
*
e
m and a hole with effective mass
*
h
m , and E is the shift in
energy band edge. In this expression, derived by Moss [7.72], the electron-defect and electron-
electron interaction are neglected.
Considering only the lower energy gap of the quaternary sulphides, e.g. the E
-gap, E
represents the energy shift between the band edge of the quaternary CuIn
1-x
Ga
x
S
2
(CIGS) and the
edge of the ternary CIS compound,
CIGS CIS
E E E E

= = . For the calculation of the carrier
concentration, the effective masses of electrons and holes in CIS,

*
0.16
e e
m m = [7.73] and
*
1.3
h e
m m = [7.74], respectively, are used, because those of the quaternaries are not known.
e
m is
the free-electron mass. For CIS, a band gap of
CIS
E
=1.5 eV, as given in Ref. [7.43] is inserted.

Taking into account the energy-gaps of the quaternary absorbers,
CIGS
E
, that have been

determined experimentally and are given in Table 7.8.1, Eq. (7.8.2) yields N =1.40 10
18
cm
-3
for
CuIn
1-x
Ga
x
S
2
with x=0.04 and N =1.43 10
19
cm
-3
for CuIn
1-x
Ga
x
S
2
with x=0.12.

7.8.2 CuIn
1-x
Ga
x
S
2
/CdS and CuIn
1-x
Ga
x
S
2
/CdS/ZnO heterostructures

The PR spectra measured at 20 K on a CIGS layer with a CdS buffer layer deposited on top
of the chalcopyrite absorber are shown in Fig. 7.8.3. Apart from the absorber bands, a band
assigned to CdS is observed on the high-energy side of these spectra. The band gap energy of the
E
a
-transition in CdS was found to be E
a
=(2.5010.002) and (2.4870.007) eV for x=0.04 and
0.12, respectively, which is in good agreement with the values known from the literature [7.46].
As in the case of the reflectance spectra of the non-etched CIGS films, already discussed in
7.8.1 (Fig. 7.8.2), the PR spectra of the CdS/CIGS layers exhibit interference fringes at the
lower-band gap energy region. The interferences influence the PR absorber line shapes: the E
a

153
gap is shadowed, while the E
b
gap is up-shifted to
b
=(1.5750.004) eV and (1.6810.008) eV
for x=0.04 and 0.12, respectively.
1.4 1.6 1.8 2.0 2.2 2.4 2.6
CdS/CuIn
1-x
Ga
x
S
2
absorber (x=0.04)/CdS
PR spectra, 20 K
R
/
R

(
x
1
0
-
3
)
Energy (eV)
CdS

absorber (x=0.12)/CdS
x2

Fig. 7.8.3 PR spectra of CdS/CIGS (x=0.04 and 0.12).

PR spectra were also recorded, at 20 K, on CIGS layers with both, CdS-buffer and ZnO-
window layers, deposited on top of the chalcopyrite absorber and are presented in Fig. 7.8.4. The
350.7 nm (3.54 eV)-line of a Kr
+
-laser was used as modulating source.
Apart from the absorber bands, bands assigned to the CdS buffer-layer and the ZnO
window-layer, constituting the n-type material of the pn junction, are observed on the high-
energy side of the PR spectra. In particular, in the PR spectra of CIGS/CdS/ZnO
heterostructures, both, the E
a
- and E
b
-bands of the quaternary chalcopyrite compound and the
lower energy E
a
- (or in certain cases both E
a
- and E
b
-bands) of the wurtzite-type CdS and ZnO
layers are present. Two TDFFs were thus used for fitting the PR bands of the absorber layer and
one or two TDFFs for fitting those of the CdS and the ZnO layers (see Evaluation example of a
PR-spectrum, Fig. 7.1.2). In case of the absorber with the larger Ga-fraction (x=0.12),
specifically, the line shapes of the E
a
- and E
b
-bands were more complex and four spectral

154
functions (TDFFs) were needed to fit the PR bands. These four contributions have been also
observed, at room temperature, in the ER spectra of solar cells based on the CIGS absorbers
studied and are discussed in detail in 7.10a) and b).
0
1
2
ZnO
CdS
CIGS
absorber (x=0.12)/CdS/ZnO
ZnO/CdS/CuIn
1-x
Ga
x
S
2

Energy (eV)

PR spectra, 20 K
R
/
R

(
x
1
0
-
3
)
1.5 2.0 2.5 3.0 3.5
0
1
2
CIGS
CdS ZnO
absorber (x=0.04)/CdS/ZnO

Fig. 7.8.4 PR spectra of ZnO/CdS/CIGS (x=0.04 and 0.12).

In the PR spectrum of the absorber with the smaller Ga-fraction (x=0.04), a narrow band
was superimposed at (1.5330.001) eV. This band was initially thought to stem from the Xe-
lamp used as light source, which exhibits very intensive emission peaks at energies below 1.5 eV
due to atomic transitions in the excited gas. Further PR-measurements were thus performed
using a Halogen lamp, which does not exhibit such lines in the reflectance spectra. The band at
1.53 eV was still present; it may be assigned either to luminescence emission of the quaternary
compound or to thickness interferences of light reflected at the front and back interface of the
absorber layer.
The fitting results for the spectra of the CIGS absorbers and the CdS and ZnO upper layers,
are given in Table 7.8.2.

155
Table 7.8.2 E
a
- and E
b
-transition energies of the CIGS, CdS and ZnO layers at 20 K.

PR 20 K Absorber
a1
(eV)
b1
(eV)
a2
(eV)
b2
(eV)
CuIn
1-x
Ga
x
S
2
with x=0.04 1.555
0.005
1.584
0.004

CdS 2.102
0.100
2.399
0.060

ZnO 2.988
0.090
3.303
0.040

CuIn
1-x
Ga
x
S
2
with x=0.12 1.613
0.002
1.626
0.004
1.649
0.001
1.657
0.001
CdS 2.386
0.040

ZnO 3.057
0.090
3.223
0.030

The band gap energies of the E
a
- and E
b
-transitions in CdS and ZnO are found at energies
lower than the ones known from the literature at low temperatures: the band gap energy of ZnO
has been reported to 3.44 eV at 5 K [7.75], and that of CdS to 2.58 eV at 4.2 K [7.76]. The shift
of both, CdS and ZnO gap energies to lower energies reveals that both layers deposited on top of
the absorber layer are strained.
At room temperature, the lattice constants of the semiconductors constituting the
heterostructure are given in Table 7.8.3. By using Eq. (3.1.9), 3.1.2, the lattice constants at low
temperatures (20 K) can be determined. The mean values of the linear thermal expansion
coefficients were calculated according to an equation referred in [7.77]: (2 ) / 3
= +
,
where
and
are the thermal expansion coefficients perpendicular and parallel to the c-axis,
respectively. The
and
values of the ternary CIS have been considered, as the corresponding

value of the CIGS quaternary compounds are not known. The lattice constants at 20 K are also
given in Table 7.8.3.
As it can be seen, the lattice constants of the quaternary chalcopyrites and the CdS and
ZnO compounds change only slightly with the temperature. On the other hand, the lattice
constant of ZnO is smaller than the lattice constant of CdS and both are much smaller than the
lattice constants of the CuIn
x
Ga
1-x
S
2
absorbers studied. As a result, both over-layers exhibit
tensile stresses. It is well known that under the influence of tensile stress the energy band gap is
narrowed [7.80].

156
Table 7.8.3 Lattice constants a (at 300 and 20 K) and mean linear thermal expansion
coefficients of CIS, CdS and ZnO.

Material Crystal Structure a ()
at 300 K

(x10
-6
K
-1
)

(x10
-6
K
-1
)

(x10
-6
K
-1
)
a ()
at 20
CuIn
1-x
Ga
x
S
2
,
x=0.04
Tetragonal 5.5094

9.88* 5.4942
CuIn
1-x
Ga
x
S
2
,
x=0.12
Tetragonal 5.4962 9.88* 5.4810
CdS
Wurtzite
(hexagonal)
4.1363 4.30 2.77 3.79 4.1319
ZnO Wurtzite
(hexagonal)
3.2495 4.31 2.49 3.70 3.2461
Ref. [7.78]
Ref. [7.79]
*The linear thermal expansion coefficient of CuInS
2
has been taken into account [7.77]

1-x
Ga
x
S
2
1-x
Ga
x
S
2
/CdS and CuIn
1-
x
Ga
x
S
2
/CdS/ZnO heterostructures by Raman spectroscopy

In Figs 7.9.1a) and b), the Raman spectra of the CIGS, CdS/CIGS, and ZnO/CdS/CIGS
samples with x=0.04, excited by two different laser wavelengths, 514.5 nm of Ar
+
-laser and
647.1 nm of Kr
+
-laser, respectively, are shown. The Raman spectra of the CIGS, CdS/CIGS and
ZnO/CdS/CIGS samples with x=0.12 are shown in Figs 7.9.2a) and b).
The Raman spectra of quaternary absorbers CIGS

exhibit peaks with frequencies very close
to the mode frequencies of the ternary CIS and CGS end-members. In addition, in the spectra of
CdS/CIGS and ZnO/CdS/CIGS heterostructures, phonon modes assigned to a CuS secondary
phase formed during growth are present. According to the selection rules of Raman scattering,
by excitation with a vertically polarized laser beam, only the A
1
, B
1
, and B
2
modes are observed
[7.12]. The Raman-frequencies were determined by fitting these modes with Lorentzians (see
Evaluation example of a Raman-spectrum (1), Fig. 7.2.2).
Following assignment is based on the phonon-mode-analysis of ternary chalcopyrites
reviewed in [7.13].

a) 514.5 nm Ar
+
-laser
The Raman spectra excited by the 514.5 nm-line of the Ar
+
-laser are shown for x=0.04, in
Fig. 7.9.1a) and for x=0.12, in Fig. 7.9.2a). The two weak peaks at 262 and 292 cm
-1
are assigned
to the B
2
(TO)-mode of CGS and the A
1
-mode of CIS, respectively. The peak at 472

cm
-1
is
assigned to the A
1
-mode of CuS [7.81], which is formed on top of the absorber layer during the
absorber growth process (4.2). Before depositing the CdS layer, CuS is removed by chemical
etching and, therefore, the peak at 472 cm
-1
is not present in the spectra of CdS/CIGS and

157
ZnO/CdS/CIGS. An intense peak at 300 cm
-1
, in the spectra of the CdS/CIGS and
ZnO/CdS/CIGS excited by the 514.5 nm (2.4 eV) laser line, is attributed to the first order
A
1
(LO) mode of the CdS buffer layer [7.82]. The phonon mode at 600 cm
-1
has twice the
frequency of the mode at 300 cm
-1
and is, therefore, assigned to the second order Raman
scattering (RS) of CdS. The high intensity of these peaks is due to the resonant Raman scattering
(5.5.2) of CdS; its energy band gap of 2.42 eV (300 K) [7.46] is close to the excitation energy
of 2.4 eV.
No significant shift of the Raman mode frequencies could be observed as expected by
substitution of In by Ga in CIS and formation of CIGS [7.83]. This is partially due to the small
Ga content of the absorber layers (x0.12) and partially due to the very high Ga concentration at
the interface to the substrate. In the first case, frequencies almost equal to those of the CIS modes
are detected, and in the latter, frequencies of the CGS modes. In case of quaternary CIGS
absorbers with small Ga fraction (x0.12), the optical properties of the ternary CIS can be
considered instead. Apart from this, both excitation wavelengths (514.5 nm of Ar
+
-laser and
647.1 nm of Kr
+
-laser) penetrate 84 and 120 nm, respectively, that is, only the upper region of
the CIGS layer with 3 m thickness (extinction coefficient k , absorption coefficient , and
penetration depth
1
for ternary CuInS

2
and CuGaS
2
compounds are given in Table 7.9.1).
The Ga-distribution within the CIGS layers has been confirmed by Energy Dispersive X-
ray (EDX) and X-Ray Diffraction (XRD) analysis reported in Ref. [7.70]. In any case, the XRD
results confirm the presence of a quaternary chalcopyrite phase in the samples studied here with
Raman-scattering techniques.

Table 7.9.1 Extinction coefficients ( k
, k
), absorption coefficients ( 4 / k = ) and

penetration depths
1
of the 514.5 nm- and the 647.1 nm-laser beams in the CIS
and CGS compounds.

Material Excitation
light
k
( ) / 2 k k k
= +

4 / k =
(10
4
cm
-1
)
1

(nm)

514.5 nm
=2.4 eV
0.499 0.471 0.485 11.846 84.4 CuInS
2
647.1 nm
=1.9 eV
0.437 0.418 0.4275 8.302 120.5
2.4 eV 0.101 0.222 0.1615 3.945 253.5 CuGaS
2
1.9 eV - - - - -

158
b) 647.1 nm Kr
+
-laser
The Raman spectra excited by the 647.1 nm-line of the Kr
+
-laser, shown in Figs. 7.9.1b)
and 7.9.2b), exhibit less intensive background and the peaks are more pronounced. Raman mode
assignment in CIGS, CdS/CIGS and ZnO/CdS/CIGS layers is based again on the phonon-mode-
analysis of ternary chalcopyrites [7.13]: the peak at 292 cm
-1
is assigned to the A
1
-mode of CIS,
the peak at 262 cm
-1
to B
2
(TO)-mode of CGS, the peak at 350 cm
-1
to B
2
(LO)-mode of CIS and
the peak at 524 cm
-1
to the second order of the 262 cm
-1
-B
2
(TO)-mode of CGS [7.13]. The
spectra of CIGS show additionally a peak at 472

cm
-1
assigned to the A
1
-mode of CuS [7.81]
formed on top of the absorber layer during the absorber growth process (4.2). Before depositing
the CdS layer, CuS is removed by chemical etching and, therefore, the peak at 472 cm
-1
is not
present in the spectra of CdS/CIGS and ZnO/CdS/CIGS. The peak at 63 cm
-1
cannot be
correlated to any mode of the ternary (or quaternary) compound according to the selection rules
for the configuration used in these Raman-scattering experiments. Possible deviations from this
configuration, as a no strictly vertically polarized laser-beam for example, could lead to violation
of the selection rules and to observation of additional Raman modes. At 65 cm
-1
, an E(TO)-mode
can be excited in CIS; however, the intensity and width of the 63 cm
-1
peak in the present Raman
spectra do not comply with those expected for a forbidden mode. On the other hand, the narrow
peaks at 95 and 233 cm
-1
are plasma lines (p.l.) of the Kr
+
-laser beam used for excitation [7.15].

159
(b)
(a)
292
2x300 (CdS)
300 (CdS)
absorber/CdS/ZnO
x0.05
absorber/CdS
absorber/CdS
absorber
absorber
647.1nm Kr
+
-laser/300mW
514.5nm Ar
+
-laser/300mW
CuIn
1-x
Ga
x
S
2
, x=0.04

472 (CuS)
262
0 100 200 300 400 500 600 700
233
(p.l.)
2x262
292
472 (CuS)
262
95
(p.l.)
63
absorber/CdS/ZnO
Raman shift (cm
-1
)
R
a
m
a
n
-
i
n
t
e
n
s
i
t
y

(
a
.

u
.
)

Fig. 7.9.1 Raman spectra of the CIGS, CdS/CIGS and ZnO/CdS/CIGS layers with x=0.04,
excited by two different laser beams.

160
0 100 200 300 400 500 600 700
472 (CuS)
262
(b)
(a)
2x262
350
262
292
292 233
(p.l.)
472 (CuS)
95
(p.l.)
63
2x300 (CdS)
300 (CdS)
absorber/CdS/ZnO
absorber/CdS/ZnO
absorber/CdS
absorber/CdS
absorber
absorber
647.1nm Kr
+
-laser/300mW
514.5nm Ar
+
-laser/300mW
CuIn
1-x
Ga
x
S
2
, x=0.12
R
a
m
a
n
-
i
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Raman shift (cm
-1
)

x0.4

Fig. 7.9.2 Raman spectra of the CIGS, CdS/CIGS and ZnO/CdS/CIGS layers with x=0.12,
excited by two different laser beams.

161
1-x
Ga
x
S
2
based solar cells by Electroreflectance (ER) spectroscopy

In Fig. 7.10.1, the ER spectra of CuIn
1-x
Ga
x
S
2
(CIGS) based solar cells (with x=0, 0.04
and 0.12) recorded at 300 K are presented. Only the low energy region of the ER spectra, related
to the band gap energy of the absorber layer, is illustrated. The room temperature ER spectra
exhibit a high intensity to noise ratio and can be easily evaluated.
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
-0.01
0.00
0.01
x=0.00
CuIn
1-x
Ga
x
S
2
solar cells
ER spectra, 300K

R
/
R

(
x
1
0
-
3
)
Energy (eV)
x=0.12
x=0.04
-0.01
0.00
0.01

-0.01
0.00
0.01

Fig. 7.10.1 ER spectra of CIGS (x=0, 0.04, and 0.12) based solar cells at 300 K (fringes at
energies below the band-gap energy are due to thickness interferences).

a) Determination of RT band-gap energies
ER spectra exhibit generally third derivative line shapes that can be fitted with a third
derivative functional form (TDFF) derived by Aspnes (Eq. (5.2.8)). The ER spectra recorded on
the CIS and CIGS solar cells, with x=0, 0.04 and 0.12, were easily fitted with TDFFs (see
Evaluation example of a PR-spectrum, Fig. 7.1.2), as follows: 1) In the ER spectra of the CuInS
2

(CIS) cells, the E
a
- and E
b
-bands of the ternary are not resolved; they were fitted using only one

162
TDFF function. 2) In the ER spectra of the CuIn
1-x
Ga
x
S
2
(CIGS) cells, both the E
a
- and E
b
-bands
of the quaternary are present. In addition, the line shapes of the E
a
- and E
b
-bands are more
complex, especially in case of the absorber with the smaller Ga-fraction (x=0.04). Four spectral
functions (TDFFs) were needed to fit the ER bands. The fitting results are demonstrated, in case
of a CuIn
1-x
Ga
x
S
2
cell with x=0.04, in Fig. 7.10.2.
The calculated energy gaps are given in Table 7.10.1.

1.3 1.4 1.5 1.6 1.7 1.8
-0.015
-0.010
-0.005
0.000
0.005
0.010
E
b2
E
a2
E
b1
E
a1
CuIn
1-x
Ga
x
S
2
solar cell, x=0.04
ER spectrum, 300 K

R
/
R

(
x
1
0
-
3
)
Energy (eV)

Fig. 7.10.2 Fitting of the ER spectrum of a CIGS cell with x=0.04 with TDFF functions.

Table 7.10.1 E
a
- and E
b
-transition energies of CIGS solar cells at room temperature.
ER 300 K Absorber
a1
(eV)
b1
(eV)
a2
(eV)
b2
(eV)
CuInS
2
1.535
0.001
1.535
0.001

CuIn
1-x
Ga
x
S
2
with x=0.04 1.486
0.001
1.521
0.001
1.552
0.002
1.580
0.004
CuIn
1-x
Ga
x
S
2
with x=0.12 1.552
0.010
1.589
0.003
1.614
0.002
1.640
0.001

The four different contributions in case of the CIGS cells are tentatively explained as
originating from two different regions of the active absorber layer. Depending on growth
mechanism, these regions are differently defined, that is, significant differences in the growth
mechanism of CIGS films with x=0.04 and 0.12 lead to differences in the distribution of gallium
across the film. This has been confirmed by energy dispersive X-ray fluorescence (EDX) and X-

163
Ray Diffraction (XRD) studies of the same films reported elsewhere [7.70]. The film with
x=0.04, grown from the Cu-free precursor, though it exhibits good film properties, has inevitably
a strong gradient in the Ga distribution perpendicular to the substrate. In case of the absorber
with x=0.12, the presence of all elements already in the first stage leads to a more homogenous
gallium depth distribution. However, there is still gallium degradation through the film volume:
the study of the kinetics of film formation in a two-step process shows that the gallium
concentration is high close to the back contact and decreases towards the film surface [7.70].
This leads to an inherent grading of the energy band gap of the absorber. Referring to that, the
energy band gaps obtained for the quaternary compounds, after fitting the ER spectra in Fig.
7.10.1, can be assigned to a Ga-rich and a Ga-poor region of the absorber layers.
The energy gaps of CuIn
1-x
Ga
x
S
2
films known from the literature [7.84] range from 1.53
eV to 2.40 eV, which are the band gap energies of the ternary CuInS
2
and CuGaS
2
, respectively.
The
a1
and
b1
band gap energies given in Table 7.10.1, are attributed, therefore, to the Ga-
poor layer region, while the
a2
and
b2
energies to the Ga-rich one. The sequence
a1
,
b1
,
a2
,
b2
has been chosen instead of
a1
,
a2
,
b1
,
b2
, because of the E
a
and E
b
split-energies
reported in the literature [7.66]. The splitting of the A-B excitons at 300 K is 0 meV for CuInS
2

and 120 meV for CuGaS
2
. The energy separation may be additionally increased in the presence
of elastic strain as discussed in the following sections a) and b). Still, split-energies in the order
of 60 meV (as in case of the second sequence,
a1
,
a2
,
b1
,
b2
) would imply that, already by
substitution of 12% (or less) of the In-content by Ga, half of the split-energy assigned to 100%
substitution is reacted.
The presence of mismatch strain due to the above discussed compositional gradient is
considered in the following b).

b) Strain effects
Strain due to the Ga-gradient in the absorber layer
The Ga distribution in the absorber layer, forming a Ga-rich and a Ga-poor region,
could lead to strain due to the lattice mismatch between the two sub-regions. According to XRD
data [7.70], the lattice constants of the quaternary CIGS

films are smaller than those of the
ternary CIS. The XRD diffractograms shift to higher angles with increasing Ga-content
(increasing x). Though this shift is relatively small and corresponds to a small variation of the
lattice constants of the quaternary compounds (=5.5094 , for x=0.04 and =5.4962 , for
x=0.12 [7.78]) compared to the lattice constant of the ternary (=5.516 , for x=0.00 [7.78]), it
is assumed to be the source of the mismatch strain between a CIS-like (Ga-poor) and a CIGS-
like (Ga-rich) region of the layer for the respective Ga-fraction (x=0.04 and 0.12). The
a1
,
b1
,

164
a2
,
b2
bands may be explained as originating from these two regions, the former situated near
the layer surface and the latter near the interface to the Mo/glass substrate. In between a gradual
change in composition, and thus in the lattice constant, may take place.
According to the above considerations, a strain/stress analysis is undertaken for each of
the quaternary systems with 4% and 12% Ga. The strain between the ternary top-layer and the
quaternary chalcopyrite near the interface to the substrate is calculated using the gap energies
obtained by fitting the ER spectra (Table 7.10.1). It should be noted that this analysis is based on
the well-described theory of elastic strain in zinc-blende type semiconductors [7.85], [7.86],
already described in 3.1.2 of the theoretical part.
Under the application of a bisotropic stress (Eq. (3.1.4)) parallel to the [100] and [010]
crystallographic directions, the calculated energy difference between the conduction and the two
upper most valence bands, noted as

and
b
in the case of chalcopyrites, at k=0, to first
order in strain, is given by [7.87]:

11 12 11 12
11 11
2
2
a
C C C C
E a b
C C
( | | | | +
=
( | |
\ \
(7.10.1)

11 12 11 12
11 11
2
2
b
C C C C
E a b
C C
( | | | | +
= +
( | |
\ \
(7.10.2)
where

and
b
are the lower band gap energies of the CIGS chalcopyrites,
bulk
E

= ,
b b bulk
E = , are the energy separations with respect to the band gap energy of the bulk
bulk
, and , b are the hydrostatic and shear deformation potentials, respectively.
bulk
represents
the band energy under strain-free conditions. In our case (two sub-layers, CIS being the top- and
CIGS the bottom-layer), it is the band gap energy obtained for CIS from the evaluation of the ER
spectra at 300 K (Table 7.10.1).
The elastic constants C
ij
of CIS have been calculated from J. Lazewski et al. [7.88] as
C
11
=83.7 GPa and C
12
=54.4 GPa. Since the hydrostatic deformation potential of CIS is not
known, the one of CuInSe
2
has been used ( =-2.23 eV). This gives a quite accurate result, since
the increase of the anion atomic number does not change much the values of [7.89]. For the
shear deformation potentials b of all I-III-VI
2
compounds and alloys, appropriate values have
been reported by Yoodee et al. [7.90]:
( 0.8 0.2)
p
b eV = (7.10.3)
( 4.3 1.5)
d
b eV = (7.10.4)
where b
p
and b
d
are the deformation potentials associated with the p- and d-orbitals, respectively.
These two deformation potentials can be combined in [7.91]:

165
a (1 a)
p d
b b b = + (7.10.5)
where 1-a is the percentage of d-orbitals that contribute to hybridization.
Shay and Tell [7.84] have estimated for CIS a percentage of 45 %-d character. Inserting
this in Eq. (7.10.5) and taking in account Eqs. (7.10.3)-(7.10.4), it is found b=-2.375 eV.
Yoodee et. al. [7.90] reported a mean value of fractional d-character 1-=0.413. Inserting
this in Eq. (7.10.5) and taking in account Eqs. (7.10.3)-(7.10.4), it is found b=-2.246 eV.
On the other hand, Shay and Tell [7.84] have calculated b for several I-III-VI
2

compounds from the plot of the crystal-field parameter
cf
versus tetragonal compression:
1.5 (2 )
cf
c
b
a
= (7.10.6)
and c are the lattice constants.
For the ternary CIS, a theoretical value of
cf
=0.05 has been published in Ref. [7.84]. Inserting
this in Eq. (7.10.6) yields b=-2.36 eV.
The strains of the CIGS cells have been calculated according to Eqs. (7.10.1) and (7.10.2)
by using the values of , b, and C
ij
given above and are presented in Table 7.10.2. Strain values
deduced from the ER spectra of CIGS with x=0.04 are in better agreement than those related to
the ER spectra of CIGS with x=0.12. Fitting errors were larger in the second case because the ER
bands (
a1
,
b1
,
a2
,
b2
) were not well resolved. Average strains were in both cases less than
1%.

Table 7.10.2 Calculated strain values of CIGS cells (deformation potentials and b and elastic
constants C
ij
of CIS were taken from Refs. [7.84],[7.90], and [7.91]).

Absorber
(
)

(
b
)
CuIn
1-x
Ga
x
S
2

with x=0.04
-0.0070

-0.0070
-0.0073
*
0.0036
0.0036
0.0039
*
CuIn
1-x
Ga
x
S
2

with x=0.12
0.0024
0.0024
0.0025* -0.014
-0.014
-0.015*
Ref. [7.84]
Ref. [7.84], [7.91]

*
Ref. [7.90], [7.91].

The mismatch strain in the CdS buffer-layer and the ZnO overlayer (window of the cell)
are considered in the following section.

166
Strain in the CdS and ZnO layers
According to the scanning electron micrographs (SEM) of the absorber layers, for both Ga-
fractions, the absorber thickness is estimated to approximately 3 m. This is quite large
compared to the thickness of the CdS and ZnO layers being 50 and 350 nm, respectively. These
two layers deposited on top of the absorber layer may then suffer under the effect of mismatch
strain and not vica versa, meaning that they cannot generate strain large enough to encounter for
the splitting of the E
a
- and E
b
-bands in the absorber layer as discussed in the previous section
a).
The ER spectra of the CIGS-based solar cells recorded in the spectral region 1.5-4.0 eV
give information on the CdS and ZnO epilayers. In Fig. 7.10.3, the ER spectrum of a CIGS

solar
cell with x=0.12 is presented in such a region. The ER band between 1.4 and 1.8 eV corresponds
to the energy band gap of the absorber active layer and it is shown enlarged in the inset. ER
bands assigned to CdS and ZnO are observed on the high-energy side of the spectrum, in the
range 2.0-4.0 eV. For CdS, the band energies of the E
a
- and E
b
- transitions were calculated to
(2.2180.018) eV and (2.4560.008) eV, which are lower than the respective values known
from the literature [7.46]. The band energies calculated for ZnO are:
a
=(3.2110.013),
b
=(3.4440.062) eV. The band gap energy of ZnO in the wurtzite structure reported in Ref. [7.47]
is E
g,o
= 3.37 eV, at room temperature, and it is significantly higher than the E
a
gap energy
measured here.
The shift of the CdS and ZnO gap energies to lower energies reveals that both layers
deposited on top of the absorber layer are strained. The lattice constant of ZnO (
ZnO
= 3.25
[7.79], [7.92], Table 7.8.3) is smaller than the lattice constant of CdS (
CdS
= 4.14 [7.79],
[7.92], Table 7.8.3) and both are much smaller than the lattice constants of the CIGS absorbers
studied (=5.5094 , for x=0.04 and =5.4962 , for x=0.12 [7.78]). Both layers exhibit,
therefore, tensile stresses. It is well known that under the influence of tensile stress the band gap
is narrowed [7.80].

167
1.5 2.0 2.5 3.0 3.5 4.0
-0.015
-0.010
-0.005
0.000
0.005
0.010
0.015
1.50 1.55 1.60 1.65 1.70 1.75 1.80
-0.020
-0.015
-0.010
-0.005
0.000
0.005
0.010
0.015

R
Energy (eV)
absorber
ZnO
CdS
CuIn
1-x
Ga
x
S
2
solar cell, x=0.12
ER-spectrum, 300 K
R
/
R

(
x
1
0
-
3
)
Energy (eV)

Fig. 7.10.3 ER spectrum of a CIGS-solar cell with x= 0.12 at 300 K. The energy gaps of CIGS,
CdS, and ZnO are marked by arrows; details of the energy gap of the absorber are
shown in the inset.

c) Determination of thickness
The ER spectra of CIGS(x=0, 0.04, and 0.12)-based solar cells, illustrated in Fig. 7.10.1,
exhibit a number of interference fringes at energies below the band gap energy, originating from
the interference of light beams reflected on the front and back face of the absorber layer. The
interferences influence the ER absorber line shapes.
Similar fringes are also observed in the reflectance spectra of the CIGS(x=0.04, and
0.12)-based solar cells, as shown in Fig. 7.10.4. These fringes can be used to calculate the
absorber thickness using a relationship derived in Ref. [7.68] and rearranged in Ref. [7.10] to
account for light propagation in a layered structure consisting of two layers:
( ) ( )
( )
( )
2 1
2 1
2 / 1
2
2 2
2 2
2 / 1
1
2 2
1 1
2
sin sin

= +
N
n t n t (7.10.7)
where
i
t is the thickness,
i
n is the refractive index of the i -layer ( i =1, 2),
i
is the angle of
incidence,
1
,
2
are the start and end wavelengths (
1 2
> ), respectively, and is the number of
fringes between
1

and
2
.

168
1.0 1.2 1.4 1.6 1.8 2.0
x2
778 nm
969.5 nm
830 nm
1012 nm
N=5
N=6
x=0.12
x=0.04
CuIn
1-x
Ga
x
S
2
cells
Reflectance spectra, 300K

R
e
f
l
e
c
t
a
n
c
e
Energy (eV)

Fig. 7.10.4 Reflectance spectra of CIGS(x= 0.04 and 0.12)-based solar cells.

The absorber thickness is determined in the following:
As already discussed in 7.8.1, the small Ga-fraction (12%) of the CIGS films allow us
to use the refractive index of the ternary CIS for the calculation of the absorber thickness.
Knowing the thickness of the ZnO layer (350 nm) and neglecting the thickness of the CdS layer
(50 nm), a two-layered structure can be thus considered:
layer 1: ZnO (thickness
1
t =350 nm) and,
layer 2: CIGS absorber (thickness
2
t )
Taking into account the wavelength dispersion of n , a value in the middle of the scanned
spectral region has been chosen. For ZnO:
1
n (1.3eV)=1.95 and
1
n (1.4eV)=1.96, in case of the
cell with x=0.04 and 0.12, respectively [7.93], while for the CIGS layer,
2
n (1.4 eV)

=2.87 in
both cases [7.43]. We use:
45
1
= for ZnO and
1 1
2
2
sin 45
sin
o
n
n

| |
=
|
\
for CIGS
,
according to
the law of refraction (Snells law).
a) in the ER spectra of the CIGS cells, shown in Fig. 7.10.1, the following values are
considered: for CIGS with x=0.04: N =4 between
1
=1015.5 nm and
2
=859.5 nm, and, for
CIGS with x=0.12: N =4 between
1
=973 nm and
2
=826 nm. Inserting these values in Eq.

169
(7.10.7), it s found:
2
t =3.7 and 3.6 m for the films with x=0.04 and 0.12, respectively. These
thickness values are in agreement with the ones derived from the SEM micrographs of the etched
absorbers.
b) in the reflectance spectra, shown in Fig. 7.10.4, the corresponding values of N,
1
and
2
yield:
2
t =3.9 m in case of both CIGS layers.

170
8. CONCLUSIONS

Alternate to Si-, CIS-, CGS- and CIGS-thin film photovoltaic technology is the main
issue of the present thesis. Homo- and heterojunction solar cells based on chalcopyrite absorbers
have been investigated aiming to an improvement of the structural and optical properties of the
absorber and replacement of the CdS- by a ZnSe-, less toxic, buffer.

- CHALCOPYRITE SELENIDE HETEROSTRUCTURES
CuIn
1-x
Ga
x
Se
2
(CIGS) epitaxial layers
1) CuIn
1-x
Ga
x
Se
2
(CIGS) epitaxial layers with six different Ga-compositions (x=0.08, 0.19,
0.33, 0.50, 0.60 and 0.82) are studied by Photoreflectance (PR) at room and low temperatures
(20 K) and by Raman spectroscopy at room temperature (RT). The fundamental band gap-
energies, determined by fitting the PR spectra with a third derivative functional form (TDFF),
show a quadratic dependence on composition. For the first time, the low temperature
fundamental band gaps of CIGS quaternary alloys are determined in a large composition range.
As expected, the low temperature energy gaps are higher than the gaps at room temperature.
Moreover, the bowing appears much larger at lower than at room temperatures, which is partially
due to the mismatch and thermal strain of the layers. The room temperature gaps agree well with
data known from the literature.
The Raman spectra, recorded under excitation with a vertically polarized Kr
+
-laser beam
operated at the 647.1 nm line in the region 50700 cm
-1
, consist mainly of peaks assigned to the
A
1
- and B
2
-phonon modes of the quaternary compounds. The A
1
-mode dominates the spectra
and shifts linearly, with the increase of the [Ga]/([In]+[Ga]) content, from 172 cm
-1
(A
1
-mode
frequency of CuInSe
2
) to 181 cm
-1
(A
1
-mode frequency of CuGaSe
2
). Combining the Raman-
and PR-results, an analytical expression is derived which correlates the band gap energy with the
A
1
Raman mode frequency for a given composition of the CIGS quaternary compound. Similar
remarks are made by Raman scattering excited by the 514.5 nm Ar
+
-laser.
2) The higher band gaps of the CIGS epitaxial layers are determined using Spectroscopic
Ellipsometry (SE) at RT. The second derivative of the imaginary part of the dielectric function
2 2
2
/ d d E shows, at energies above 2.7 eV, three main minima, attributed to the
1
(), ()
and
1
() band gaps of the CIGS absorbers, from smaller to larger energy. The E
1
- and ()-
transitions are assigned to critical points at the Brillouin-zone centre () and edge N- point,
respectively. In some cases, a peak assigned to the E(X) transition at the edge T-point is also
observed, while the films with x0.33 exhibit a peak due to the () transition of the ternary
CuGaSe
2
compound formed at the CIGS/GaAs interface. The higher gaps of the quaternary
absorbers are varying between the band gaps of the ternary CuInSe
2
and CuGaSe
2
end-members.

171
Below 2.7 eV, intensive interference fringes are observed, originating from the interference of
light beams reflected at the front surface and an internal pseudo-interface in the absorber layer.
This pseudo-interface is formed due to the step-like concentration gradient assumed within
CIGS films. The fringes shadow the signals due to the chalcopyrite phase and hinder the
determination of the fundamental band gaps of the CIGS layers by complementary to PR and
ER, Spectroscopic Ellipsometry techniques.
3) The lattice defects of the CIGS epitaxial layers are studied by Photoluminescence (PL)
and Photoluminescence Excitation (PLE) spectroscopy at 7 K. The PL spectra consist, in
general, of a single PL band shifted to higher energies with the increase of the Ga-content. Their
compositional dependence is similar to that of the band gap energy of CIGS layers measured by
PR. On films with intermediate Ga-content, x=0.33 and 0.60, however, two different broad PL
bands are observed, associated with the presence of two different phases within these films.
These results are in agreement with the corresponding XRD data of these layers. PLE
spectroscopy studies the incorporation of defects in the quaternary alloy system by recording the
luminescence signal with the detection energy set to the PL band maximum and at the flanks of
it. By combining the PL, the PLE and the PR results at low temperatures, down to 2 K, the
energies of the donor and acceptor states contributing to the luminescence mechanism of the
CIGS layers are determined.

CuIn
1-x
Ga
x
Se
2
(CIGS) polycrystalline films and solar cells
4) CuIn
1-x
Ga
x
Se
2
(CIGS) solar cells deposited on glass and Ti-foil substrates are
characterized by Photoreflectance (PR) and Electroreflectance (ER) techniques at RT. Absorbers
with a fraction of 30 % Ga, giving rise to CIGS solar cells of optimum, up to now, efficiency
(=19.5 %) are studied. Using a previously obtained calibration curve of band-gap energy versus
Ga fraction of the CIGS absorber, the absorber energy gap, and thus the cell operational range,
can be determined for a given Ga concentration and vice-versa. PR spectroscopy can be
selectively applied to probe the Ga concentration across the absorber layer by wavelength
selection of the modulating laser beam. PR, thus, gives information on the upper region of the
absorbers, while ER explores the overall volume of the chalcopyrite layers, in accordance to the
structural XRF-analysis of the same films.

- CHALCOPYRITE SULPHIDE HETEROSTRUCTURES
CuIn
1-x
Ga
x
S
2
(CIGS) polycrystalline films and CdS/CIGS, ZnO/CdS/CIGS
heterostructures
5) The structural and optical properties of CuIn
1-x
Ga
x
S
2
(CIGS), CdS/CuIn
1-x
Ga
x
S
2
, and
ZnO/CdS/CuIn
1-x
Ga
x
S
2
polycrystalline films, with applications in photovoltaics, are studied by

172
Raman and Photoreflectance (PR) spectroscopy for two different compositions, [Ga]/([In]+[Ga])
= 0.04 and 0.12, of the CuIn
1-x
Ga
x
S
2
absorber. The absorber with x=0.12 is already at the upper
limit of the quaternary that can lead to good quality CIGS solar cells with maximum widened
energy gap, while the one with x=0.04 is expected to give results very close to the ternary CIS
chalcopyrite. Due to the polycrystallinity of the films, PR signals can be recorded only at low
temperatures (20 K). The energy band gaps of the absorber films are determined by fitting the
PR spectra with a third derivative functional form. Evaluation of the PR spectra of the
CdS/CuIn
1-x
Ga
x
S
2
, and ZnO/CdS/CuIn
1-x
Ga
x
S
2
heterostructures gives the band gaps of the CdS
and ZnO overlayers at 20 K. Both layers are tensile strained due to the lattice mismatch of the
CIGS/CdS and CdS/ZnO interfaces.
Raman scattering is excited by the 514.5 nm line of Ar
+
-laser and the 647.1 nm line of
Kr
+
-laser at RT. The Raman spectra of the absorber films consist of phonon-modes assigned to
the CuInS
2
and CuGaS
2
ternary chalcopyrites and the CuS phase formed on the surface of Cu-
rich layers. The results of the present study are discussed together with the results of SEM and
XRD studies of the films and the results of electrical measurements performed on solar cells
based on the CIGS absorbers.

CuIn
1-x
Ga
x
S
2
(CIGS)-based solar cells
6) CuIn
1-x
Ga
x
S
2
(CIGS)-based solar cells are characterised by Electroreflectance (ER)
spectroscopy at RT for two different compositions, [Ga]/([In]+[Ga]) = 0.04 and 0.12, of the
CuIn
1-x
Ga
x
S
2
absorber. Evaluation of the ER spectra of the CIGS solar cells gives the absorber
band gaps: due to the Ga-gradient within the layers, the
a
E and
b
E bands are split into four sub-
bands originated by differently strained regions of the active absorber layer. The strain evolution
in the absorber layers is analysed with respect to the band separation and is found to be smaller
than 1% (0.50.8%).

- CHALCOPYRITE SELENIDE HOMOSTRUCTURES
CuGaSe
2
and Ge doped CuGaSe
2
polycrystalline films
7) The structural properties of Ge doped polycrystalline CuGaSe
2
films with potential
applications in solar cell device technology are studied by Raman spectroscopy at RT and by
Photoluminescence (PL) spectroscopy at RT and 2 K. The films are intentionally doped with
max. 200 keV Ge ions using one- and three-stage ion implantation processes. The Raman spectra
of as grown films are dominated by the A
1
-mode (breathing mode) of the CuGaSe
2
absorber at
184 cm
-1
. It is found, that, in doped films, the Raman mode intensities are reduced and the B
2
-
modes (TO at 249 cm
-1
and LO at 273 cm
-1
) take over. This implies an increase in structural
disorder induced, probably, by bond reorientation effects that favor excitation of asymmetric

173
lattice vibrations (B
2
) instead of the symmetric ones (A
1
). Moreover, it is found, that the Raman
bands of doped films exhibit asymmetric broadening representative of a Fano line-shape.
Changes are more pronounced in films doped at one-stage. The PL emission of films subjected
to one-stage process is enhanced, which supports an increase in structural disorder particularly
for these films. On the contrary, for films doped in three-stages, the PL bands are less intensive
and the Raman bands are less broadened.

Conclusively, CIGS quaternary chalcopyrite compounds are great candidates for
absorbers in solar cell devices; they have extremely high absorption coefficients (>10
5

cm
-1
) and
band-gap energies that match the solar spectrum: By varying the Ga-content, absorbers with gaps
in the range of 1-2.5 eV can be obtained. The optical properties (band-gap energy, refraction
index and absorption coefficient) of CIGS are very sensitive to the absorber composition, and
thus its structure, and can alter significantly even for small variations of the absorber from
stoichiometry. The [Cu]/([Ga]+[In]) and [Ga]/([Ga]+[In]) ratios, controlled by growth
conditions, are very critical in the material properties. Additionally, CIGS absorbers exhibit a
great inhomogeneity due to the Ga-incorporation within the films and, usually, the Ga-content is
increasing towards the back surface of the layer. Bearing in mind that, in all cells based on Cu-
poor CIGS quaternary selenides the limiting factor for the open circuit voltage V
oc
, and thus the
cell efficiency is the recombination in the bulk of the absorber material while in cells based on
Cu-rich CIGS sulphides interface recombination is dominant, the following are proposed as
future perspectives:
Further investigation on quaternary sulphide and selenide absorbers concerns first, the
mapping of CIGS, so as to correlate the absorber composition with the lattice defects present and
the recombination mechanisms degrading the cell performance. Since defects in CIGS play an
important role on the band gap energy and the charge transport within the absorber and the
CIGS/CdS and CdS/ZnO interfaces, the investigation of the Ga-incorporation within the CIGS
layers would help to understand the different behavior of the quaternary compounds compared to
the widely studied ternary CIS and CGS end-points. The calculation of the band-structure in
quaternary chalcopyrites would be also useful for better knowledge of these materials aiming to
the increase of the efficiency and the improvement of the properties (optical, electrical) of the
corresponding heterojunction solar cells. The improvement of the material and growth properties
would enhance definitely the development of homojunction cells.

174
In this PhD-thesis:

with respect to the optimization of Chalcopyrite (CIS, CGS, CIGS) thin film properties
towards the development of CIGS-based solar-cell device Technology:

1. CIGS selenide absorbers, containing up to 30% Ga, exhibit very good structural and optical
properties; depending on composition, the band-gap of CIGS absorbers can be tuned from 1.0-
2.5 eV to match the entire region of the solar-energy spectrum.

2. Heterojunction cells based on CIGS exhibit inhomogeneous Ga-incorporation within the
absorber, with the Ga being accumulated, usually, at the absorber/substrate interface. This
phenomenon is more pronounced in sulphides, appearing already at compositions of 12% Ga,
while selenides are more tolerant to Ga addition. The problem can be over passed by controlling
the growth conditions.

3. Homojunctions are potential competitors of the heterojunctions, under the condition, that the
type-inversion of the absorber surface conductivity (n-type) will not degrade the material quality.

With respect to the Optical Characterization Techniques used:

4. Modulation spectroscopy (PR, ER) has proven to be a powerful tool for band-gap studies on
chalcopyrite absorbers and other components of chalcopyrite based solar cells; ER can give
results even at room-temperature, independently of the degree of the material crystallinity
(epitaxial or polycrystalline layer). Modulation spectroscopy has been used in a complementary
way with Spectroscopic Ellipsometry to determine the optical properties of chalcopyrite layers
and devices.

5. Raman spectroscopy contributed significantly to structural studies and calibration of band-
gap energies on Raman phonon-shift (via compositional dependence) in multi-component
systems.

6. PL and PLE have been combined in lattice-defect studies to detect shallow and deep defect
states in the chalcopyrite band-gap and reveal excitonic states at the band-edges.

175
9. REFERENCES

Ch. 1

1.1 PV News, published by Prometheus Institute, April 2006, ISSN 0739-4829
1.2 A. Jger-Waldau, Research, Solar Cell Production and Market Implementation of
Photovoltaics, PV Status Report 2006, EUR 22346 EN
1.3 http://www.solarbuzz.com/Marketbuzz2007-intro.htm
1.4 K.L. Chopra, P.D. Paulson, V. Dutta, Thin Film Solar Cells: An Overview, Progress in
1.5 PV News, February and May 2003 http://www.pv.pl/Eng/PVCData2.php?m=04&d=04-01
1.6 S.M. Sze, Physics of Semiconductor Devices, 2
nd
ed., John Wiley & Sons (New York, 1981)
1.7 D.A. Neamen, Semiconductor Physics & Devices: Basic Principles, 2
nd
ed., Irwin-McGraw-
Hill Comp (USA, 1997)
1.8 F. Jay, (ed) IEEE Standard Dictionary of Electrical and Electronics Terms (Second Edition),
The Institute of Electrical and Electronic Engineers, Inc. (New York, 1977)
1.9 C.E. Backus, Solar Cell, IEEE Press (New York, 1980)
1.10 A.Goetzberger, Ch. Hebling, H.-W. Schock, Photovoltaic Materials, history, status and
outlook, Materials Science and Engineering R 40 (2003) 1-46
1.11 C. H. Henry, Limiting efficiencies of ideal single and multiple energy gap terrestrial solar
cells, Journal of Applied Physics 51 (1980) 4494-4450
1.12 J.H. Werner, J. Mattheis, U. Rau, Efficiency limitations of polycrystalline solar cells: case
of Cu(In,Ga)Se
2
, Thin Solid Films 480-481 (2005) 399-409
1.13 http://www.nrel.gov/pv/thin_film/docs/kaz_best_research_cells.ppt
Technology A 23(4) (2005) 1208-1214
1.15 A Romeo, M. Terheggen, D. Abou-Ras, D.L. Btzner, F.-J. Haug, M. Klin, D. Rudmann,
A.N. Tiwari, Development of Thin-film Cu(In,Ga)Se
2
and CdTe Solar Cells, Progress in
1.16 M.A. Contreras, T. Nakada, M. Hongo, A.O. Pudov, J.R. Sites,
ZnO/ZnS(O,OH)/Cu(In,Ga)Se
2
/Mo Solar cell with 18.6% efficiency, Proceedings 3
rd
World
Conference of Photovoltaic Energy Conversion, Osaka, Japan 2003, pp. 570-573
1.17 M.A. Contreras, K. Ramanathan, J. AbuShama, F. Hasoon, D. L. Young, B. Egaas, R.
Noufi, Diode Characteristics in State-of-the-Art ZnO/CdS/Cu(In
1-x
Ga
x
)Se
2
Solar Cells,
Progress in Photovoltaics and Research Applications 13 (2005) 209-216
1.18 M.A. Contreras, J. Tuttle, A. Gabor, A. Tennant, K. Ramanathan, S. Asher, A. Franz, J.
Keane, L. Wang, J. Scofield, R. Noufi, 1
st
World Conference of Photovoltaic Solar Energy
Conversion, Hawaii, 1994, pp. 6875
2
solar cells
from a rapid thermal process (RTP), Solar Energy Materials and Solar Cells 67(14)
(2001) 159166
1.20 R. Kaigawa, A. Neisser, R. Klenk, M.-Ch. Lux-Steiner, Improved performance of thin film
2
, Thin Solid Films 415 (2002) 266271
1.21 V. Nadenau, D. Hariskos, H.W. Schock, CuGaSe
2
based Thin Film Solar Cells with
Improved Performance, 14
th
European Photovoltaic Solar Energy Conference and
Exhibition, Barcelona, 1997, pp. 12501253
1.22 S. Siebentritt, Wide gap chalcopyrites: material properties and solar cells, Thin Solid Films
403-404 (2002) 1-8

176
Ch. 2

2.1 L. Shay and J.H. Wernick, Ternary Chalcopyrite Semiconductors: Growth, Electronic
Properties and Applications, Pergamon (Oxford, 1974)
2.2 J.E. Jaffe and A. Zunger, Electronic structure of the ternary chalcopyrite semiconductors
CuAlS
2
, CuGaS
2
, CuAlSe
2
, CuGaSe
2
and CuInSe
2
, Physical Review B, 28 (10) (1983) 5822-
5847
2.3 J.L. Shay, B. Tell, Energy Band Structure of I-III-VI
2
Semiconductors, Surface Science 37
(1973) 748-762
2.4 J.E. Jaffe and A. Zunger, Theory of the band-gap anomaly ABC
2
chalcopyrite compounds,
Physical Review B 29(4) (1984) 1882-1906
2.5 J.J.M. Binsma, L.J. Giling, J. Bloem, Phase Relations in the system Cu
2
S-In
2
S
3
, Journal of
Crystal Growth 50 (1980) 429-436
2.6 P. Villars, A. Prince, and H. Okamoto (Ed.) Handbook of Ternary Alloy Phase Diagrams,
ASM (New York, 1995)
2.7 Y. Tomm, S. Fiechter, Crystal growth of materials for photovoltaics, Journal of Ceramic
Processing Research 6(2) (2005) 141-145
2.8 R. Scheer, H.J. Lewerenz, Formation of secondary phases in evaporated CuInS
2
thin films: A
surface analytical study, Journal of Vacuum and Science Technology A 13(4) (1995) 1924-
1929
2.9 M.S. Branch, P.R. Berndt, J.R. Botha, A.W.R. Leitch, J. Weber, Structure and morphology
of CuGaS
2
thin films, Thin Solid Films 431-432 (2003) 9498
2.10 M.T.S. Nair, L. Guerrero, P.K. Nair, Conversion of chemically deposited CuS thin films to
Cu
1.8
S and Cu
1.96
S by annealing, Semiconductor Science Technology 13 (1998) 11641169
2.11 R.W.G. Wyckoff, Crystal Structures, Vol. 2, John Wiley & Sons (New York, London 1964)
2.12 E.Z. Kurmaev, J. van Ek, D.L. Ederer, L. Zhou, T.A. Callcott, R.C.C. Perera, M.
Cherkashenko, S.N. Shamin, V.A. Trofimova, S. Bartkowski, M. Neumann, A. Fujimori,
V.P. Moloshag, Experimental and theoretical investigation of the electronic structure of
transition metal sulphides: CuS, FeS
2
and FeCuS
2
, J. Physics: Condensed Matter 10 (1998)
16871697
2.13 J. Alvarez-Garcia, A. Perez-Rodriguez, A. Romano-Rodriquez, J.R. Morante, L. Calvo-
Barrio, R. Scheer, R. Klenk, Microstructure and secondary phases in coevaporated CuInS
2

films: Dependence on growth temperature and chemical composition, Journal of Vacuum
Science and Technology A 19(1) (2001) 232-239
2.14 S.B. Zhang, S-H. Wei, A. Zunger, H. Katayama-Yoshida, Defect physics of the CuInSe
2

chalcopyrite compound, Physical Review B 57(16) (1998), 9642-9656
2.15 S.B. Zhang, S-H. Wei, A. Zunger, Stabilization of Ternary Compounds via Ordered Arrays
of Defect Pairs, Physical Review Letters 78(21) (1997) 4059-4062
2.16 U.C. Boehnke, G. Khn, Phase Relations in the ternary system Cu-In-Se, Journal of
Materials Science 22 (1987) 1635-1641
2.17 C.H. Chang, A. Davydov, B.J. Stanbery, T.J. Anderson, Thermodynamic Assessment of the
Cu-In-Se System and Application to Thin Film Photovoltaics, The Conference Record of
the 25
th
IEEE Photovoltaic Specialists Conference, Institute of Electrical and Electronic
Engineers (IEEE), New York, 1996, pp. 849-852
2.18 P. Fons, S. Niki, A. Yamada, M. Uchino, H. Oyanagi, High resolution X-ray measurements
of strain-mediated diffusion in CuInSe
2
, Advances in X-ray Analysis 43 (2000) 201-211
2.19 J.C. Mikkelsen, Ternary Phase Relations of the Chalcopyrite Compound CuGaSe
2
, Journal
of Electronic Materials 10(3) (1981) 541-558
2
Thin Films for Solar
Cell Device Applications, NTUA, Athens 2003

177
2
(1999) 131-147
2.22 . Zunger, S. Zhang, S. Wei, Revisiting the Defect Physics in CuInSe
2
and CuGaSe
2
, Proc.
26
th
IEEE Photovoltaic Specialists Conference, U.S.A, 1997, pp. 313-318
2.23 S. Schuler, S. Siebentritt, S. Nishiwaki, N. Rega, J. Beckmann, S. Brehme, M.Ch. Lux-
Steiner, Self-compensation of intrinsic defects in the ternary semiconductor CuGaSe
2
,
Physical Review B 69 (2004) 045210-1-9
2.24 H. Neumann, Vacancy formation enthalpies in A
I
B
III
C
2
VI
chalcopyrite semiconductors,
Crystal Research and Technology 18(7) (1983) 901-906
2.25 F.A. Abou-Elfotouh, H.R. Moutinho, A. Bakry, T.J. Coutts, L.L. Kazmerski,
Characterization of the defect levels in copper indium diselenide, Solar Cells 30 (1991)
151-160
2.26 F.W. Ohrendorf, H. Haeuseler, Lattice Dynamics of Chalcopyrite Type Compounds. Part I.
Vibrational Frequences, Crystal Research and Technology, 34(3) (1999) 339-349
2.27 J. Camassel, L. Artus, J. Pascual, Lattice dynamics of AgGaSe
2
. I. Experiment, Physical
Review B 41 (1990) 5717-5726
2.28 H. Tanino, T. Maeda, H. Fujikake, H. Nakanishi, S. Endo, T. Irie, Raman spectra of
CuInSe
2
, Physical Review B 45(23) (1992) 13323-13330
2.29 M. Cardona, Modulation Spectroscopy, Academic Press (New York, 1969)
2.30 H. Kuzmany, Solid-State Spectroscopy: An Introduction, Springer-Verlag (Berlin, 1998)
2
, CuGaSe
2
,

CuInS
2
, and CuGaS
2
(2001) 075203-1-13
2.32 J.J. Hopfield, Fine Structure in the Optical Absorption edge of Anisotropic Crystals,
Journal of Physics and Chemistry of Solids 15 (1960) 97-107
2.33 M.I. Alonso, M. Garriga, C.A. Durante Rincn, E. Hernndez, M. Len, Optical functions
of chalcopyrite CuGa
x
In
1x
Se
2
alloys, Applied Physics A 74 (2002) 659664

Ch. 3

3.1 S. Siebentritt, Wide gap chalcopyrites: material properties and solar cells, Thin Solid Films
403-404 (2002) 1-8
3.2 R. Klenk, Characterisation and modelling of chalcopyrite solar cells, Thin Solid Films 387
(2001) 135140
3.3 S.-H. Wei, A. Zunger, Band offsets at the CdS/CuInSe
2
heterojunction, Applied Physics
Letters 63 (1993) 2549-2551
3.4 S.-H. Wei and H. Krakauer, Local-Density-Functional-Calculation of the Pressure-Induced
Metallization of BaSe and BaTe, Physical Review Letters 55 (1985) 1200-1203
3.5 A.J. Nelson, C.R. Schwerdtfeger, S.-H. Wei, A. Zunger, D. Rioux, R. Patel, and H. Hochst,
Theoretical and experimental studies of the ZnSe/CuInSe
2
heterojunction band offset,
Applied Physics Letters 62 (1993) 2557-2559
3.6 D. Schmid, M. Ruckh, H.W. Schock, A comprehensive characterization of the interfaces in
Mo/CIS/CdS/ZnO solar cell structures, Solar Energy Materials & Solar Cells 41-42 (1996)
281-294
3.7 T. Schulmeyer, R. Hunger, A. Klein, W. Jaegermann, S. Niki, Photoemission study and band
alignment of the CuInSe
2
(001)/CdS heterojunction, Applied Physics Letters 84 (2004) 3067-
3069
3.8 D. Schmid, M. Ruckh, H.W. Schock, Photoemission studies on Cu(In,Ga)Se
2
thin films and
related binary selenides, Applied Surface Science 103 (1996) 409-429

178
2
(1999) 131-147
3.10 U. Rau, M. Schmidt, Electronic properties of ZnO/CdS/Cu(In,Ga)Se
2
solar cells-aspects of
heterojunction formation, Thin Solid Films 387 (2001) 141-146
3.11 M. Gloeckler, J.R. Sites, Efficiency limitations for wide-band-gap chalcopyrite solar cells,
Thin Solid Films 480-481 (2005) 241-245
3.12 R. Herberholz, V. Nadenau, U. Rhle, C. Kble, H.W. Schock, B. Dimmler, Prospects of
wide-gap chalcopyrites for thin film photovoltaic modules, Solar Energy Materials and
Solar Cells 49 (1997) 227-237
2
solar cells
from a rapid thermal process (RTP), Solar Energy Materials and Solar Cells 67(1-4) (2001)
159166
3.14 U. Fiedeler, PhD-thesis, Recombination and Diffusion in CuGaSe
2
Solar Cells, FU-Berlin,
Berlin 2001
http://www.diss.fu-berlin.de/2002/26/index.html
3.15 U. Rau, M. Shmidt, A. Jasenek, G. Hanna, H.W. Schock, Electrical characterization of
Cu(In,Ga)Se
2
thin-film solar cells and the role of defects for the device performance, Solar
Energy Materials & Solar Cells 67 (2001) 137-143
3.16 M. Turcu, O. Pakma, U. Rau, Interdependence of absorber composition and recombination
mechanism in Cu(In,Ga)(Se,S)
2
heterojunction solar cells, Applied Physics Letters 80
(2002) 2598-2600
3.17 H. Asai, K. Oe, Energy band-gap shift with elastic strain in Ga
x
In
1-x
P epitaxial layers on
(001) GaAs substrates, Journal of Applied Physics 54(4) (1983) 2052-2056
Semiconductors and Semimetals, Vol. 55, Academic Press (New York, 1998)
3.19 J.F. Nye, Physical Properties of Crystals, Clarendon Press (Oxford, 1985)
3.20 I. Goroff, L. Kleinman, Deformation Potentials in Silicon. III. Effects of a General Strain
on Conduction and Valence Levels, Physical Review 132 (1963) 1080-1084
3.21 A. Gavini, M. Cardona, Modulated Piezoreflectance in Semiconductors, Physical Review
B 1 (1970) 672-682
3.22 F.H. Pollak, M. Cardona, Piezo-Electroreflectance in Ge, GaAs and Si, Physical Review
172 (1968) 816-837
3.23 Y. Harada, H. Nakanishi, S.F. Chichibu, Band gap energy bowing and residual strain in
CuAl(S
x
Se
1-x
) chalcopyrite semiconductor epilayers grown by low-pressure metalorganic
vapor phase epitaxy, Journal of Applied Physics 91(9) (2002) 5909-5914
3.24 B. Tell, J.L. Shay, H.M. Kasper, Room-Temperature Electrical Properties of ten I-III-VI
2

Semiconductors, Journal of Applied Physics 43 (1972) 2469-2470
3.25 Z.B. Zhang, S.-H. Wei, A. Zunger, A phenomenological model for systematization and
prediction of doping limits in II-VI and I-III-VI
2
compounds, Journal of Applied Physics 83
(1998) 3192-3196
3.26 J.H. Schen, J. Oestreich, O Schenker, H. Riazi-Nejad, M. Klenk, N. Fabre, E. Arushanov,
n-type conduction in Ge-doped CuGaSe
2
, Applied Physics Letters 75 (1999) 2969-2971
3.27 Z.B. Zhang, S.-H. Wei, A. Zunger, Microscopic Origin of the Phenomenological
Equilibrium Doping Limit Rule in n-type III-V Semiconductors, Physical Review Letters
84 (2000) 1232-1235
3.29 S.H. Kwon, B.T. Ahn, A.K. Kim, K.H. Yoon, J. Song, Growth of CuIn
3
Se
5
layer on
CuInSe
2
films and its effect on the photovoltaic properties of In
2
Se
3
/CuInSe
2
solar cells,
Thin Solid Films 323 (1998) 265-269
3.30 D. Schmid, hl. Ruckh, F. Grunwald, and H. W. Schock, Chalcopyrite/defect chalcopyrite
heterojunctions on the basis of CuInSe
2
, Journal of Applied Physics 73 (1993) 2902-2909

179
3.31 C.D. Kim, G.C. Park, M.S. Jin, D.T. Kim, Structural and Optical Properties of Cu(In
1-
x
Ga
x
)
3
Se
5
Mixed Crystals, Journal of the Korean Physical Society 48 (2006) 951-955
3.32 T. Schulmeyer, R. Hunger, R. Fritsche, B. Jckel, W. Jaegermann, A. Klein, R. Kniese, M.
Powalla, Interfaces of chalcogenide solar cells: a study of the composition at the
Cu(In,Ga)Se
2
/CdS contact, Thin Solid Films 480-481 (2005) 110-117
3.33 F.M. Livingstone, W.M. Tsang, A.J. Barlow, R.M. De la Rue, W. Duncan, Si/CdS
heterojunction solar cells, Journal of Physics D 10 (1977) 1959-1963

Ch. 4

1-x
Ga
x
Se
2

Proceedings 763 (2003) 183-188
4.2 N. Rega, S. Siebentritt, J. Albert, S. Nishiwaki, A. Zajogin, M.-Ch. Lux-Steiner, R. Kneise,
M.J. Romero, Exitonic luminescence of Cu(In,Ga)Se
2
, Thin Solid Films 480-481 (2005) 286-
290
2
, Thin Solid Films 415 (2002) 266-271
4.4 N.G. Dhere
,
R.G. Dhere, Thin-film photovoltaics, Journal of Vacuum Science & Technology
A 23(4) (2005) 1208-1214
4.5 M. Rusu, S. Wiesner, D. Fuertes Marrn, A. Meeder, S. Doka, W. Bohne, S. Lindner, Th.
Schedel-Niedrig, Ch. Giesen, M.Ch. Lux-Steiner, CuGaSe
2
thin films prepared by a novel
CCSVT technique for photovoltaic application, Thin Solid Films 451-452 (2004) 556-561
2
Thin
2
solar cells and modules,
Thin Solid Films 480-481 (2005) 99-109
2
thin film solar
cells to flexible substrates using an in situ process control, Thin Solid Films 480481 (2005)
515-519
1-x
Ga
x
)Se
2

Ch. 5

5.1 M. Cardona, Modulation Spectroscopy, Academic Press (New York, 1969)
5.2 U. Rossow, W. Richter, Spectroscopic Ellipsometry, in: Optical Characterization of Epitaxial
Semiconductor Layers by Electromagnetic Radiation, Springer Berlin (Heidelberg, 1995)
5.3 K. Durose, S.E. Asher, W. Jaegermann, D. Levi, B.E. McCandless, W. Metzger, H.
Moutinho, P.D. Paulson, C.L. Perkins, J.R. Sites, G. Teeter, M. Terheggen, Physical
Characterization of Thin-film Solar Cells. Progress in Photovoltaics and Research and
Applications 12 (2004) 177-217
5.4 F.H. Pollak, Study of semiconductor surfaces and interfaces using electromodulation,
Surface and Interface Analysis 31 (2001) 938-953
5.5 D.E. Aspnes, Third-Derivative Modulation Spectroscopy with Low-Field
Electroluminescence, Surface Science 37 (1973) 418-442
5.6 B.O. Seraphin, N. Bottka, Franz-Keldysh Effect of the Refractive Index in Semiconductors,
Physical Review 139 (1965) A560-A565
5.7 D.E. Aspnes, Handbook on Semiconductors ed. by T.S. Moss (North-Holland, New York,
1980)

180
5.8 H. Shen, M. Dutta, Franz-Keldysh oscillations in modulation spectroscopy, Journal of
Applied Physics 78 (1995) 2151-2176
5.9 M. Cardona, Renormalization of the Optical Response of Semiconductors by Electron-
Phonon Interaction, Physica Status Solidi (a) 188 (2001) 1209-1232
5.10 Y.P. Varshni, Temperature dependence of the energy gap in semiconductors, Physica 34
(1967) 149-154
5.11 P. Lautenschlager, M. Garriga, M. Cardona, Temperature dependence of the interband
critical-point parameters of InP, Physical Review B 36(9) (1987) 4813-4820
5.12 P. Lautenschlager, P.B. Allen, M. Cardona, Phonon-induced lifetime broadenings and
electronic states and critical points in Si and Ge, Physical Review B 33(8) (1986) 5501-
5511
5.13 S. Guha, Q. Cai, M. Chandrasekhar, H.R. Chandrasekhar, H. Kim, A.D. Alvarenga, R.
Vogelgesang, A.K. Ramdas, M.R. Melloch, Photoluminescence of short-period GaAs/AlAs
superlattices: A hydrostatic pressure and temperature study, Physical Review B 58 (1998)
7222-7229
5.14 H. Kuzmany, Solid-State Spectroscopy: An Introduction, Springer-Verlag (Berlin, 1998)
5.15 A.H. Kitai, Solid State Luminescence. Theory, Materials and Devices, Chapman & Hall
(London, 1993)
5.16 P.Y. Yu, M. Cardona, Fundamentals of Semiconductors. Physics and Material Properties,
Springer-Verlag (Berlin, 1996)
5.17 P.J. Dean, Absorption and Luminescence of Excitons at Neutral Donors in Gallium
Phosphide, Physical Review, 157(3) (1976), 655-667
5.18 G.R. Wilkinson, Raman spectra of solids, in: Molecular Spectroscopy, Vol. 3 Chemical
Society (London, 1975)
5.19 P. Bruesch, Phonons: Theory and Experiments, Vol. I and II, Springer-Verlag (Heidelberg,
1983)
5.20 M. Cardona and G. Gntherodt, Light Scattering in Solids II, in: Topics in Applied Physics,
Vol. 50, Springer-Verlag (Berlin, 1982)
5.21 R.M. Martin, L.M. Falikov, in: M. Cardona (ed.), Light Scattering in Solids I, 2
nd
ed.,
Springer (Berlin, 1983)

Ch. 7

1-x
Ga
x
)Se
2
7.2 J.H. Werner, J. Mattheis, U. Rau, Efficiency limitations of polycrystalline thin film solar
cells: case of Cu(In,Ga)Se
2
, Thin Solid Films 480-481 (2005) 399-409
7.3 P.D. Paulson, R.W. Birkmire, and W.N. Shafarman, Optical characterization of CuIn
1-
x
Ga
x
Se
2
alloy thin films by spectroscopic ellipsometry, Journal of Applied Physics 94 (2)
(2003) 879-888
7.4 M.I. Alonso, M. Garriga, C.A. Durante Rinon, E. Hernndez, and M. Len, Optical
functions of chalcopyrite CuGa
x
In
1x
Se
2
alloys, Applied Physics A 74 (2002) 659-664
7.5 N. Rega, S. Siebentritt, J. Albert, S. Nishiwaki, A. Zajogin, M.C. Lux-Steiner, R. Kniese, and
M.J. Romero, Excitonic Luminescence of Cu(In,Ga)Se
2
, Thin Solid Films 480-81 (2005)
286-290
7.6 N. Rega, S. Siebentritt, J. Albert, M.Ch. Lux-Steiner, Photoluminescence of CuIn
1-x
Ga
x
Se
2

Proceedings 763 (2003) 183-188
7.7 N. Rega, PhD thesis, Photoluminescence of Cu(In,Ga)Se
2
epitaxial layers, Freie Universitt
Berlin, Berlin 2004

181
7.8 D.J. Shroeder, G.D. Berry, A.A. Rockett, Gallium diffusion and diffusivity in CuInSe
2

epitaxial layers, Applied Physics Letters 69(26) (1996) 4068-4070
7.9 A. Bauknecht, S. Siebentritt, J. Albert, Y. Tomm, and M.Ch. Lux-Steiner, Excitonic
Photoluminescence from CuGaSe
2
Single Crystals and Epitaxial Layers: Temperature
Dependence of the Band Gap Energy, Japanese Journal of Applied Physics 39, Suppl. 39-1
(2000) 322-325
2
Thin Films for
Solar Cell Device Applications, NTUA, Athens 2003
7.11 A. Bauknecht, U. Blieske, T. Kampschulte, J. Bruns, K. Diesner, Y. Tomm, S. Chichibu,
M.Ch. Lux-Steiner, Characterisation of High Quality CuGaSe
2
Heteroepitaxial Layers
Grown by MOVPE, Inst. Phys. Conf. Ser. 152 (1997) 269-272
7.12 G.R. Wilkinson, Raman spectra of solids, in: Molecular Spectroscopy, Vol. 3 Chemical
Society (London, 1975)
7.13 F.W. Ohrendorf, H. Haeuseler, Lattice Dynamics of Chalcopyrite Type Compounds. Part
I. Vibrational Frequencies, Crystal Research and Technology, 34(3) (1999) 339-349
7.14 L. Genzel, T.P. Martin, C.H. Perry, Model for Long-Wavelength Optical-Phonon Modes
of Mixed Crystals, Physica Status Solidi B 62 (1974) 83-92
7.15 C. Julien and C. Hirlimann, Calibration of a Raman Spectrometer using the Kr
+
laser
plasma lines, Journal of Raman Spectroscopy 9 (1) (1980) 62-66
7.16 E. Ahmed, R.D. Tomlinson, R.D. Pilkington, A.E. Hill, W. Ahmed, N. Ali, I.U. Hassan,
Significance of substrate temperature on the properties of flash evaporated CuIn
0.75
Ga
0.25
Se
2

thin films, Thin Solid Films, 335 (1998) 54-58
7.17 H. Miyazaki, R. Mikami, A. Yamada, M. Konagai, Cu(In,Ga)Se
2
thin film absorber with
high Ga contents and its application to the solar cells, Journal of Physics and Chemistry of
Solids 64 (2003) 2055-2058
7.18 A. Bauknecht, S. Siebentritt, J. Albert, M.Ch. Lux-Steiner, Radiative recombination via
intrinsic defects in Cu
x
Ga
y
Se
2
, Journal of Applied Physics 89(8) (2001) 4391-4400
7.19 J.I. Pankove, Optical Processes in Semiconductors, Dover Publications (New York,
1975)
7.20 B.I. Schklovskji, A.L. Efros, Electronic Properties of Doped Semiconductors, Springer-
Verlag (Berlin, 1984)
7.21 K.P. ODonnell, R.W. Martin, P.G. Middleton, Origin of Luminescence from InGaN
diodes, Physical Review Letters 82(1) (1999) 237-240
7.22 M.A. Reshchikov, G.C. Yi, B.W. Wessels, Behavior of 2.8- and 3.2- eV
photoluminescence bands in Mg-doped GaN at different temperatures and excitation
densities, Physical Review B 59 (20) (1999) 13176-13183
7.23 A.P. Levanyuk, V.V. Osipov, Edge luminescence of direct-gap semiconductors, Soviet
Physics Uspekhi-24 (3) (1981) 187-215
7.24 M. Cardona, Renormalization of the Optical Response of Semiconductors by Electron-
Phonon Interaction, Physica Status Solidi (a) 188 (2001) 1209-1232
7.25 M. Cardona, M.L.W. Thewalt, Isotope effects on the optical spectra of semiconductors,
Review of Modern Physics 77 (2005) 1173-1224
7.26 A. Gbel, T. Ruf, M. Cardona, C.T. Lin, J. Wrzesinski, M. Steube, K. Reimann, J.C.
Merle, M. Joucla, Effects of the isotopic composition on the fundamental gap of CuCl,
Physical Review B 57 (1998) 15183-15190
7.27 P.W. Yu, W.J. Anderson, Y.S. Park, Anomalous Temperature dependence of the energy
gap of AgGaS
2
, Solid State Communications 13 (1973) 1883-1887
7.28 I.H. Choi, S.H. Eom, P.Y. Yu, The optical and vibrational properties of the quaternary
chalcopyrite semiconductor alloy Ag
x
Cu
1-x
GaS
2
, Journal of Applied Physics 87 (2000) 3815-
3822

182
7.29 A.V. Mudriy, I.V. Bodnar, I.A. Viktorov, V.F. Gremenok, M.V. Yakushev, R.D.
Tomlinson, A.E. Hill, R.D. Pilkington, Optical properties of high-quality CuInSe
2
single
crystals, Applied Physics Letters 77(16) (2000) 2542-2544
7.30 Yakushev, A.V. Mudryi, I.V. Viktorov, J. Krustok, E.Mellikov, Energy of excitons in
CuInS
2
single crystals, Applied Physics Letters 88 (2006) 011922-1-3
7.31 P.G. Eliseev, P. Perlin, J. Lee, M. Osinski, Blue temperature-induced shift and band-tail
emission in InGaAs-based light sources, Applied Physics Letters 71 (1997) 569-571
7.32 T.M. Hsu, J.H. Lin, Anomalous temperature-dependent band gaps in CuInS
2
studied by
surface-barrier electroreflectance, Physical Review B 37(8) (1988) 4106-4110
7.33 I.H. Choi, S.H. Eom, P.Y. Yu, Soft phonon mode and the anomalous temperature
dependence of band gap in AgGaS
2
, Physica Status Solidi (b) 215 (1999) 99-104
7.34 A. Olkhovets, R.C. Hsu, A. Lipovskii, F.W. Wise, Size-dependent temperature variation of
the energy gap in lead-salt quantum dots, Physical Review Letters 81(16) (1998) 3539-
3542
7.35 P.B. Allen, M. Cardona, Temperature dependence of the direct gap of Si and Ge, Physical
Review B 27(8) (1983) 4760-4769
7.36 M. Cardona, Electron-phonon interaction in tetrahedral semiconductors, Solid State
Communications 133 (2005) 3-18
7.37 H.Y. Fan, Temperature dependence of the energy gap in semiconductors, Physical Review
82 (1951) 900-905
7.38 N. Rega, S. Siebentritt, I. Beckmann, J. Albert, M.Lux-Steiner, MOVPE of epitaxial
CuInSe
2
on GaAs, Journal of Crystal Growth 248 (2003) 169-174
7.39 M. Wagner, D.M. Hofmann, I. Dirnstorfer, M.D. Lampert, F. Karg, B.K. Meyer,
Characterization of CuIn(Ga)Se
2
thin films II. Magneto-Optical Properties of Cu- and In-
rich layers, physica status solidi (a) 168 (1998) 153-161
7.40 A.H. Kitai, Solid State Luminescence. Theory, Materials and Devices, Chapman & Hall
(London, 1993)
7.41 M. Wagner, I. Dirnstorfer, D.M. Hofmann, M.D. Lampert, F. Karg und B.K. Meyer,
Characterization of CuIn(Ga)Se
2
Thin Films: I. Cu-Rich Layers, Physica Status Solidi a)
167 (1998) 131-142
7.42 A. Meeder, D. Fuertes Marron, V. Tezlevan, E. Arushanov, A. Rumberg, T. Schedel-
Niedrig, M.Ch. Lux-Steiner, Radiative recombination in CVT-grown CuGaSe
2
single
crystals and thin films, Thin Solid Films 431-432 (2003) 214-218
2
, CuGaSe
2
,

CuInS
2
, and CuGaS
2
(2001) 075203-1-13
2
thin film solar
cells to flexible substrates using an in situ process control, Thin Solid Films 480481
(2005) 515-519
7.45 N.G. Dhere, A.A. Kadam, A.H. Jahagirdar, S.S. Kulkarni, L. Weinhardt, D. Gross, C.
Heske, E. Umbach, Spectroscopic analysis of CIGS2/CdS thin film solar cell
heterojunctions on stainless steel foil, Journal of Physics and Chemistry of Solids 66
(2005) 1872-1875
7.46 S. Ninomiya, S. Adachi, Optical properties of wurtzite CdS, Journal of Applied Physics 78
(2) (1995) 1183-1190
7.47 G.E. Jellison, Jr. and L.A. Boatner, Optical functions of uniaxial ZnO determined by
generalized ellipsometry, Physical Review B 58 (1998) 3586-3589
7.48 S. Chichibu, T. Mizutani, K. Murakami, T. Kurafuji, H. Nakanishi, S. Niki, P.J. Fons, A.
Yamada, Band gap energies of bulk, thin-film, and epitaxial layers of CuInSe
2
and
CuGaSe
2
, Journal of Applied Physics 83 (1998) 3678-3689
7.49 S. Shirakata, S. Chichibu, S. Isomura, H. Nakanishi, Electroreflectance of CuInSe
2
single
crystals, Japanese Journal of Applied Physics 36 (1997) L543-L546

183
7.50 S. Shirakata, S. Chichibu, Photoreflectance of Cu-based I-III-VI
2
heteroepitaxial layers
grown by metalorganic chemical vapor deposition, Journal Applied Physics 79 (1996)
2043-2054
7.51 K. Doll and H. Stoll, Cohesive properties of alkali halides, Physical Review B 56 (1997)
10121-10127
7.52 J. E. Jaffe, A. Zunger, Theory of the band-gap anomaly in ABC
2
chalcopyrite
semiconductors, Physical Review B 29 (1984) 1882-1906
2
solar cells and
7.54 D. Papadimitriou, G. Roupakas, S. Theodoropoulou, Ch.N. Panagopoulos, M. Georgiou,
A.G. Mamalis, D.E. Manolakos, Growth and Characterization of ZnSe Thin Films on
CuGaSe
2
Photovoltaic Absorbers (submitted)
7.55 S.B. Zhang, S.H. Wei, A. Zunger, A phenomenological model for systematisation and
prediction of doping limits in II-VI and I-III-VI
2
compounds Journal of Applied Physics 83
(6) (1998) 3192-3196
7.56 H. Tanino, T. Maeda, H. Fujikake, H. Nakanishi, S. Endo, T. Irie, Raman spectra of
CuInSe
2
, Physical Review B 45 (23) (1992) 13323-13330]
7.57 J. Camassel, L.Artus, J. Pascual, Lattice dynamics of AgGaSe
2
. I. Experiment, Physical
Review B 41 (9) (1990) 5717-5726
7.58 U. Fano, Effects of Configuration Interaction on Intensities and Phase Shifts, Physical
Review 124 (6) (1961) 1866-1878
7.59 F. Cerdeira, T.A. Fjeldly, M. Cardona, Interaction between electronic and vibronic Raman
scattering in heavily doped Silicon, Solid State Communications 13 (1973) 325-328
7.60 E. Altendorf, X.K. Chen, J.C. Irwin, B. Liang, W.N. Hardy, Temperature dependences of
the 340-. 440-, and 500 cm
-1
Raman modes of YBa
2
Cu
3
O
y
for 6.7y7.0, Physical Review
B 47 (13) (1993) 8140-8150
7.61 N.H. Nickel, P. Lengsfeld, I. Sieber, Raman spectroscopy of heavily doped polycrystalline
silicon thin films, Physical Review B 61 (23) (2000) 15558-15561
7.62 D. Bersani, P.P. Lottici, X.-Z. Ding, Phonon confinement effects in the Raman scattering
by TiO
2
nonocrystals, Applied Physics Letters 72 (1998) 73-75
2
Thin
Films, Materials Research Society Symposium Proceedings 865 (2005) F5.27.1- F5.27.5
7.64 C. Xue, D. Papadimitriou, Y.S. Raptis, N. Esser, W. Richter, S. Siebentritt, M. Ch. Lux-
Steiner, Compositional dependence of Raman scattering and photoluminescence emission
in Cu
x
Ga
y
Se
2
thin films, Journal of Applied Physics 94 (7) (2003) 4341-4347
7.65 B. Tell, J.L. Shay, H.M. Kasper, Electrical Properties, Optical Properties, and Band
Structure of CuGaS
2
and CuInS
2
, Physical Review B 4 (1971) 2463-2471
7.66 J.L. Shay, B. Tell, H.M. Kasper, L.M. Shiavone, p-d Hybridization of the Valence Bands of
I-III-VI
2
Compounds, Physical Review B 5(12) (1972) 5003-5005
7.67 T.M. Hsu, J.S. Lee, H.L. Hwang, Photoreflectance of sulfur-annealed copper indium
disulfide, Journal of Applied Physics 68(1) (1990) 283-287
7.68 E.A. Corl, H. Wimpfheimer, Thickness Measurement of Silicon Dioxide Layers by
Ultraviolet-Visible Interference Method, Solid-State Electronics 7 (1964) 755-761
7.69 M.J. Sun, Refractive-index dispersion of garnet films derived from accurate measurement
of film thickness, Applied Physics Letters 33(4) (1978) 291-293
2
, Thin Solid Films 415 (2002) 266-271
7.71 K.S. Ramaiah, V.S. Raja, A.K. Bhatnagar, F.S. Juang, S.J. Chang, Y.K. Su, Effect of
annealing and -irradiation on the properties of CuInSe
2
thin films, Materials Letters 45
(2000) 251-261

184
7.72 T.S. Moss, The Interpretation of the Properties of Indium Antimonide, Proceedings of the
Physics Society B 67 (1954) 775-782
7.73 R. Mrquez, C. Rincn, Defect physics of ternary chalcopyrite semiconductors, Materials
Letters 40 (1999) 66-70
7.74 D.C. Look, J.C. Manthuruthil, Electron and hole conductivity in CuInS
2
, Journal of Physics
and Chemistry of Solids 37(2) (1976) 173-180
7.75 L. Wang, N.C. Giles, Determination of the ionisation energy of nitrogen acceptors in zinc
oxide using photoluminescence spectroscopy, Applied Physics Letters 84(16) (2004) 3049-
3051
7.76 D.G. Thomas, J.J. Hopfield, Exciton Spectrum of Cadmium Sulphide, Physical Review 116
(3) (1959) 573-582
7.77 P. Kistaiah, K.Satyanarayana Murthy, K.V. Krishna Rao, Thermal expansion of
CuGa
0.5
In
0.5
Se
2
, Journal of Physics D: Applied Physics 15 (1982) 1265-1272
7.78 T. Kato, S. Hayashi, T. Kiuchi, Y. Ishihara, Y. Nabetani, T. Matsumoto, Structural
properties of Cu(Ga
1-x
In
x
)
y
S
z
bulk alloys, Journal of Crystal Growth 237-239 (2002) 2005-
2008
7.79 H. Iwanaga, A. Kunishige, S. Takeuchi, Anisotropic thermal expansion in wurtzite-type
crystals, Journal of Materials Science 35 (2000) 2451-2454
7.80 T. Yao, Y. Okada, S. Matsui, K. Ishida, I. Fujimoto, The effect of lattice deformation on
optical properties and lattice parameters of ZnSe grown on (100) GaAs, Journal of Crystal
Growth 81 (1987) 518-523
7.81 S.-Y. Wang, W. Wang, Z.-H. Lu, Asynchronous-pulse ultrasonic spray pyrolysis
deposition of Cu
x
S (x=1,2) thin films, Materials Science and Engineering B103 (2003) 184-
188
7.82 E. Boone, C. Shannon, Properties of Ultrathin Electrodeposited CdS Films Probed by
Resonance Raman Spectroscopy and Photoluminescence, Journal of Physical Chemistry
100 (1996) 9480-9484
7.83 A. Neisser, I. Hengel, R. Klenk, Th.W. Matthes, J. Alvarez-Garcia, A. Perez-Rodriguez, A.
Romano-Rodriguez, M.Ch. Lux-Steiner, Effect of Ga incorporation in sequentially
prepared CuInS
2
thin film absorbers, Solar Energy Materials and Solar Cells 67 (2001) 97-
104
7.84 J.L. Shay, B. Tell, Energy band structure of I-III-VI
2
semiconductors, Surface Science 37
(1973) 748-762
7.85 A. Gavini and M. Cardona, Modulated Piezoreflectance in Semiconductors, Physical
Review B 1(2) (1970) 672-682
Semiconductors and Semimetals, Academic Press (New York, 1998)
7.87 H. Asai and K. Oe, Energy band-gap shift with elastic strain in Ga
x
In
1-x
P epitaxial layers
on (001) GaAs substrates. Journal of Applied Physics 54 (1983) 2052-2056
7.88 J. Lazewski, P.T. Jochym and K. Parlinski. Band Structure, Born effective charges, and
lattice dynamics of CuInS
2
from ab initio calculations, Journal of Chemical Physics 117(6)
(2002) 2726-2731
7.89 S.H. Wei, A. Zunger, I.H. Choi, P.Y. Yu, Trends in band-gap pressure coefficients in
chalcopyrite semiconductors, Physical Review B 58(4) (1998) R1710-R1713
7.90 K. Yoodee, J.C. Wooley, V.Sa-yakanit, Effects of p-d hybridization on the valence band of
I-III-VI
2
chalcopyrite semiconductors, Physical Review B 30(10) (1984) 5904-5915
7.91 L. Artus, Y. Bertrand, C. Ance, Crystal-field and spin-orbit interactions at the fundamental
gap of AgGaSe
2
chalcopyrite compound, Journal of Physics C: Solid State Physics 19
(1986) 5937-5943

185
7.93 M. Rebien, W. Henrion, M. Br, Ch.H. Fischer, Optical properties of ZnO thin films: Ion
layer gas reaction compared to sputter deposition, Applied Physics Letters 80 (2002)
3518-3520

CURRICULUM VITAE

Personal Information
First Name: Sofia
Last Name: Theodoropoulou

Studies
2007-2003: PhD in Physics
*
(National Technical University of Athens, School of Applied
Sciences, Department of Physics)
2003-2001: MSc in the Inter-disciplinary Postgraduate Program
*
of the National Technical
University of Athens: Materials Science and Technology

2001-1996: BSc in Chemistry
*
(University of Athens)

Distinctions/prizes
Thomaidion prize for the publications:

Composites, S. Theodoropoulou, D. Papadimitriou, L. Zoumpoulakis, I. Simitzis, Diamond
and Related Materials (2004), 13 (2) 371-375.
1-x
Ga
x
Se
2
Solid Films 511-512 (2006) 690-694.
2
Schedel-Niedrig, M. Ch. Lux-Steiner, Thin Solid Films 515(15) (2007) 5904-5908.

Foreign Languages
English (Proficiency of Michigan)

_____________________________________
09/03-12/07: PhD Thesis on the CIGS Thin Film Photovoltaic Technology. Energy Band Gap
and Lattice Defect Analysis in Chalcopyrite Semiconductor Heterostructures under the
supervision of Assist. Prof. Dr. Dimitra Papadimitriou (NTUA, School of Applied Sciences,
Department of Physics).

09/02-06/03: MSc Thesis on the Preparation of carbonaceous materials from novolac
resin/olive stone biomass and Study of their structural and optical properties by spectroscopic
methods under the supervision of Prof. Dr. J. Simitzis (NTUA, School of Chemical
Engineering) and Assist. Prof. Dr. D. Papadimitriou (NTUA, School of Applied Sciences,
Department of Physics).

10/99-02/01: BSc Thesis on Comparative study of the antioxidant activity of red and white
wines in the presence of oxygen free radicals by means of EPR and other spectroscopic
methods, under the supervision of Assist. Prof. Dr. A. Valavanidis (University of Athens,
Department of Chemistry).
List of Publications

1. Alcoholic beverages and Mediterranean diet in human health. Wine phenolics and ethyl
alcohol as antioxidants and scavengers of oxygen free radicals. Toxicological implications
for moderate and high alcohol consumption, A. Valavanidis, V. Zonaras, S.
Theodoropoulou, Review of Clinical Pharmacology & Pharmacokinetics. Epitheorese
Klinikes Farmakologias kai Farmacokinetikes, International Edition 15(2) (2001) 85-96.

2. Red Wine and the French Paradox. Beneficial Effects to Human Health. Myth or Reality?
A comparative study of the antioxidant potential of alcohol and polyphenols in red and
white wine. S. Theodoropoulou, V. Zonaras, M. Charalabaki, E. Nicolopoulos and A.
Valavanidis, Pharmakeftiki 15(4) (2002) 107-118.

3. Structural and Optical Characterization of Pyrolytic Carbon derived from Novolac Resin.
S. Theodoropoulou, D. Papadimitriou, L. Zoumpoulakis, J. Simitzis, Analytical and
Bioanalytical Chemistry, Special Issue (Springer-Verlag 2004, 10.1007/s00216-003-2453-
5).

Composites. S. Theodoropoulou, D. Papadimitriou, L. Zoumpoulakis, I. Simitzis, Diamond
and Related Materials 13(2) (2004) 371-375.

5. Photoreflectance Spectroscopy: A Powerful Tool Applied in the Bandgap Measurement of
Photovoltaic Absorbers, D. Papadimitriou, S. Theodoropoulou, H.Y. Xu, C. Xue, Proc.
ISTM 2005, vol. 1, 998-1001.

,
Ga)S
2
Films and Solar-Cells, S.
Theodoropoulou, D. Papadimitriou, S. Bakehe, R. Klenk, M.Ch. Lux-Steiner, IASME
TRANSACTIONS, vol. 2(3) (2005) 287-293.

1-x
Ga
x
Se
2
Solid Films 511-512 (2006) 690-694.

2
Schedel-Niedrig, M.Ch. Lux-Steiner, Thin Solid Films 515(15) (2007) 5904-5908.

9. Test and Measurement of Chalcopyrite based Solar cells by Optical Modulation
Techniques, S. Theodoropoulou, D. Papadimitriou, Proc. ISTM 2007, vol. 4, 2881-2885.

10. Band-gap energies and strain effects in CuIn
1-x
Ga
x
S
2
based solar cells, S.
Theodoropoulou, D. Papadimitriou, A.G. Mamalis, D.E. Manolakos, R. Klenk, M.Ch. Lux-
Steiner, Semiconductor Science & Technology 22 (2007) 933-940.

11. Lattice Defect Analysis in Chalcopyrite Semiconductor Heterostructures by
Photoluminescence Excitation Spectroscopy, S. Theodoropoulou, D. Papadimitriou, and A.
Hoffmann (in preparation).

1-x
Ga
x
Se
2
Quaternary Alloys for Solar-Energy Conversion, S.
Theodoropoulou, D. Papadimitriou, Ch. Cobet, and N. Esser (in preparation).

13. Performance of rigid- and flexible-substrate chalcopyrite thin film solar-cells, S.
Theodoropoulou, D. Papadimitriou, Ch. Kaufmann (in preparation).

List of Conferences

1. Comparative study of the antioxidant activity of red and white wines in the presence of
oxygen free radicals by means of EPR and other spectroscopic methods, 2
nd
Panhellenic
Conference of Free Radicals and Oxidant Stress, Thessaloniki 2000.

2. Structural and optical properties of pyrolytic carbon derived from novolac resin
International Conference on NSTRUMENTAL ETHODS OF NALYSIS (IMA)
2003, Thessaloniki 2003.

3. ptical Properties of carbon materials formed by pyrolysis of novolac-resin/biomass
composites, UROPEAN MATERIALS RESEARCH SOCIETY (EMRS) Spring
Meeting 2003, Strasbourg 2003.

1-x
Ga
x
Se
2
Epitaxial Layers, UROPEAN
MATERIALS RESEARCH SOCIETY (EMRS) Spring Meeting 2005, Strasbourg 2005.

,
Ga)S
2
Films and Solar-Cells, 2005 IASME /
WSEAS International Conference on ENERGY, ENVIRONMENT,
ECOSYSTEMS&SUSTAINABLE DEVELOPMENT, Athens 2005.

2
Photoluminescence Spectroscopy, UROPEAN MATERIALS RESEARCH SOCIETY
(EMRS) Spring Meeting 2006, Nice 2006.

7. Characterization of ZnSe Thin Films Grown by EBE on Glass and Chalcopyrite-
Semiconductor Substrates, G. Roupakas, G. Kastrinaki, S. Theodoropoulou, M. Kokkoris,
D. Papadimitriou, M. Giorgiou, Ch. Panagopoulos, XXII Panhellenic Conference of Solid
State Physics and Material Science, Patras 2006.

8. THIN FILM PHOTOVOLTAICS: Preparation and Characterization of Chalcopyrite Thin
Films and Heterojunction Solar Cells, D. Papadimitriou, S. Theodoropoulou, G. Roupakas,
G. Manolis, Technical Chamber of Greece (TCG): Research and Technology Days,
Athens 2006.

9. Development of Optical Characterization Devices-Implementation on the
Characterization of Chalcopyrite Thin Films, D. Papadimitriou, G. Karras, Ch. Cobet, S.
Theodoropoulou, K. Anestou, G. Roupakas, W. Richter, PYTHAGORAS: Conference on
the Scientific Research in the National Technical University of Athens (NTUA), Lesvos
2007.

1-x
Ga
x
Se
2
Quaternary Alloys for Thin Film Photovoltaic
Technology, S. Theodoropoulou, D. Papadimitriou, K. Anestou, Ch. Cobet, and N. Esser,
XXIII Panhellenic Conference of Solid State Physics and Material Science, Athens
2007.

Scholarships:

1. EPEAEK II-Herakleitos-Research Scholarships in the National Technical University of
Athens (Fundamental Research),
CIGS Thin Film Photovoltaic Technology. Energy Band Gap and Lattice Defect Analysis in
Chalcopyrite Semiconductor Heterostructures, PhD, NTUA 8/11/02 - 7/11/05

2. ERASMUS-SOCRATES, NTUA-TU-Berlin 01/07/05-31/09/05

3. DAAD, CIGS Thin Film Photovoltaic Technology. Energy Band Gap and Lattice Defect
Analysis in Chalcopyrite Semiconductor Heterostructures, Hahn-Meitner Institute Berlin
1/10/06-31/07/07

145

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

145

Uploaded by

Copyright:

Available Formats

-

according to the formula 3[Cu

, and 21 optic modes:

and taking into account the long-range electrostatic interaction

of the 514.5 nm-line Ar

-values are not given in Table 7.5.1. The 457.9

=1.5 eV, as given in Ref. [7.43] is inserted.

, that have been

values of the ternary CIS have been considered, as the corresponding

for ternary CuInS

), absorption coefficients ( 4 / k = ) and

Ref. [7.84], [7.91]

You might also like