Semiconductors: Data Handbook (Ch. 6 & 7) (Ed: O. Madelung)

6 I-III-VI2 compounds
(included are I-Fe-VI2 compounds)
6.0 Crystal structures and electronic structure

Nearly all semiconducting I-III-VI2 compounds crystallize in the chalcopyrite lattice (Fig. 6.0.1). Hightemperature phases show a disordered zincblende lattice, high-pressure phases a disordered rocksalt lattice.
Fig. 6.2 shows the Brillouin zone of fcc (zincblende) lattice and two Brillouin zones of chalcopyrite. Each point
point
in the chalcopyrite Brillouin zone maps on to 4 different points of the zincblende zone. Thus the
corresponds to , X and two W points.
A useful starting point for a description of the electronic properties of compounds with chalcopyrite structure is
the band structure of the zincblende parent compound represented in the smaller Brillouin zone of the ternary
(see Fig. 6.0.2). These "folded back" curves can be labelled with the irreducible representations to which they
correspond in both the chalcopyrite or zincblende space groups.
The tetragonal symmetry of the chalcopyrite lattice leads to a change in the band structure even at the center of
the Brillouin zone .
Non-degenerate band-edges at ( 1... 4) are shaped according to E(k) = E( ) + ( 2/2)(kz2/m`` + (kx2+ky 2)/m )
with the z-axis parallel to the c-axis. Electrons are thus characterized by two effective masses: m`` and m . From
these two other effective masses are often defined: a density of states effective mass mds3 = m 2m`` and a
conductivity effective mass (1/mc) = (1/3)(1/m`` + 2/m ).
The
5-band
is split at k
0 into two bands:
E(k) = E( ) +
2k 2/2m(
z
) + ( 2/2m)(a (b2 + c2cos(4 ))1/2)(kx2 + ky2)
where is the angle between k and kx in the kxky plane, with k the direction of k perpendicular to the z-axis.
Finally the 6- and 7-bands contain terms linear in k.
This simple picture is somewhat complicated by the effects of spin-orbit coupling which splits the 5 state. This
splitting is given by the formula: E1,2 = 1/2( so + cf) 1/2[( so + cf)2 8/3 so cf]1/2, where so is the spinorbit splitting in a cubic crystal field and cf is the crystal field splitting of the valence bands in the absence of
spin-orbit coupling. The two solutions E1 and E2 give the separation of the two 7 states from the 6. In
chalcopyrite it is found that the crystal field splitting is negative, that is 4 lies above 5 and that this splitting is
due almost entirely to the tetragonal compression. It compares very well with that expected from the
corresponding zincblende compound under uniaxial pressure.
Fig. 6.0.3 ... 6.0.9 show the band structures of the most important semiconductors dealt with in this chapter.
Figures to 6.0
Fig. 6.0.1
The chalcopyrite lattice
Fig. 6.0.2
Brillouin zone of the chalcopyrite lattice
Fig. 6.0.3
Band structure of CuAlS2.
Fig. 6.0.4
Band structure of CuAlSe2.
Fig. 6.0.5
Band structure of CuGaS2.
Fig. 6.0.6
Band structure of CuGaSe2.
Fig. 6.0.7
Band structure of CuInS2.
Fig. 6.0.8
Band structure of CuInSe2.
Fig. 6.0.9
Band structure of CuFeS2.
6.1 Copper aluminum sulfide (CuAlS2)

Crystal structure
CuAlS2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
Electronic properties
band structure : see Fig. 6.0.3, Brillouin zone: Fig. 6.0.2.
energy gap
Eg
3.42 eV
3.34 eV
dEg/dT
1.5g
2.3 10
T = 300K
T = 300K
4
eV K
transmission, E c
transmission, E `` c
85B
85B
from modulated phase-shiftdifference spectroscopy
91S
absorption
73B
excitonic energy gap

Egx (A)
(B, C)
3.54 eV
3.71 eV
T = 78 K
excitonic energy gap fine structure (from photoluminescence)

Egx
3.475 eV
3.500 eV
3.532 eV
3.540 eV
3.550 eV
3.525 eV
T = 10 K
T = 77 K
bound exciton
bound exciton
bound exciton
bound exciton
free exciton
epitaxial layer on GaAs
92S
95C
electroreflectance
75S1
RT
75S2
RT
53H
calculated from plasmon energy
96K
splitting energies (at

0.13 eV
0 eV
cf
so
T = 300 K
T = 300 K
Lattice properties
lattice parameters
a
c
c/a
5.32(1)
10.430(15)
1.960(1)
density
d
3.45 g cm
bulk modulus
B
82.44 GPa
melting temperature
Tm
1570 K
75S
wavenumbers of infrared and Raman active phonons

at RT
LO/
TO
Symmetry
I 4 2d (F 4 3m)
( 15)
4
( 15)
5
(W2)
3
(W4)
5
(W1)
1
(W2)
4
(X5)
5
(X3)
3
(W3)
5
(W4)
5
(W2)
4
(W2)
3
(X5)
5
418/446 cmn1
497/444 cmn1
443 cmn1
/432 cmn1
315 cmn1
284/271 cmn1
266/263 cmn1
268 cmn1
217/216 cmn1
137/137 cmn1
112/112 cmn1
98 cmn1
76/76 cmn1
all are Raman active;

are IR active
4,
75K
Transport and optical properties

carrier concentration, resistivity, mobility
p-type samples
p
n-type samples
p
n
5 1017 cm 3
3 1015 cm 3
1 cm
104g105 cm
103 cm
< 3 cm2 V 1 s 1
RT
RT
RT
0.5g102
RT
cm
< 3 cm2 V 1s
RT
epitaxial layer, As-doped
92M
87D
epitaxial layer, As-doped

single crystals, as grown
single crystals, annealed in S-atmosphere
single crystals
92M
89A
87D
89A
single crystals, annealed in Cd-, Al-,

and Zn-atmosphere
single crystals
89A
89A
The temperature dependence of the electrical conductivity of CuAlS 2 crystals grown by CVT annealed under
different conditions is given in Fig. 6.1.1 [89A].
activation energy
EA
0.32 eV
activation energy of donors
89A
from infrared reflection
95A
from infrared reflection
95A
dielectric constants
(0)
( )
7.05
8.14
4.8
4.9
E `` c
E c
E `` c
E c
References to 6.1
53H
73B
75K
75S
85B
87D
89A
91S
92M
92S
95A
95C
96K
Hahn, H., Frank, G., Klingler, W., Meyer, A. D., Strger, G.: Z. Anorg. Allgem. Chem. 271 (1953) 153.
Bettini, M.: Solid State Commun. 13 (1973) 599.
Koschel, W. H., Bettini, M.: Phys. Status Solidi (b) 72 (1975) 729.
Shay, J. L., Wernick, J. H.: Ternary Chalcopyrite Semiconductors: Growth, Electronics, Properties and
Applications. Pergamon, 1975.
Bodnar, I.V., Orlova, N.S.: Phys. Status Solidi A 91 (1985) 503.
Drabkin, I.A., Moizhes, B.Ya.: Fiz. Tekh. Poluprovodn. 21 (1987) 1715; Sov. Phys. Semicond. (Engl.
Transl.) 21 (1987) 1037.
Aksenov, I.A., Gulakov, I.R., Lipnitskii, V.I., Lukomskii, A.I., Makovetskaya, L.A.: Phys. Status Solidi
A 115 (1989) K113.
Sato, K., Kudo, Y., Kijima, S., Samanta, L.K.: J. Cryst. Growth 115 (1991) 740.
Morita, Y., Narusawa, T.: Jpn. J. Appl. Phys., Part 2 (Letters), 31 (1992) 1396.
Shirakata, S., Aksenov, I., Sato, K., Isomura, S.: Jpn. J. Appl. Phys., Part 2 (Letters), 31 (1992) L1071.
Andriesh, A.M., Syrbu, N.N., Iovu, M.S., Tazlavan, V.E.: Phys. Status Solidi B 187 (1995) 83.
Chichibu, S., Nakanishi, H., Shirakata, S.: Appl. Phys. Lett. 66 (1995) 3513.
Kumar, V., Prasad, G.M., Chandra, D.: Cryst. Res. Technol. 31 (1996) 501.
Figures to 6.1
Fig. 6.0.1
Fig. 6.0.2
Fig. 6.0.3
Band structure of CuAlS2.
Fig. 6.1.1
CuAlS2. The electrical conductivity versus inverse temperature for single crystals, grown by the CVT method
(1), and annealed in the presence of sulphur (2), zinc (3), and cadmium/aluminum (4) [89A].
6.2 Copper aluminum selenide (CuAlSe2)

Crystal structure
CuAlSe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir
Eg,dir (A)
(B)
(C)
2.68 eV
2.65 eV
2.88 eV
3.02 eV
RT
T = 110 K
from optical absorption

phase-shift-difference spectroscopy
93M
77Y
T = 20 K
free exciton from photoreflectance

93C
77Y
calculated
from photoreflectance, bulk material
from photoreflectance, thin film
film thickness: 0.26 0.3 m
calculated
calculated
from photoreflectance, bulk material
73B
93S
93S
calculated
95W

Egx
Egx (A)
(B)
(C)
2.739 eV
2.77 eV
2.85 eV
2.96 eV

cf
0.17 eV
0.145 eV
n0.18g0.19 eV
0.16 eV
0.18 eV
0.18g0.19 eV
so
T = 77 K
T = 77 K
T = 77 K
0.152
95W
93S
Lattice properties
lattice parameters
a
c
c/a
5.61(1)
10.92(6)
1.95(1)
RT
75S2
RT
53H
density
4.69 g cm
melting temperature
Tm
1470 K
75S1
Transport properties
carrier concentration, resistivity, mobility
p-type samples
p
3 1018...
10 cm 3
2.8 102...
7.1 109 cm
35 cm2 V 1 s 1
Hall measurements, epilayers
93C
RT
single crystal, undoped
91C
RT
from Hall-measurements on single crystals 91C
n-type samples
n
n
4 1018 cm 3
0.02 cm
60 cm2 V 1s
epilayer
epilayer
epilayer
91M
91M
91M
The temperature dependence of the Hall hole mobility is given in Fig. 6.2.1.
Optical properties
refractive indices
no
ne
2.7797
2.5293
2.4969
2.4851
2.4795
2.4759
2.4733
2.4712
2.4685
2.4659
2.7886
2.5179
2.4852
2.4734
2.4676
2.4638
2.4609
2.4586
2.4559
2.4533
[m]
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
5.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
5.00
2.603
75S
calculated from
96R
Refractive index dispersion of ordinary and extraordinary beams for CuAlSe2 is given in Fig. 6.2.2 [90B].
(0)
( )
8.28
5.2
6.0
6.67
E c
E `` c
E c
E `` c
from IR reflectivity
95A
from IR reflectivity
95A
References to 6.2
53H
73B
75S1
75S2
77Y
90B
91C
91M
93C
93M
93S
95A
95W
96R
Bettini, M.: Solid State Commun. 13 (1973) 599.
Suzuki, K., Kambara, T., Gondaira, K., Sato, K., Kondo, K., Teranishi, T.: J. Phys. Soc. Jpn. 39 (1975)
1310.
Yamamoto, N., Horinka, H., Okada, K., Miyauchi, T.: Jpn. J. Appl. Phys. 16 (1977) 1817.
Bodnar, I.T., Bodnar, I.V.: Phys. Status Solidi A 121 (1990) K247.
Chichibu, S., Shishikura, M., Ino, J., Matsumoto, S.: J. Appl. Phys. 70 (1991) 1648.
Morita, Y., Narusawa, T.: Jpn. J. Appl. Phys., Part 2 (Letters), 30 (1991) L1238.
Chichibu, S., Matsumoto, S., Shirakata, S., Isomura, S.: J. Appl. Phys. 74 (1993) 6446.
Moon-Seog Jin, Suk-Ki Min, Han-Jo Lim, Hong-Lee Park, Wha-Tek Kim: Jpn. J. Appl. Phys.,
Supplement 32 (1993) 593.
Shirakata, S., Chichibu, S., Matsumoto, S., Isomura, S: Jpn. J. Appl. Phys., Supplement 32 (1993) 494.
Abdelghany, A.: Appl. Phys. A 60 (1995) 77.
Wei, S., Zunger, A.: J. Appl. Phys. 78 (1995) 3846.
Reddy, R.R., Nazeer Ahammed, Y., Reddy, C.V.K., Buddhudu, S.: Cryst. Res. Technol. 31 (1996) 827.
Figures to 6.2
Fig. 6.0.1
Fig. 6.0.2
Fig. 6.0.4
Band structure of CuAlSe2.
Fig. 6.2.1
CuAlSe2. Dependence of the Hall hole mobility on the temperature of a single crystal [91C].
Fig. 6.2.2
CuAlSe2. Refractive index dispersion of ordinary and extraordinary beams for a single crystal [90B].
6.3 Copper aluminum telluride (CuAlTe2)

Crystal structure
CuAlTe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir (A)
(B,C)
dEg/dT (A)
dEg/dp (A)
2.43 eV
T = 300 K, E `` c
2.55 eV
E c
2.2(2)10 4 eV K 1 T = 80...300 K
3.410 6 eV bar 1 T =300 K
electroreflectance
75S1
absorption
79H
76J
cathodoluminescence
modulated phase difference
78S
78H

Egx (A)
(B,C)
2.467(2) eV
2.596(1) eV
T = 300 K
Temperature coefficient of the exciton energy:
96I
wavelength derivative reflectance

wavelength derivative reflectance
( so 0!) (unresolved in other
experiments [75S1, 75Y])
75T
75T
phase-shift-difference
77Y
RT
75S2
RT
53H
1.8 10
eVK
splitting energies (at )

valence band splitting
0.13 eV
0.017 eV
cf
so
T = 77 K
T = 77 K
effective masses
mn
mp
0.13 m0
0.69 m0
Lattice properties
lattice parameters
a
c
c/a
5.96(1)
11.77(3)
1.97
density
d
5.47 g cm
thermal expansion coefficient

a [nm] = 0.600818 + 3.26 10 6T + 6.09 10 9T2 1.45 10
c [nm] = 1.190740 + 4.24 10 5T + 3.33 10 9T2 + 1.19 10
12T3 (T
in K)
87O
12T3
resistivity
p-type samples
106
cm
polycrystalline thin films
95E
The temperature dependence of the electrical conductivity for CuAlTe 2 thin films in the range of 100g300 K is
given in Fig. 6.3.1 [95E].
activation energies
EA
0.25 eV
0.96 eV
T = 100g200 K
T = 200g300 K
activation energy of conductivity

of thin films
95E
Optical properties
refractive index
n
2.874
calculated from
96R
calculated
95M
``
0
0
||
10.8
11.0
10.9
7.4
7.6
7.5
References to 6.3
53H
75S1
75S2
75T
75Y
76J
77Y
78H
78S
79H
87O
95E
95M
96I
96R
1310.
Tell, B., Bridenbaugh, P. M.: Phys. Rev. B 12 (1975) 3330.
Yamamoto, N., Tohge, N., Miyauchi, T.: Jpn. J. Appl. Phys. 14 (1975) 192.
Jayaraman, A., Narayanamurti, V., Kasper, H. M., Chin, M. A., Maines, R. G.: Phys. Rev. B 14 (1976)
3516.
Horinaka, H., Yamamoto, N., Miyauchi, T.: Jpn. J. Appl. Phys. 17 (1978) 521.
Sermage, B.: Solid State Electron. 21 (1978) 1361.
Hrig, W., Neumann, H., Reccius, E., Weinert, H., Khn, G., Schumann, B.: Phys. Status Solidi (a) 51
(1979) 57.
Orlova, N.S., Bodnar, I.V.: Cryst. Res. Technol. 22 (1987) 1409.
El Assali, K., Chahboun, N., Bekkay, T., Ameziane, E.L., Boustani, M., Khiara, A.: Solar Energy
Mater. Solar Cells 39 (1995) 33.
Marquez, R., Rincon, C.: Phys. Status Solidi B 191 (1995) 115.
In-Hwan Choi, Yu, P.J.: J. Phys. Chem. Solids 57 (1996) 1695.
Figures to 6.3
Fig. 6.0.1
Fig. 6.3.1
CuAlTe2. Temperature dependence of the conductivity for thin films in the range of 100g300 K [95E].
1cm 1.
=1
6.4 Copper gallium sulfide (CuGaS2)

Crystal structure
CuGaS2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir (A)
(B,C)
dEg/dT (A)
2.43 eV
T = 300 K, E `` c
2.55 eV
E c
2.2(2)10 4 eV K 1 T = 80...300 K
electroreflectance
75S1
absorption
79H

Egx (A)
(B,C)
2.467(2) eV
2.596(1) eV
T = 300 K
cathodoluminescence
modulated phase difference
78S
78H
Egx
2.51 eV
T=5K
96B
T = 4.2 K
T = 4.2 K
T = 4.2 K
T = 4.2 K
free-exciton emission
(D0/X) exciton complex
(A0/X) exciton complex
(A0/X) exciton complex
90S
T = 80 K
from photocurrent excitation spectra
91S
88S
RT
75S2
RT
77B
no temperature or orientation given
80B
exciton emissions from photoluminescence

2.504 eV
2.501 eV
2.495 eV
2.493 eV
valence band splitting energies (at )

cf
so
0.129 eV
7 meV
Lattice properties
lattice parameters
a
c
c/a
5.35(2)
10.46(2)
1.960(2)
density
4.38 g cm
linear thermal expansion coefficient

7.710 6 K 1
Debye temperature
D
356 K
0K
75A
melting temperature
Tm
1550 K
76K
wavenumber of infrared and Raman active phonons

( in cm 1, T = 300 K)
LO/
TO
[75K]
[80C]
401/368
384/363
358
352/332
312
281/267
276/262
203
160/156
393/367
385/367
401
347/332
312
288/286
283/273
238
167/167
147/147
95/95
116
75/75
95/95
97
74/
Symmetry
I 4 2d (F 4 3m)
4
5
3
5
1
4
5
3
5
5
4
3
5
( 15)
( 15)
(W2)
(W4)
(W1)
(W2)
(X5)
(X3)
(W3)
(W4)
(W2)
(W2)
(X5)
resistivity
p-type samples
106g107
cm
87O
epilayers on GaAs,
activation energy for conductivity
93M
p-type sample, annealed under

maximum S-pressure;
no anisotropy reported
75S1
calculated
84M
activation energy
EA
0.05...0.056 eV
resistivity, carrier concentration and mobility

p
p
1 cm
41017 cm 3
15 cm2 V 1 s
T = 300 K
T = 300 K
T = 300 K
thermal conductivity
5.09 W m
1K 1
Optical properties
refractive index
The dispersion of the refractive index is given in Fig. 6.4.1 [90B].
coefficients in the formula: n2 = A + B/(1 C/ 2) + D/(1 E/ 2)

A
3.9064
4.3165
4.0984
4.4834
2.3065
1.8692
2.1419
1.7316
0.1149 m2
0.1364 m2
0.1225 m2
0.1453 m2
1.5479
1.7575
1.5955
1.7785
738.43 m2
738.43 m2
T = 290 K
T = 390 K
T = 290 K
T = 390 K
T = 290 K
T = 390 K
T = 290 K
T = 390 K
T = 290 K
T = 390 K
79B
ordinary index(O)
extraordinary index(E)
O
E
O
F
O
F
O
F
O
F
O
F
O
E
O+E
O+E
[m]
no
ne
2.7630
2.5517
2.5051
2.4945
2.4884
2.4843
2.4774
2.4714
2.4639
2.4539
2.4429
2.4311
2.4171
2.3999
2.7813
2.5464
2.4991
2.4880
2.4816
2.4772
2.4694
2.4621
2.4539
2.4435
2.4311
2.4179
0.55
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
0.55
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
75S1
75S1
linear electrooptic coefficient

r41
r63
1.76 10 12 m/V
1.9 10 12 m/V
1.1 10 12 m/V
1.35 10 12 m/V
1.66 10 12 m/V
1.05 10 12 m/V
[nm]
633
1150
3390
633
1150
3390
RT
74T
(0)
( )
7.6
8.9
6.1
6.2
T = 300 K, E `` c
E c
T = 300 K, E `` c
E c
75S1
77S
References to 6.4
74T
75A
75K
75S1
75S2
76K
77B
77S
78H
78S
79B
79H
80B
80C
84M
87O
88S
90B
90S
91S
93M
96B
Turner, E. H., Buehler, F., Kasper, H.: Phys. Rev. B 9 (1974) 558.
Abrahams, S. C., Hsu, F. S. L.: J. Chem. Phys. 63 (1975) 1162.
1310.
Kokta, M., Carruthers, J. R., Crasso, M., Kasper, H. M., Tell, B.: J. Electron. Mater. 5 (1976) 69.
Bachmann, K. J., Hsu, F. S. L., Thiel, F. A., Kasper, H. M.: J. Electron. Mater. 6 (1977) 431.
Sermage, B., Voos, M.: Phys. Rev. B 15 (1977) 3935.
Horinaka, H., Yamamoto, N., Miyauchi, T.: Jpn. J. Appl. Phys. 17 (1978) 521.
Sermage, B.: Solid State Electron. 21 (1978) 1361.
Bhar, G. C., Ghosh, G.: J. Opt. Soc. Am. 69 (1979) 730.
Hrig, W., Neumann, H., Reccius, E., Weinert, H., Khn, G., Schumann, B.: Phys. Status Solidi (a) 51
(1979) 57.
Bhar, G. C., Ghosh, G. C.: Appl. Opt. 19 (1980) 1029.
Carlone, C., Olego, D., Jayaraman, A., Cardona, M.: Phys. Rev. B 22 (1980) 3877.
Makovetskaya, L.A., Belevich, N.N., Bodnar, I.V., Grutso, S.A., Yaroshevich, G.P.: Izv. Akad. Nauk
SSSR, Neorg. Mater. 20 (1984) 382; Inorg. Mater. (Engl.Transl.) 20 (1984) 322.
Orlova, N.S., Bodnar, I.V.: Phys. Status Solidi A 101 (1987) 421.
Shirakata, S., Murakami, K., Isomura, S.: Jpn. J. Appl. Phys., Part 1, 27 (1988) 1780.
Bodnar, I.V., Bodnar, I.T.: Opt. Spektrosk. 68 (1990) 373; Opt. Spectrosc. (Engl. Transl.) 68 (1990)
218.
Shirakata, S., Saiki, K., Isomura, S.: J. Appl. Phys. 68 (1990) 291.
Susaki, M., Horinaka, H., Yamamoto, N.: Jpn. J. Appl. Phys., Part 1, 30 (1991) 2797.
Morohashi, M., Tsuboi, N., Terasako, T., Iida, S., Okamoto, S.: Jpn. J. Appl. Phys., Supplement, 32-3
(1993) 621.
Bellabarba, C., Gonzalez, J., Rincon, C.: Phys. Rev. B 53 (1996) 7792.
Figures to 6.4
Fig. 6.0.1
Fig. 6.0.2
Fig. 6.0.5
Band structure of CuGaS2.
Fig. 6.4.1
CuGaS2. Values of the refractive indices of the ordinary and extraordinary rays as a function of wavelength for
single crystals [90B]. T not given.
6.5 Copper gallium selenide (CuGaSe2)

Crystal structure
CuGaSe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir (A)
(B)
(C)
1.68 eV
1.75 eV
1.96 eV
T = 300 K
electroreflectance
75S1
Variation of the band gap with the temperature for CuGaSe2 is given in Fig. 6.5.1 [93B]
Egx (A)
1.695 eV
T = 20 K (n = 1)
77T
exciton binding energy

Eb (A)
1610
3 eV
77Y

0.139 eV
0.238 eV
cf
so
T = 77 K
T = 77 K
from photoreflectance
from photoreflectance
94C
94C
RT
75S2
RT
77B2
a axis
c axis
80B
Lattice properties
lattice parameters
5.61(1)
11.00(2)
1.960(4)
a
c
c/a
density
5.57 g cm

13.1(14)10 6 K
5.2(7)10 6 K 1
T = 300...670 K
Debye temperature
262.0(7) K
0K
82B
melting temperature
1310...1340 K
Tm
75S1
wavenumbers of IR active phonons (at RT)

Symmetry
I 4 2d (F 4 3m)
LO/
TO
278/254
276/250
196/178
190/170
4
5
4
5
( 15)
( 15)
(W2)
(W4)
infrared absorption
77B1
(p-type samples)
carrier concentration, resistivity, mobility, thermoelectric power
p-type samples
p
p
0.26g14 10 19 cm 3 RT
0.05g6 cm
3.12g
RT
2
1
1
21.4 cm V s
0.084g
RT
0.24 mV K 1
thin films
thin films
thin films
95M
92L
95M
thin films
95M
The temperature dependence of the resistivity in undoped and Sn-doped p-type CuGaSe 2 single crystals is shown
in Fig. 6.5.2 [96S].
The temperature dependence of the Hall mobilities of undoped and Sn-doped CuGaSe 2 single crystals is shown
in Fig. 6.5.3 [96S].
electrical conductivity
1.3g86
1 cm 1
RT
thin films, four probe method
95M
T = 390 450 K
T = 300 390 K
94M
calculated
95R
activation energy
EA
0.240g0.270 eV
0.080 0.090 eV
0.129 W cm
1K 1
Optical properties
refractive index
no
ne
2.9580
2.8358
2.7430
2.7273
2.7211
2.7170
2.7133
2.7101
2.7060
2.7021
2.6974
2.6926
2.6872
3.0093
2.8513
2.7510
2.7344
2.7276
2.7232
2.7192
2.7158
2.7111
2.7065
2.7014
2.6981
2.6898
?mm]
0.78
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
0.78
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
75S1
75S1
References to 6.5
75S1
75S2
77B1
77B2
77T
77Y
80B
82B
92L
93B
94C
94M
95M
96R
96S
97S
1310.
Bodnar, I. V., Karoza, A. G., Smirnova, G. F.: Phys. Status Solidi (b) 84 (1977) K65.
Teranishi, T., Sato, K., Saito, Y.: Inst. Phys. Conf; Ser. 35 (1977) 59.
Bhar, G. C., Ghosh, G. C.: Appl. Opt. 19 (1980) 1029.
Bohmhammel, K., Deus, P., Khn, G., Mller, W.: Phys. Status Solidi (a) 71 (1982) 505.
Leon, M., Diaz, R., Rueda, F., Berghol, M.: Solar Energy Mater. Solar Cells 26 (1992) 295.
Bellabarba, C., Rincon, C.: Jpn. J. Appl. Phys., Supplement, 32 (1993) 599.
Chichibu, S., Harada, Y., Uchida, M., Wakiyama, T., Matsumoto, S., Shirakata, S., Isomura, S.,
Higuchi, H.: J. Appl. Phys. 76 (1994) 3009.
Miyake, H., Hata, M., Hamamura, Y, Sugiyama, K.: J. Cryst. Growth 144 (1994) 236.
Mansour, B.A., El-Hagary, M.A.: Thin Solid Films 256 (1995) 165.
Susaki, M., Yamamoto, N., Prevot, B., Schwab, C.: Jpn. J. Appl. Phys., Part 1, 35 (1996) 1652.
Schoen, J. H., Alberts, V., Bucher, E.: J. Appl. Phys. 81 (1997) 2799.
Figures to 6.5
Fig. 6.0.1
Fig. 6.0.2
Fig. 6.0.6
Band structure of CuGaSe2.
Fig. 6.5.1
CuGaSe2. Variation of the band gap with the temperature [93B]. Solid line calculated.
Fig. 6.5.2
CuGaSe2. Resistivity versus temperature for various undoped (UD) and Sn-doped single crystals [96S].
Fig. 6.5.3
CuGaSe2. Temperature dependence of the Hall mobility of undoped (UD) and Sn-doped (SN1, SN2) single
crystals. The values of the mobility are due to scattering at acoustic phonons ac, nonpolar acoustic phonons
acnpo, impurities (neutral and ionized) IN, and the resulting fits are shown as solid lines [96S]. Dotted lines are
not explained.
6.6 Copper gallium telluride (CuGaTe2)

Crystal structure
CuGaTe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir
(A)
(B)
(C)
1.23g1.26 eV
1.227 eV
1.280 eV
1.97 eV
RT
RT
RT
thin films, optical transmission

transmission in polycrystalline,
thin films
92L
79N
transmission in "thin" polycrystalline

films
79N
RT
75S2
RT
77B
from XRD measurements
86B

0.08(4) eV
0.71(4) eV
cf
so
T = 300 K
T = 300 K
Lattice properties
lattice parameters
a
c
c/a
6.00(1)
11.93(2)
1.985(5)
density
5.95 g cm

``c
c
6.6 10 6 K 1
11.7 10 6 K 1
Debye temperature
226.2(8) K
D
RT
RT
T
0K
82B
melting temperature
Tm
1140 K
75S1
phonon wavenumbers
209.2(1) cm
201.4(1) cm
166.4(5) cm
T = 300 K
thin films
79N
1
1

(p-type samples)
carrier concentration, mobility, conductivity and Seebeck coefficient
p
p
1018 cm 3
50 cm2 V 1 s 1
11 1 cm 1
2.710 1 VK 1
75S1
activation energy
EA
0.006g0.019 eV
87W
The thermal conductivity as a function of temperature for p-type CuGaTe 2 is shown in Fig. 6.6.1 [87W].
(0)
( )
12.7
8.5
calculated
calculated
95M
95M
refractive index
n
2.83(9)
h = 0.5 eV
80H
References to 6.6
75S1
75S2
77B
79N
80H
82B
86B
87W
92L
95M
1310.
Neumann, H., Hrig, W., Reccius, E., Sobotta, H. . Schumann, B., Khn, G.: Thin Solid Films 61
(1979) 13.
Hrig, W., Neumann, H., Savalev, V., Lagzdonis, J.: Phys. Lett. 78A (1980) 189.
Bohmhammel, K., Deus, P., Khn, G., Mller, W.: Phys. Status Solidi (a) 71 (1982) 505.
Bodnar, I.V., Orlova, N.S.: Cryst. Res. Technol. 21 (1986) 1091.
Wasim, S.M., Noguera, A.: Solid State Commun. 64 (1987) 439.
Leon, M., Diaz, R., Rueda, F., Berghol, M.: Solar Energy Mater. Solar Cells 26 (1992) 295.
Marquez, R., Rincon, C.: Phys. Status Solidi B 191 (1995) 115.
Figures to 6.6
Fig. 6.0.1
Fig. 6.6.1
CuGaTe2. Thermal conductivity as a function of temperature for p-type samples [87W].
6.7 Copper indium sulfide (roquesite, CuInS2)

Crystal structure
CuInS2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
band structure : Fig. 6.0.7, Brillouin zone: Fig. 6.0.2.
energy gap
1.53 eV
1.519 eV
Eg,dir
4.3 10 5 eV K 1
8.7 10 5 eV K
dEg/dT
Eg,dir (A,B,C)
1.53 eV
86H
RT
from electroreflectance
from EER, 1012 phosphorus doped
T = <120 K
T = >120 K
single crystal
single crystal
88H
88H
T = 300 K
electroreflectance, bulk crystal
75S1
T=2K
(n = 1) absorption
(n = 1)
75S1

Egx
(A)
(B)
1.536 eV
1.554 eV

cf(
)
(
so )
>
0.005 eV
0.02 eV
75S1
effective masses
mn
mp
0.03 m0
1.3 m0
from electrolyte electroreflectance

Hall effect
87H
80H
RT
75S2
RT
77B
Lattice properties
lattice parameters
a
c
c/a
5.52(1)
11.08(6)
2.00(1)
density
4.74 g cm
Debye temperature
D
273 K
0K
77B
melting temperature
Tm
1270...1320 K
75S1

Symmetry
I 4 2d (F 4 3m)
LO/
TO
352/323 cmn1
339/321 cmn1
314/295 cmn1
294 cmn1
266/234 cmn1
260/244 cmn1
/140 cmn1
/88 cmn1
/79 cmn1
/67 cmn1
4
5
5
1
4
5
5
4
3
5
( 15)
( 15)
(W4)
(W1)
(W2)
(X5)
(W3)
(W2)
(W2)
(X5)
T = 4.5 K, 4,
Raman active
are IR active, all are
75K
resistivity, carrier concentration, mobility
p-type samples
p
p
3 1017 cm 3
10g104 cm
499 cm2 V 1 s 1
RT
single crystals, sulfur-annealed

thin films from reactive sputtering
single crystal, p-doped
90H
95K
86L
1016g1017 cm 3
1 cm
103g104 cm
1g10 cm
0.1g1 cm
80 cm
40 cm2 V 1s 1
20g50 cm2 V 1s
165 cm2 V 1s 1
RT
RT

single crystals, Zn-doped (0.25 %)
In-rich thin films
single crystal, as grown
polycrystalline tablets by sintering
single crystal
90H
93H
90U
90U
90U
95P
90H
90Y
93K
n-type samples
n
RT
1
RT
For temperature dependence of resistivity and mobilities, see Figs. 6.7.1...3.
Optical properties
refractive index
no
2.7907
2.7225
2.6020
2.5838
2.5760
2.5699
2.5645
2.5587
2.5522
2.5448
2.5366
2.5274
2.5166
2.5108
[m]
0.90
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
12.50
75S1
ne
2.7713
2.7067
2.5918
2.5741
2.5663
2.5598
2.5539
2.5474
2.5401
2.5311
2.5225
2.5112
2.4987
0.90
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
75S1
References to 6.7
75K
75S1
75S2
76L
77B
77M
80H
86H
86L
87H
88H
90H
90U
90Y
93H
93K
95K
95P
1310.
Look, D. C., Manthuruthil, J. C.: J. Phys. Chem. Solids 37 (1976) 173.
Mittleman, S. D., Singh, R.: Solid State Commun. 22 (1977) 659.
Hwang, H. L., Tu, C. C., Maa, J. S., Sun, C. Y.: Solar Energy Mater. 2 (1980) 433.
Hsu, T.M.: J. Appl. Phys. 59 (1986) 2538.
Lin, J.L., Lue, J.T., Yang, M.H., Hwang, H.L.: Appl. Phys. Lett. 48 (1986) 1057.
Haworth, L.I., Al-Saffar, I.S., Tomlinson, R.D.: Phys. Status Solidi A 99 (1987) 603.
Hsu, T.M., Lin, J.H.: Phys. Rev. B 37 (1988) 4106.
Hsu, T.M., Lee, J.S., Hwang, H.L.: J. Appl. Phys. 68 (1990) 283.
Ueng, H.Y., Hwang, H.L.: J. Phys. Chem. Solids 51 (1990) 11.
Yamamoto, N., Ogihara, J., Horinaka, H.: Jpn. J. Appl. Phys., Part 1, 29 (1990) 650.
Hsu, T.M.: Jpn. J. Appl. Phys., Supplement, 32 (1993) 537.
Koscielniak-Mucha, B., Opanowicz, A.: Phys. Status Solidi A 139 (1993) K73.
Kobayashi, S., Dan Yang Yu, Sarinanto, M.M., Kobayashi, Y., Kaneko, F., Kawakami, T.: Jpn. J. Appl.
Phys., Part 2, 34 (1995) L513.
Park, G.C., Yoo, Y.T., Lee, J.: Synth. Met. 71 (1995) 1745.
Figures to 6.7
Fig. 6.0.1
Fig. 6.0.2
Fig. 6.0.7
Band structure of CuInS2.
Fig. 6.7.1
CuInS2. Electron mobility vs. temperature for various annealing temperatures (given as parameters) [76L].
Annealing atmosphere: In; single crystalline samples.
Fig. 6.7.2
CuInS2. Resistivity vs. reciprocal temperature for crystals annealed in Zn, Cd at T = 920 K, 1070 K [77M].
Fig. 6.7.3
CuInS2. Electron Hall mobility vs. temperature [77M].
6.8 Copper indium selenide (roquesite, CuInSe 2)

Crystal structure
CuInSe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir
(1.010 0.001) eV RT, single crystal
dEg/dT
1.110
eV K
absorption, lower Eg s at RT are due to

increased electron and ionized impurity
concentration n and NI respectively
T = 100...300 K
86N
87N

epitaxial films on GaAs (001) substrates
EX1
1.0386 eV
T=2K
PL, free exciton, n = 1 [FEn=1]
94N
In 4d core state
positive!
87T
75S
PL
97S

so
cf
so
0.8 eV
+ 0.006 eV
0.23 eV
T = 77 K
T = 77 K

Eb
4.3 meV
T=2K
effective masses
The Fermi surface of electrons is spherical and located at the center of the Brillouin zone [93A].
m*c
m*0
mn = mp
0.082(2) m0
0.077(2) m0
0.087 m0
cyclotron mass value

eff. mass at minimum of conduction band
T = 300 K
93A
92R
Lattice properties
lattice parameters
a
c
c/a
5.78(1)
11.55(2)
2.00
RT
77H
RT
77B
along c - axis
along a - axis
85B
density
5.77 g cm
coefficient of thermal expansion

X-ray studies on powder prepared from single crystals
7.9010 6 K 1
11.2310 6 K 1
RT
RT
Debye temperature
D
243.7 K
0K
90F
melting temperature
Tm
1260 K
75S
compressibility
2.310
11
Pa
87N
phonon dispersion
for measured acoustic and optical phonon dispersion relations in [001]-, [110]- and [100]-direction see
Fig. 6.8.1a-c [93F].
wavenumbers of Raman active phonon
174 cm 1
76 cm 1
LO/
A1 mode
B1 mode
230/227 cm
229 cm 1
179 cm 1
178 cm 1
78/78 cm 1
67 cm 1
60/61 cm 1
TO
176 cm 1
77/77 cm
60/58 cm
Raman on thin films

1
[W4u]
3 [W2u]
3 [X3]
1 [W1]
5 [W4l]
3 [W2l]
5 [X5l]
5
90Y
92T
second order elastic moduli

c11
c33
c44
c66
c12
c13
9.70 1010 Nm 1
10.89 1010 Nm 1
3.62 1010 Nm 1
3.16 1010 Nm 1
5.97 1010 Nm 1
8.60 1010 Nm 1
T = 300 K
inelastic neutron scattering

on single crystal
93F
4.821012 Pa
RT
dynamic pulse-echo overlap method
90F
RT
RT
dynamic pulse echo overlap method

dynamic pulse echo overlap method
90F
90F
bulk modulus
B
sound velocity
vL
3.77105 cm s
vT
2.10105 cm s
1
1
single crystals:
p-type
n
p
(6 3) cm2 V 1 s 1
(3.1 0.15) cm2 V 1 s
51015 cm 3
RT
RT
RT
surface-acoustic-wave technique
93T
See also Figs. 6.8.2 and 6.8.3.
Optical properties
refractive index
n
2.05...2.72
h = 0.5...0.9 eV
91C
(0)
( )
15.2
16.0
8.5
9.5
T = 300K, E `` c
E c
E `` c
E c
infrared
78R
infrared
78R
References to 6.8
75S
77B
77H
78N
78R
79I
85B
86N
87N
87T
90F
90Y
91C
92R
92T
93A
93F
93T
94N
97S
Haupt, H., Hess, K.: Inst. Phys. Conf. Ser.35 (1977) 5.
Neumann, H., Nguyen Van Nam, Hbler, H. J., Khn, G.: Solid State Commun. 25 (1978) 899.
Riede, V., Sobotta, H., Neumann, H., Hoang Xuan Nguyen: Solid State Commun. 28 (1978) 449.
Irie, T., Endo, S., Kimura, S.: Jpn. J. Appl. Phys. 18 (1979) 1303.
Bodnar, I. V., Orlova, N. S.: Inorg. Mater. 21 (1985) 967.
Neumann, H., Tomlinson, R. D.: Solid States Commun. 57 (1986) 591.
Nakanishi, H., Endo, S., Irie, T., Chang, B. H.: Ternary Multinary Compd., Mater. Res. Soc. (1987) 99.
Takarabe, K., Irie, T.: Jpn. J. Appl. Phys. 26 (1987) 1828.
Fernndez, B., Wasim, S. M.: Phys. Status Solidi A 122 (1990) 235.
Yamanaka, S., Tanda, M., Horino, K., Ito, K., Yamada, A., Konagai, M., Takahashi, K.: IEEE PVSC 1
(1990) 132.
Chichibu, S., Shishikura, M., Ino, J., Matsumoto, S.: J. Appl. Phys. 70 (1991) 1648.
Rincon, C., Fernandez, B.: Phys. Status Solidi B 170 (1992) 531.
Tanino, H., Maeda, T., Fujikake, H., Nakanishi, H., Endo, S., Irie, T.: Phys. Rev. B 45 (1992) 13323.
Arushanov, E., Essaleh, L., Galibert, J., Leotin, J., Askenazy, S.: Physica B 184 (1993) 229.
Fouret, R., Hennion, B., Gonzales, J., Wasim, S. M.: Phys. Rev. B (Condensed Matter) 47 (1993) 8269.
Tabib-Azar, M., Moller, H. J., Shoemaker, N.: IEEE Transaction on Ultrasonics, Ferroelectrics and
Frequency Control 40 (1993) 149.
Niki, S., Makita, Y., Yamada, A., Shibata, H., Fons, P. J., Obara, A.: 24th IEEE PVSC and First
WCPEC 1 (1994) 132.
Schoen, J. H., Alberts, V., Bucher, E.: J. Appl. Phys. 81 (1997) 2799.
Figures to 6.8
Fig. 6.0.1
Fig. 6.0.2
Fig. 6.0.8
Band structure of CuInSe2.
Fig. 6.8.1a
CuInSe2. Phonon dispersion curves of TA[100] and LA[100] modes [93F].
Fig. 6.8.1b
CuInSe2. Phonon dispersion curves of LA[001], TA[001] and TO[001] modes [93F].
Fig. 6.8.1c
CuInSe2. Phonon dispersion curves of TA1[110], TA2[110], LA[110] and TO2[110] modes [93F].
Fig. 6.8.2
CuInSe2. Resistivity and Hall coefficient vs. reciprocal temperature for four p-type samples [79I].
Fig. 6.8.3
CuInSe2. Electron mobility vs. temperature for four n-type samples [78N].
6.9 Copper indium telluride (CuInTe2)

Crystal structure
CuInTe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir
0.983 eV
T = 370 K
89M
T = 300 K
from intervalence-band absorption

Fe-doped
87N
RT
75S2
RT
77B
from sound velocities
90F
77B
spin orbit splitting energy (at

so
0.63 eV
Lattice properties
lattice parameters
a
c
c/a
6.17(1)
12.34(2)
2.00
density
6.10 g cm
Debye temperature
D
197.5 K
191.4 K
0K
melting temperature
Tm
1050 K
75S1
wavenumbers of infrared active phonons (data in cm 1, at RT)

172,157,126,50
170,101,46
E modes (E c)
B2 modes(E `` c)
infrared reflectivity
81H
p-type samples
p
3.69 1019 cm 3
1.87 1017 cm 3
1.35 10 3 cm
6.60 10 1 cm
125 cm2 V 1 s 1
50.6 cm2 V 1 s 1
T = 300 K
T = 300 K
T = 300 K
T = 300 K
T = 300 K
T = 300 K
single crystal, grown by PDF

single crystal, grown by Bridgman
87H
1.08 1017 cm 3
189.2 cm2 V 1s
T = 300 K
T = 300 K
single crystal
single crystal
88W
88W
n-type samples
n
n
The temperature dependence of resistivity, hole concentration, and Hall mobility is shown in Fig. 6.9.1 [87H].
Optical properties
refractive index
n
3.05
2.71(9)
T = 300 K
T = 300 K
h = 0.5 eV, polycrystalline film
78D
80H
(0)
( )
10.5(8)
12.9(8)
8.7(5)
11.0(5)
T = 300 K, E c
E `` c
T = 300 K, E c
E `` c
80R
80R
References to 6.9
75S1
75S2
77B
78D
80H
80R
81H
87H
87N
88W
89M
90F
1310.
Davis, J. G., Bridenbaugh, P. M., Wagner, S.: J. Electron. Mater. 7 (1978) 39.
Hrig, W., Neumann, H., Savalev, V., Lagzdonis, J.: Phys. Lett. 78A (1980) 189.
Riede, V., Neumann, H., Sobotta, H., Tomlinson, R. D., Elliott, F., Howarth, L.: Solid State Commun.
33 (1980) 557.
Holah, G. D., Schenk, A. A., Perkovitz, S.: Phys. Rev. B 23 (1981) 6288.
Haworth, L.I., Al-Saffar, I.S., Tomlinson, R.D.: Phys. Status Solidi A 99 (1987) 603.
Nakanishi, H., Endo, S., Irie, T., Chang, B. H.: Ternary Multinary Compd., Mater. Res. Soc. (1987) 99.
Wasim, S.M., Albornoz, J.G.: Phys. Status Solidi A 110 (1988) 575.
Mochizuki, K., Masumoto, K.: J. Cryst. Growth 98 (1989) 855.
Fernndez, B., Wasim, S. M.: Phys. Status Solidi A 122 (1990) 235.
Figures to 6.9
Fig. 6.0.1
Fig. 6.9.1
CuInTe2. Temperature dependence of (a) resistivity, (b) hole concentration, and (c) Hall mobility of various
samples [87H].
6.10 Silver gallium sulfide (AgGaS2)

Crystal structure
AgGaS2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir
dEg/dT
2.714 eV
1.0 10 4 eV K 1
2.2 10 4 eV K
T=5K
T <80 K
T >110 K
from reflectivity measurements

from reflectivity measurements
87A2
87A1
The temperature variation of the AgGaS2 energy gap between 5 and 295 K is shown in Fig. 6.10.1 [87A1].
Egx
2.700 eV
86A

Eb
0.0292 eV
from two-photon spectroscopy
95R

cf
0.28 eV
T = 77 K
so
T = 77K
75S1
Lattice properties
lattice parameters
a
c
c/a
5.75(1)
10.29(2)
1.790(1)
RT
75S2
RT
72A
density
d
4.70 g cm
Debye temperature
255 K
D
0K
75A
melting temperature
Tm
12643 K
1220...1320 K
at pS2 = 4.1 105 Pa
89M
75S1

The temperature dependence of the thermal expansion coefficients between 0 and 800 K is given in Fig. 6.10.2.
phonon dispersion : The calculated phonon spectrum and the density of states of AgGaS 2 are shown in Fig.
6.10.3 [92T].

(wavenumbers in cm 1, T = 300 K)
Symmetry
I 4 2d
(F 4 3m)
LO/
TO
392/368
393/367
340/321
334
224
295
240/213
215/213
230/223
190.5
160
161/157
95/95
65/65
54
36/36
5
4
5
3
1
4
5
3
5
5
4
3
5
( 15)
( 15)
(W4)
(W2)
4, 5 are IR
active, all
are Raman
active
(W1)
(W2)
(W4)
(X3)
(W3)
(W4)
(W2)
(W2)
(X5)
77L, 74H, 75L, 80C

74H, 75L,80C
74H, 75L, 77L
75L, 75K
74H
74H, 75L, 80C
74H, 75L
80C
74H,75L
75L
74H
77L, 74H, 75L, 80C
74H, 75L, 80C
77L, 75L, 80C

c11
c33
c44
c66
c12
c13
8.5 1011 dyn/cm2

5.4 1011 dyn/cm2
3.6 1011 dyn/cm2
3.5 1011 dyn/cm2
4.3 1011 dyn/cm2
3.9 1011 dyn/cm2
calculated
92T2
resistivity
1.0 106 cm
1 cm
3.0 1010 cm
1.0 1011 cm
5.0 1013 cm
1.0 108 cm
yellow amorphous film

84V
black amorphous film
polycrystalline film, as grown
polycrystalline, annealed (500C), vacuum
polycrystalline, annealed (500C), S-vapor
single crystal
The temperature dependence of electrical conductivity for as-grown AgGaS 2 crystals with or without
illumination is shown in Fig. 6.10.4.
activation energies
EA
0.11 eV
0.03 eV
shallow traps
shallow traps
93M
|| optical axis
optical axis
94B
94B
p
s
0.014 W cm
0.015 W cm
1K 1
1K 1
Optical properties
refractive index
coefficients in the formula n2 = A + B/(1 C/ 2) +D/(1 E/ 2).
no
A
B
C
D
E
ne
3.6280
4.0172
2.1686
1.5274
0.100310 12 m2
0.131010 12 m2
2.1753
2.1699
95010 12 m2
95010 12 m2
valid for = (0.49...12.0) m
76B
dielectric constants (at T = 300 K)

(0)
( )
8.21
8.51
5.50
5.90
E `` c
E c
E `` c
E c
75S1
References to 6.10
72A
74H
75A
75K
75L
75S1
75S2
76B
77L
80C
84V
85B
86A
87A1
87A2
89M
92T
93M
94B
95R
Adams, R., Russo, P., Arnofi, R., Wold, A.: Mater. Res. Bull. 7 (1972) 93.
Holah, G. D., Webb, J. S., Montgomery, H.: J. Phys. C: Solid State Phys. 7 (1974) 3875.
Abrahams, S. C., Hsu, F. S. L.: J. Chem. Phys. 63 (1975) 1162.
Lockwood, D.J., Montgomery, H.: J. Phys. C.: solid State Phys. 8 (1975) 3241.
1310.
Bhar, G. C.: Appl. Opt. 15 (1976) 305.
Lockwood, D. J.: Inst. Phys. Conf. Ser. 35 (1977) 97.
Carlone, C., Olego, D., Jayaraman, A., Cardona, M.: Phys. Rev. B 22 (1980) 3877.
Von Campe, H.: Thin Solid Films 111 (1984) 17.
Bodnar, I.V., Orlova, N.S.: Phys. Status Solidi A 91 (1985) 503.
Aicardi, J.P., Aguero, G.: Phys. Status Solidi A 95 (1986) 679.
Artus, L., Bertrand, Y.: Solid State Commun. 61 (1987) 733.
Artus, L., Bertrand, Y.: J. Phys. C 20 (1987) 1365.
Tyuterev, V.G., Skachkov, S.I.: Nuovo Cimento D 14 (1992) 1091.
Moon-Seog Jin, Suk-Ki Min, Han-Jo Lim, Hong-Lee Park, Wha-Tek Kim: Jpn. J. Appl. Phys.,
Supplement 32 (1993) 593.
Beasley, J.D.: Appl. Opt. 33 (1994) 1000.
Reimann, K., Rbenacke, S., Steube, M.: Solid State Commun. 96 (1995) 279.
Figures to 6.10
Fig. 6.0.1
Fig. 6.10.1
AgGaS2. Temperature variation of the energy gap between 5 and 295 K [87A].
Fig. 6.10.2
AgGaS2. Temperature dependence of the coefficients of thermal expansion , ||, BC, K = || - , AC, and
x [85B]. AC: expansion coefficient along A C bonds, BC: expansion coefficient along B C bonds x: x =
location of C atom relative to A and B atom.
Fig. 6.10.3
AgGaS2. The calculated phonon spectrum and the density of states.
wavevector and tetragonal axis [92T].
is the angle between the phonon
Fig. 6.10.4
AgGaS2. The temperature dependence of electrical conductivity for as-grown crystals with or without
illumination by high pressure Hg lamp. Open circles and triangles show the conductivity of the samples grown
from the charges with stoichiometric and with Ga2S3 excess compositions, respectively [93M].
6.11 Silver gallium selenide (AgGaSe2)

Crystal structure
AgGaSe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
1.814 eV
1.8 10 4 eV K 1
3.2 10 4 eV K
Eg,dir
dEg/dT
RT
T = 10 60 K
T = 95 300 K
from photoluminescence
pure single crystal
pure single crystal
96P
91S
91S
The temperature dependence of the band gap in AgGaSe 2 is shown in Fig. 6.11.1 [86A].
0.25 eV
0.30 eV
cf
so
T = 303 K
T = 303 K
from photoconductivity
from photoconductivity
91M
91M
RT
75S2
RT
72A
Lattice properties
lattice parameters
5.98(1)
10.88(1)
1.820(3)
a
c
c/a
density
5.70 g cm

6.4 10 6 K 1
16.0 10 6 K

.4 10
18.0 10

K
6K
T = 298...423 K
T = 423...873 K
91E
T = 298...423 K
T = 423...873 K
melting temperature
1130 K
Tm
75S
Calculated phonon dispersion curves for AgGaSe2 are shown in Fig. 6.11.2 [90A].
wavenumbers of infrared and Raman active phonons (wavenumbers in cmn1, RT values)
Symmetry
I 4 2d
(F 4 3m)
LO/
TO
274/248
162/158
80/76
( 15)
(X5)
5
5
5
4,
5:
IR active, all Raman active
77K
77K
77K

c11
c33
c44
c66
c12
c13
89.8 GPa
58.0 GPa
21.7 GPa
13.3 GPa
65.7 GPa
45.1 GPa
91E
resistivity, electrical conductivity, Seebeck coefficient
105 cm
8.8 1 cm
710 2 V K
1
1
T = 300 K
T = 300 K
T = 300 K
different samples
75S1
single crystals, as-grown

single crystals, annealed (700C)
single crystals, annealed in Se-vapor
96N
96N
96N
<10 8
2 10 1
6 10 6
cm 1
cm 1
1 cm 1
1
Temperature dependence of electrical conductivity: Fig. 6.11.3, variation of the electrical conductivity with
inverse temperature for AgGaSe 2 thin films of different thicknesses: Fig. 6.11.4 [89M2].
activation energies
EA
0.12 eV
0.86 eV
T = 303...450 K
T = 500...573 K

89M1
Optical properties
refractive index
coefficients in the formula: n2 = A + B/(1 C/ 2) + D/(1 E/ 2)
A
B
C
D
E
no
ne
4.6453
2.2057
0.137910 12 m2
1.8377
1.60010 12 m2
5.2912
1.3970
0.284510 12 m2
1.9282
1.60010 12 m2
valid for 0.725 m <
76B
< 13.5 m
(0)
( )
7.76
8.94
6.11
6.18
T = 300 K, E `` c
E c
T = 300 K, E `` c
E c
infrared
76M
infrared
76M
References to 6.11
72A
75S1
75S2
76B
76M
77K
86A
89M1
89M2
90A
91E
91M
91S
96N
96P
1310.
Bhar, G. C.: Appl. Opt. 15 (1976) 305.
Miller, A., Holah, G. D., Dunnett, W. D., Iseler, G. W.: Phys. Status Solidi (b) 78 (1976) 569.
Kanellis, G., Kampas, K.: J. Phys. (Paris) 38 (1977) 833.
Artus, L., Bertrand, Y., Ance, C., Lopez-Soler, A.: Phys. Status Solidi B 138 (1986) 633.
Mal sagov, A.U.: Izv. Akad. Nauk SSSR, Neorg. Mater. 25 (1989) 25; Inorg. Mater. (Engl.Transl.) 25
(1989) 17.
Artus, L., Pujol, J., Pascual, J., Camassel, J.: Phys. Rev. B 41 (1990) 5727.
Eimerl, D., Marion, J., Graham, E.K., McKinstry, H.A., Hausshl, S.: IEEE J. Quantum Electron. 27
(1991) 142.
Murty, Y.S., Uthanna, S., Naidu, B.S., Reddy, P.J.: Solid State Commun. 79 (1991) 277.
Shukla, R., Khurana, P., Srivastava, K.K.: Philos. Mag. B 64 (1991) 389.
Nigge, K.-M., Baumgartner, F.P., Bucher, E.: Solar Energy Mater. Solar Cells 43 (1996) 335.
Petcu, M.C., Giles, N.C., Schunemann, P.G., Pollak, T.M.: Phys. Status Solidi B 198 (1996) 881.
Figures to 6.11
Fig. 6.0.1
Fig. 6.11.1
AgGaSe2. Temperature dependence of the band gap [86A]. AgInSe 2 for comparison.
Fig. 6.11.2
AgGaSe2 (a). Calculated phonon dispersion curves [90A]. Zn 0.5Cd0.5Se (b) and ZnCdSe (c) for comparison.
Fig. 6.11.3
AgGaSe2. Electrical conductivity vs. reciprocal temperature for n-type sample [75S1].
Fig. 6.11.4
AgGaSe2. Variation of the electrical conductivity with inverse temperature for AgGaSe 2 thin films of different
thicknesses [89M1]. Activation energies are indicated.
6.12 Silver gallium telluride (AgGaTe2)

Crystal structure
AgGaTe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir
dEg/dT
1.32 eV
3.6 10 4 eV K
T = 300 K
T = 80 350 K
from optical transmission
89K
RT
75S2
RT
72A2
Lattice properties
lattice parameters
a
c
c/a
6.29(1)
11.95(1)
1.90
density
6.08 g cm
Debye temperature
D
182.4 K
0K
77B2
melting temperature
Tm
950 K
76K1

Raman
IR
43 cm
62 cm
64 cm 1
93 cm 1
106 cm 1
129 cm
142 cm
152 cm
201 cm
220 cm
RT
96J
1
1
115 cm
132 cm
201 cm
205 cm
1
1

carrier concentration, resistivity, mobility (p-type samples)
1g5 1013 cm
20g200
p
T = 300 K
cm
5g8 cm2 V 1 s
T = 300 K
single crystal
89K
thin films
89P
single crystal
89K
(0)
( )
14.5
15.0
11.0
11.86
E `` c, T = 300 K
E c
E `` c, T = 300 K
E c
77K
References to 6.12
72A2
75S2
76K1
77B2
77K
89K
89P
96J
1310.
Kanellis, G., Kambas, C., Spyridelis, J.: Mater. Res. Bull. 11 (1976) 429.
von Bardeleben, H. J., Goltzen, A., Schwab, C.: Inst. Phys. Conf. Ser. 35 (1977) 43.
Kanellis, G., Kampas, K.: J. Phys. (Paris) 38 (1977) 833.
Kobayashi, S., Ohno, T., Kaneko, F., Maruyama, T., Tsuboi, N.: Jpn. J. Appl. Phys., Part 1, 28 (1989)
189.
Patel, S.M., Patil, M.C.: Mater. Lett. 7 (1989) 338.
Julien, C., Balkanski, M.: Mater. Sci. Eng. B38 (1996) 1.
Figures to 6.12
Fig. 6.0.1
6.13 Silver indium sulfide (AgInS2)

Crystal structure
AgInS2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir (A)
(B, C)
1.87 eV
2.02 eV
T = 300 K
74S
T = 77 K
74S

Egx (A)
(B)
1.880 eV
2.045 eV
splitting energy (at

0.165 eV
cf
T = 77 K
electroreflectance
74S
RT
75S2
RT
53H
Lattice properties
lattice parameters
a
c
c/a
5.82(1)
11.17(2)
1.92
density
4.97 g cm
melting temperature
Tm
1150(10) K
74S

||
8.33 10n6 Kn1

6.90 10n6 Kn1
c-axis
|| c-axis
87O
The temperature dependence of the coefficients of thermal expansion in AgInS 2 is shown in Fig. 6.13.1 [87O].
References to 6.13
53H
74S
75S
87O
Shay, J. L., Tell, B., Shiavone, L. M., Kasper, H. M., Thiel, F.: Phys. Rev. B 9 (1974) 1719.
1310.
Figures to 6.13
Fig. 6.0.1
Fig. 6.13.1
AgInS2. Temperature dependence of the coefficients of thermal expansion
|| to c-axis; m = ( ||+ 2 )/3; ! 2 n c/a, tetragonal distortion; c/a = || n
||;
m;
c/a; d
d [87O].
,||: ,
6.14 Silver indium selenide (AgInSe2)

Crystal structure
AgInSe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir (A)
(B)
(C)
1.24 eV
1.33 eV
1.60 eV
T = 300 K
electroreflectance
75S1
T=2K
absorption, reflectivity,
photoluminescence
75S1

Egx (A)
1.245 eV
splitting energies
0.12 eV
0.30 eV
cf
so
T = 300 K
75S1
Lattice properties
lattice parameters
6.095(15)
11.69(3)
1.92(1)
a
c
c/a
RT
75S2
RT
72A2
density
5.82 g cm
melting temperature
1055 K
Tm
74S

8.48 10n6 Kn1
4.16 10n6 Kn1
||
c-axis
|| c-axis
The temperature dependence of the coefficients of thermal expansion in AgInSe 2 is shown in Fig. 6.14.1 [87O].
wavenumbers of IR active phonons
Symmetry
LO/
TO
235/217 cmn1
164/155 cmn1
161/148 cmn1
62/66 cmn1
43/43 cmn1
5
4
4
5
4
RT, infrared reflectivity
75K

carrier concentration, resistivity, mobility, Seebeck coefficient
n-type samples
n
n
8 1015 cm 3
50 150 cm
25 cm2 V 1s 1
106 cm2 V 1s 1
460 cm2 V 1s 1
RT
RT
thin films
thin films
thin film
thin films
single crystal
96R
96R
96R
87I
87I
in the solid state

in the liquid state
95A
activation energies for electrical conductivity

EA
0.06 eV
0.37 eV

refractive indices
no
ne
2.8265
2.6761
2.6542
2.6463
2.6416
2.6381
2.6352
2.6318
2.6286
2.6251
2.6210
2.6167
2.6838
2.6592
2.6504
2.6451
2.6414
2.6379
2.6343
2.6310
2.6274
2.6229
2.6183
[m]
1.05
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
75S1
dielectric constant
(0)
( )
10.73
11.94
7.16
7.20
T = 300 K, E `` c
E c
T = 300 K, E `` c
E c
78K
References to 6.14
72A
74S
75K
75S1
75S2
87I
87O
95A
96I
96R
Shay, J. L., Tell, B., Shiavone, L. M., Kasper, H. M., Thiel, F.: Phys. Rev. B 9 (1974) 1719.
Kaufmann, U., Ruber, A., Schneider, J.: J. Phys. C: Solid State Phys. 8 (1975) L381.
1310.
Isomura, S., Tomioka, S., Hayashi, H.: Ternary Multinary Compd., Mater. Res. Soc.(1987) 201.
Abdelghany, A.: Appl. Phys. A 60 (1995) 77.
In-Hwan Choi, Yu, P.J.: J. Phys. Chem. Solids 57 (1996) 1695.
Figures to 6.14
Fig. 6.0.1
Fig. 6.14.1
AgInSe2. Temperature dependence of the coefficients of thermal expansion ;
n c/a, tetragonal distortion, : to c-axis, ||: || to c-axis, c/a = || n , m = (
||;
m;
|| + 2
c/a; d /dT [87O].

)/3.
=2
Fig. 6.14.2
AgInSe2. Temperature dependence of the electrical properties of an n-type vacuum evaporated film [87I].
Fig. 6.14.3
AgInSe2. Temperature dependence of the Hall mobility for a thin film deposited at 300 K [96I].
6.15 Silver indium telluride (AgInTe2)

Crystal structure
AgInTe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
energy gap
Eg,dir
0.964 eV
T = 300 K
optical absorption, polycrystalline bulk
90Q
The variation of energy gap with temperature for AgInTe2 is given in Fig. 6.15.1 [90Q].
Lattice properties
lattice parameters
6.43(3)
12.59(4)
1.96
a
c
c/a
RT
75S
RT
77B
density
3
6.05 g cm

9.08 10n6 Kn1
2.00 10n6 Kn1
||
T = 300 K
c-axis
|| c-axis
The temperature dependence of the coefficients of thermal expansion in AgInTe 2 is shown in Fig. 6.15.2 [87O].
Debye temperature
155.9 K
0K
77B
melting temperature
960(10) K
Tm
76K
wavenumbers of IR active phonons

LO/
TO
Symmetry
E [111 ]
E `` [111 ]
E [ 111 ]
E [ 111 ]
E `` [ 111 ]
E `` [ 111 ]
E [ 111 ]
/173 cm 1
181/168 cm 1
181/166 cm 1
138/136 cm 1
136/131 cm 1
44/44 cm 1
43/42 cm 1
infrared reflectivity at 300 K,

unconventional polarization
78K

10 4
10
T = 290 331 K
5
cm
91S
The temperature dependence of dc conductivity in bulk AgInTe 2 is shown in Fig. 6.15.3 [93S].
activation energy
EA
0.327 eV
93S
(0)
( )
7.68
8.10
6.38
6.48
T = 300 K, E `` [ 111 ]
E [ 111 ]
T = 300 K, E `` [ 111 ]
E [ 111 ]
78K
References to 6.15
75S
76K
77B
78K
87O
90Q
91S
93S
1310.
Kanellis, G., Kambas, C., Spyridelis, J.: Mater. Res. Bull. 11 (1976) 429.
Kanellis, G., Kampas, K.: Mater. Res. Bull. 13 (1978) 9.
Quintero, M., Tovar, R., Bellabarba, C., Woolley, J.C.: Phys. Status Solidi B 162 (1990) 517.
Sato, K., Kudo, Y., Kijima, S., Samanta, L.K.: J. Cryst. Growth 115 (1991) 740.
Shukla, R.: Indian J. Pure Appl. Phys. 31 (1993) 894.
Figures to 6.15
Fig. 6.0.1
Fig. 6.15.1
AgInTe2. Variation of energy gap with temperature. Circles: experimental data; continuous curve: fitted to the
Manoogian-Leclerc equation [90Q].
Fig. 6.15.2
AgInTe2. Temperature dependence of the coefficients of thermal expansion ; ||; m;
, || to the c-axis; m = ( || n 2 )/3; c/a = || n ; = 2 n c/a, tetragonal distortion.
c/a;
d /dT [87O].
,||:
Fig. 6.15.3
AgInTe2. Temperature dependence of dc conductivity in bulk AgInTe 2 [93S].
=1
n1cmn1.
6.16 Copper thallium sulfide (CuTlS2)

CuTlS2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
lattice parameters
a
c
c/a
5.58
11.16
2.00
RT
75S
density
d
6.13 g cm
RT
79G
The energy gap is estimated to be Eg = 1.39 eV [83D].
References to 6.16
75S
79G
1310.
Gardes, B., Brun, G., Raymond, A., Tedenac, J. C.: Mater. Res. Bull. 14 (1979) 943.
Figures to 6.16
Fig. 6.0.1
6.17 Copper thallium selenide (CuTlSe2)

crystal structure
CuTlSe2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 6.0.1).
lattice parameters
a
c
c/a
5.83
11.60
1.99
RT
75S2
RT
53H
density
d
7.08 g cm
melting temperature
Tm
680 K
electrical conductivity, Seebeck coefficient

S
6103 1 cm
10 2 V K 1
T = 300 K
T = 300 K
no anisotropy
75S1
References to 6.17
53H
75S1
75S2
1310.
Figures to 6.17
Fig. 6.0.1
6.18 Copper thallium telluride (CuTlTe2)

electrical conductivity, Seebeck coefficient, melting temperature
S
Tm
2.8103 1 cm
810 2 V K 1
650 K
T = 300 K
T = 300 K
no anisotropy
75S
References to 6.18
75S
6.19 Silver thallium selenide (AgTlSe2)

S
Tm
10 5 1 cm
0.8 V K 1
600 K
T = 300 K
300 K
no anisotropy
75S
References to 6.19
75S1
6.20 Silver thallium telluride (AgTlTe2)

S
4.1102 1 cm
610 2 V K 1
T = 300 K
T = 300 K
no anisotropy
75S
For transport properties of AgTlSe2, see also [82A].

Tm
560 K
References to 6.20
75S
6.21 Copper iron sulfide, chalcopyrite (CuFeS2)

Electronic structure
energy gap
0.6 eV
Eg
absorption edge
72A
Lattice properties
lattice parameters
5.292
10.407
a
c
72A
density
4.19 g cm
74P
melting temperature
1120 K or 1150 K
Tm
contradictory reports
75S
wavenumbers of IR and Raman active phonons

Symmetry
I 4 2d
(F 4 3m)
LO/
TO
385/360 cmn1
371/357 cmn1
330/322 cmn1
296 cmn1
272/262 cmn1
267/263 cmn1
/179 cmn1
/105 cmn1
/90 cmn1
/72 cmn1
T = 300 K
T = 300 K
T = 300 K
T = 4.5 K
T = 300 K
T = 300 K
T = 4.5 K
T = 4.5 K
T = 4.5 K
T = 4.5 K
4
5
5
1
4
5
5
5
4
5
( 15)
( 15)
(W4)
(W1)
(W2)
(X5)
(W3)
(W4)
(W2)
(X5)
all modes IR and

Raman active,
except 1
75K
Hall mobility
H
7 cm2 V
1s 1
74P
carrier concentration, mobility, electrical conductivity

n-type samples
n
n
1016 1017 cm
1021 cm 3
~1 cm2 V 1s 1
35
T = 1.5 K
T = 20-300 K
cm2 V 1s 1
from Hall measurements

single crystal
from Hall measurements
single crystal
93K
87K
93K
87K
(no anisotropy)
75S
p-type sample
100 1 cm 1
30 cm2 V 1 s 1
T = 300 K
T = 300 K
References to 6.21
72A
74P
75K
75S
78K
93K
Adams, R., Beaulieu, R., Vassiliadis, M., Wold, A.: Mater. Res. Bull. 7 (1972) 87.
Pitt, G. D., Vyas, M. K. R.: Solid State Commun. 15 (1974) 899.
Kaufmann, U., Ruber, A., Schneider, J.: J. Phys. C: Solid State Phys. 8 (1975) L381.
Kanellis, G., Kampas, K.: Mater. Res. Bull. 13 (1978) 9.
Koscielniak-Mucha, B., Opanowicz, A.: Phys. Status Solidi A 139 (1993) K73.
Figures to 6.21
Fig. 6.0.2
Fig. 6.0.9
Band structure of CuFeS2.
6.22 Copper iron selenide (CuFeSe2)

electrical conductivity, mobility, melting temperature
p
Tm
700 1 cm 1
20 cm2 V 1 s 1
850 K
T = 300 K
T = 300 K
p-type
(no anisotropy)
75S
References to 6.22
75S
6.23 Copper iron telluride (CuFeTe2)

p
Tm
400 1 cm 1
50 cm2 V 1 s 1
1015 K
T = 300 K
T = 300 K
p-type
(no anisotropy)
75S
References to 6.23
75S
6.24 Silver iron selenide (AgFeSe2)

n
Tm
1500 1 cm 1
250 cm2 V 1 s 1
1009 K
T = 300 K
T = 300 K
n-type
(no anisotropy)
75S
References to 6.24
75S
6.25 Silver iron telluride (AgFeTe2)

n
Tm
700 1 cm
2000 cm2 V
953 K
1
1s 1
T = 300 K
T = 300 K
n-type
(no anisotropy)
75S
References to 6.25
75S
7 II-IV-V2 compounds
7.0 Crystal structures and electronic structure
7.0.1 Crystal structure
Almost all semiconducting II-IV-V2 compounds crystallize in the chalcopyrite lattice (Fig. 7.0.1).
7.0.2. Electronic structure

Fig. 7.0.2 shows the Brillouin zone of fcc (zincblende) and two Brillouin zones of chalcopyrite. Each point in the
chalcopyrite Brillouin zone maps on to 4 different points of the zincblende zone. Thus the point corresponds to
, X and two W points.
A useful starting point for a description of the electronic properties of compounds with chalcopyrite structure is
the band structure of the zincblende parent compound represented in the smaller Brillouin zone of the ternary
(see Fig. 7.0.2). These "folded back" curves can be labelled with the irreducible representations to which they
correspond in both the chalcopyrite etc. or zincblende space groups.
The tetragonal symmetry of the chalcopyrite lattice leads to a change in the band structure even at the center of
the Brillouin zone .
Non-degenerate band-edges at ( 1... 4) are shaped according to E(k) = E( ) + ( 2/2)(kz2/m`` + (kx2+ky 2)/m )
with the z-axis parallel to the c-axis. Electrons are thus characterized by two effective masses: m`` and m . From
these two other effective masses are often defined: a density of states effective mass mds3 = m 2m`` and a
conductivity effective mass (1/mc) = (1/3)(1/m`` + 2/m ).
The
5-band
is split at k
0 into two bands:
E(k) = E( ) +
2k 2/2m(
z
) + ( 2/2m)(a (b2 + c2cos(4 ))1/2)(kx2 + ky2)
where is the angle between k and kx in the kxky plane, with k the direction of k perpendicular to the z-axis.
Finally the 6- and 7-bands contain terms linear in k.
This simple picture is somewhat complicated by the effects of spin-orbit coupling which splits the 5 state. This
splitting is given by the formula: E1,2 = 1/2( so + cf) 1/2[( so + cf)2 8/3 so cf]1/2, where so is the spinorbit splitting in a cubic crystal field and cf is the crystal field splitting of the valence bands in the absence of
spin-orbit coupling. The two solutions E1 and E2 give the separation of the two 7 states from the 6. In
chalcopyrite it is found that the crystal field splitting is negative, that is 4 lies above 5 and that this splitting is
due almost entirely to the tetragonal compression. It compares very well with that expected from the
corresponding zincblende compound under uniaxial pressure.
Fig. 7.0.3 ... 7.0.12 show the band structures of the most important semiconductors dealt with in this chapter.
Figures to 7.0
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.3
Band structure of MgSiP2.
Fig. 7.0.4
Band structure of ZnSiP2.
Fig. 7.0.5
Band structure of ZnSiAs2.
Fig. 7.0.6
Band structure of ZnGeP2.
Fig. 7.0.7
Band structure of ZnSnSb2.
Fig. 7.0.8
Band structure of CdSiP2.
Fig. 7.0.9
Band structure of CdSiAs2.
Fig. 7.0.10
Band structure of CdGeAs2.
Fig. 7.0.11
Band structure of CdSnP2.
Fig. 7.0.12
Band structure of CdSnAs2.
7.1 Magnesium silicon phosphide (MgSiP2)

Crystal structure
MgSiP2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
The band structure of MgSiP2 was calculated by the use of the ab initio density-functional method [85M].
energy gaps
Eg,pseu
Eg,ind
Eg,dir
dEg/dT
2.03 eV
2.26 eV
2.64 eV
2.82 eV
2.88 eV
4.510
eV K
E c, RT
E c
E c
E ``( ) c
E c
T = 77...300 K
photoconductivity
maybe pseudodirect
78A
maybe pseudodirect
main feature of spectrum
splitting energies
0.08 eV
0.16 eV
cf
so
T = 300 K
T = 300 K
experiment
78A
Lattice and transport properties

lattice parameters
a
c
c/a
5.72(2)
10.12(25)
1.766(3)
RT
75S
electrical resistivity
103...104
10...102
cm
cm
T = 300 K
T = 300 K
n-type sample
(no anisotropy reported)
In doped sample
75T,
78A
78A
References to 7.1
75S
75T
78A
85M
Shay, T. L., Wernick, T. H.: "Ternary Chalcopyrite Semiconductors" Growth, Electronics, Properties
and Applications. Pergamon, 1975.
Trykozko, R. T.: Mater. Res. Bull. 10 (1975) 489.
Averkieva, G. K., Mamedov, A., Prochukhan, V. D., Rud', Yu. V.: Fiz. Tekh. Poluprovodn. 12 (1987)
1732; Sov. Phys. Semicond. (English Transl.) 12 (1978) 1025.
Martins, J.L., Zunger, A.: Phys. Rev. B 32 (1985) 2689.
Figures to 7.1
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.3
Band structure of MgSiP2.
7.2 Zinc silicon phosphide (ZnSiP2)

Crystal structure
ZnSiP2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 5.0.1).
The energy band structure of ZnSiP2 calculated by the pseudopotential method [85Z].
energy gap
Eg,ind
2.00 eV
RT
87H
Eg,dir
3.03 eV
T = 80 K;
4v( 15v)
1c( 1c)
T = 80 K;
5v( 15v)
1c( 1c)
T = 300 K;
4v( 15v)
1c( 1c)
T = 300 K;
5v( 15v)
1c( 1c)
thermoreflection
75R
electroreflectance
75S
absorption
75H,
75S
T = 4.2 K
T = 4.2 K
86M
0.022 eV
T = 124 K
absorption (E
75H
0.4(1) m0
0.11(2) m0
T = 300 K
Hall effect
3.16 eV
2.96 eV
3.06 eV
dEg/dT
2.8(1)10
4 eV K 1
T = 80...300 K

cf
so
n 0.12 eV
0.05 eV

Eb
c)
effective masses
mp
mn
76P
Lattice properties
lattice parameters
a
c
c/a
5.400(1)
10.438(3)
1.933(1)
RT
75S
3.35 g cmn3
RT
69B
a axis
c axis
volume
79K,
75M
density
d
coefficients of thermal expansion

7.810 6 K 1
3.510 6 K 1
19.210 6 K 1
T = 300...1400 K
T = 300...1400 K
Debye temperature
445.2(23) K
0K
from heat capacity
81B
melting temperature
1520...1640 K
Tm
75S
wavenumbers of Raman and infrared active phonons

Symmetry
I 4 2d
(F 4 3m)
LO/
TO
518/494 cm
518/494 cm
466 cm 1
464/461 cm
359/343 cm
337 cm 1
335 cm 1
327/321 cm
264/246 cm
187/185 cm
145/145 cm
102/102 cm
5
3
4
1
3
( 15)
( 15)
(W2)
(W4)
(W2)
(W1)
(X3)
(X5)
(W3)
(W4)
(W2)
(X5)
RT, Raman and infrared spectra;

4, 5 IR-active,
all Raman active
77H,
79G,
75P
carrier concentration, electron mobility, activation energy, electrical resistivity
n-type samples
n
n
imp
EA
1017 cm 3
70...100 cm2 V 1 s
0.02...0.35 cm2 V
0.015...0.024 eV
2.7 105
1.8 106
T = 300 K
T = 300 K
s 1 T = 300 K
T = 77...1000 K
RT
conductivity
Halleffect; see also Figs. 7.2.1, 7.2.2
for temperature dependence
of , n, RH
in impurity band
activation energy of hopping
75S,
65G,
76G
single crystal
87H
76S
cm
p-type samples
p
p
61013...31017 cm
4...11 cm 2 V 1 s 1
T = 300 K
T = 300 K
78G
activation energies
EA
0.62 eV
0.26...0.33 eV
T < 773 K

single crystal
92E
87H
11.7(6)
11.15(10)
9.26
9.68
T = 300 K; E c
E `` c
T = 300 K; E c
E `` c
75P
3.31
T = 300 K;
= 600 nm
= 900 nm
(0)
( )
refractive index
n
3.06
75B
References to 7.2
65G
69B
75B
75H
75M
75P
75R
75S
76G
761
77H
78G
78Z
79G
79K
81B
85Z
86M
87H
92E
Goryunova, N. A., Kesamanly, F. P., Nasledov, D. N., Negreskul, V. V., Rud'Yu, V., Slobodchikov, S.
V.: Fiz. Tverd. Tela 7 (1965) 1312; Sov. Phys. Solid State (English Transl.) 7 (1965) 1060.
Berger, L. T., Prochokhan, V. D.: "Ternary Diamond Like Semiconductors", New York, London:
Consultants Bureau, 1969.
Bondriot, H., Foeller, B., Schneider, H. A.: Phys. Status Solidi (a) 30 (1975) K121.
Humphreys, R. G., Pamplin, B. R.: J. Phys. (Paris) 36 (1975) C3155.
Miller, A., Humphreys, R. G., Chapman, B.: J. Phys. (Paris) 36 (1975) C331.
Poplavnoi, A. S., Tyuterev, V. G.: Fiz. Tverd. Tela 17 (1975) 1055; Sov. Phys. Solid State (English
Transl.) 17 (1975) 672.
Raudonis, A. V., Shileika, A. Yu.: Fiz. Tekh. Poluprovodn. 9 (1975) 1539; Sov. Phys. Semicond.
(English Transl.) 9 (1975) 1014.
Grishchenko, G. A., Ljubchenko, A. V., Tychina, I. I., Ukr. Fiz. Zh. 21 (1976) 303.
Pasemann, L., Cordts, W., Heinrich, A., Monecke, J.: Phys. Status Solidi (b) 77 (1976) 527.
Humphreys, R. G.: Inst. Phys. Conf. Ser. 35 (1977) 105.
Grishchenko, G. A., Ljubchenko, A. V., Tychina, I. I.: Ukr. Fiz. Zh. 23 (1978) 958.
Ziegler, F., Siegel, W., Khnel, G.: Phys. Status Solidi (a) 49 (1978) K205.
Gorban, I. S., Gorynya, V. A., Lugovoi, V. I., Krasnolob, N. P., Salivon, G. I., Tychina, I. I.: Phys.
Status Solidi (b) 93 (1979) 531.
Kozkina, I. I.: Vestn. Leningr. Univ. Fiz. Khim. 13 (1979) 83.
Bohmhammel, K., Deus, P., Schneider, H. A.: Phys. Status Solidi (a) 65 (1981) 563.
Zakharov, N.A., Chaldyshev, V.A.: Fiz. Tekh. Poluprovodn. 19 (1985) 842; Sov. Phys. Semicond.
(Engl. Transl.) 19 (1985) 518.
Madelon, R., Hurel, J., Paumier, E.: Phys. Status Solidi B 136 (1986) 679.
He-Sheng Shen, Guang-Qing Yao, Kershaw, R., Dwight, K., Wold, A.: J. Solid State Chem. 71 (1987)
176.
Endo, T., Sato, Y., Takizawa, H., Shimada, M.: J. Mater. Sci. Lett. 11 (1992) 567.
Figures to 7.2
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.4
Band structure of ZnSiP2.
Fig. 7.2.1
ZnSiP2. Conductivity and Hall coefficient of an n-type sample vs. (reciprocal) temperature [75S].
Fig. 7.2.2
ZnSiP2. Electron mobility vs. temperature for an undoped and three Ga doped samples (n-type) [78Z].
7.3 Zinc silicon arsenide(ZnSiAs2)

Crystal structure
ZnSiAs2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
energy gap
thin film data
Eg(0)
dEg/dT
1.93 eV
5.5 10

85N
85N
Eg,pseu
1.74 eV
1.84 eV
1.93 eV
2.03 eV
2.09 eV
E c, T = 300 K
E (``) c
E ``( ) c
E c
E c
photoconductivity
76R
T = 300 K
electroreflectance
71S,
75T
from band gap calculations
84Z
5.606(5)
10.886(5)
1.940(3)
RT
75S
4.69 g cmn3
RT
69B
a axis
c axis
88D
eV K
T = 223 323 K
splitting energies
0.13 eV
0.286(6) eV
cf
so
effective masses
mn||(
mn (
mp||(
mp (
)
)
)
)
0.92 m0
0.28 m0
0.13 m0
0.54 m0
Lattice properties
lattice parameters
a
c
c/a
density
d

a
c
7.6(3) 10
3.3(2) 10
6
6
K
K
1
1
T = 300 K
T = 300 K
The temperature dependence of the principal linear thermal expansion coefficients is given in Fig. 7.3.1 [88D].
Debye temperature
D
346.6(12) K
0K
from heat capacity
81B
melting temperature
Tm
1370 K
75S
wavenumbers of Raman active phonons

Symmetry
I 4 2d
LO/
TO
417/405 cm
401/388 cm
269/ cm 1
262 cm 1
236/ cm 1
210/ cm 1
203 cm 1
162 cm 1
133/ cm 1
108 cm 1
77/ cm 1
75M
4
4
3
5
5
1
1
5
3
5
carrier concentration, electrical resistivitiy, hole mobility
p-type samples
p
1.11 1014
5.26 1016 cm
RT
87C
RT
epitaxial layers by MOVPE

91A1
p: drift mobility; single crystals, as grown 87C
0.02 800 cm
1827 cm2 V 1 s 1
see also Fig. 7.3.2

n-type(non-stoichiometric) sample (RT values)
n
n
109 cm 3
40 cm2 V
76R
1s 1
0.14 W cm
1K 1
T = 300 K
75S
Optical properties
energy dependence of reflection coefficient R, the dielectric constant
2,
and Im
1: Fig. 7.3.3.
refractive index
Coefficients in the formula: n2 = A +B/(1 C/ 2)+ D/(1 E/ 2) (T = 300 K) [76B1]:
A
B
C
D
E
no
ne
4.6066
5.6912
0.143710 12 m2
1.316
7.10 10 m2
4.9091
5.5565
0.157810 12 m2
1.287
710 10 m2
References to 7.3
69B
71S
75M
75S
75T
76B
76R
81B
84Z
85N
87B
87C
88D
91A
Shay, T. L., Buehler, F., Wernick, T. H.: Phys. Rev. B3 (1971) 2004.
Markov, Yu. F., Gromova, T. M., Rud', Yu. B., Tashtanova, M.: Fiz. Tverd. Tela 17 (1975) 1226; Sov.
Phys. Solid State (English Transl.) 17 (1975) 796.
Bhar, G. C.: Appl. Opt. 15 (1976) 305.
Rud', Yu. V., Ovezov, K.: Fiz. Tekh. Poluprovodn. 10 (1976) 951; Sov. Phys. Semicond. (English
Transl.) 10 (1976) 561.
Zakharov, N.A., Chaldyshev, V.A.: Fiz. Tekh. Poluprovodn. 18 (1984) 217; Sov. Phys. Semicond.
(Engl. Transl.) 18 (1984) 135.
Naseem, H.A., Burton, L.C., Andrews, J.E.: Thin Solid Films 129 (1985) 49.
Boudriot, H., Deus, K., Grundler, R., Schneider, H.A., Stockert, T.: Phys. Status Solidi B 143 (1987)
K125.
Chippaux, D., Mercey, B., Deschanvres, A.: J. Phys. Chem. Solids 48 (1987) 447.
Deus, P., Voland, U., Neumann, H.: Phys. Status Solidi A 108 (1988) 225.
Achargui, N., Benachenhou, A., Foucaran, A., Bougnot, G., Coulon, P., Laurenti, J.P., Camassel, J.: J.
Cryst. Growth 107 (1991) 410.
Figures to 7.3
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.5
Band structure of ZnSiAs2.
Fig. 7.3.1
ZnSiAs2. Temperature dependence of the principal linear thermal expansion coefficients
and
[88D].
Fig. 7.3.2
ZnSiAs2. Resistivity, Hall coefficient and hole mobility vs. (reciprocal) temperature for a p-type sample [75S].
Fig. 7.3.3
ZnSiAs2. The energy dependence of reflection coefficient R, the dielectric constant
transmission electron energy loss measurements [87B].
2,
and Im
1 from
7.4 Zinc germanium nitride (ZnGeN2)

Crystal structure
ZnGeN2 has a wurtzite-like monoclinic structure [70M]
energy gap
Eg
2.67 eV
T = 300 K
absorption (unpolarized)
74L
RT
70M

lattice parameters
a=c
b
3.167
5.194
118o53'
carrier concentration, electrical resistivity, electron mobility

n
n
1018...1019 cm 3
0.3...0.4 cm
0.5...5 cm2 V 1 s
T = 300 K
T = 300 K
T = 100...300 K
n-type sample
References to 7.4
70M
74L
Maunaye, M., Lang, T.: Mater. Res. Bull. 5 (1970) 793.

Larson, W. L., Maruska, H. P., Stevenson, D. A.: J. Electrochem. Soc. 121 (1974) 1674.
74L
7.5 Zinc germanium phosphide (ZnGeP2)

Crystal structure
ZnGeP2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
band structure: Fig. 7.0.6, Brillouin zone: Fig. 7.0.2.
energy gaps and other band-band transitions
reflectivity (T = 5 K)
Eg,pseu
Eg,dir
Eg,ind
74V
2.14 eV
2.51 eV
2.63 eV
2.67 eV
1.80 eV
( 15v X1c)
4v 1c ( 15v 1c)
5v 1c ( 15v 1c)
5v 1c ( 15v 1c)
87H
electroreflectance
75S
theory
75S
5v
3c
splitting energies
0.08 eV
0.09 eV
cf
so
T = 300 K
effective masses
mn,
mn,``
mn,ds
mn,c
mp1,
mp1,``
mp1,ds
0.108 m0
0.105 m0
0.11 m0
0.11 m0
( 1.8) m0
0.15 m0
0.79 m0
(mds: density of states mass,

mc: conductivity mass)
Lattice properties
lattice parameters
a
c
c/a
5.463(3)
10.74(3)
1.965(5)
RT
75S
4.04 g cmn3
RT
58P
a axis
c axis
volume
75M
density
d

1.810 6 K
5.010 6 K
2010 6 K 1
T = 300...1300 K
T = 300...1300 K
Debye temperature
D
428 K
0K
75A
melting temperature
Tm
1300(3) K
75S

Symmetry
I 4 2d (F 4 3m)
LO/
TO
408/399 cmn1
404/387 cmn1
389 cmn1
376/369 cmn1
364 cmn1
359/344 cmn1
331/329 cmn1
328 cmn1
247 cmn1
204/202 cmn1
142 cmn1
120 cmn1
96 cmn1
4
5
3
5
2
4
5
1
3
5
5
3
5
( 15)
( 15)
(W2)
(W4)
(X1)
(W2)
(X5)
(W1)
(X3)
(W3)
(W4)
(W2)
(X5)
T = 78 K, 4, 5 IR active,
all Raman active
75B,
75G2,
74B,
75G1
calculated [75B1]
elastic moduli
c11
c33
c44
c66
c12
c13
8.32 1011 dyn cm

8.43 1011 dyn cm
3.50 1011 dyn cm
3.23 1011 dyn cm
4.47 1011 dyn cm
4.91 1011 dyn cm
calculated
96Z
single crystal, after electron irradiation

single crystals
single crystal, from LEC
84B
84B
93H
single crystal, from high

pressure vapor transport
90X
87H
2
2
2
2
2
For temperature dependence of , RH, , see also Fig. 7.5.1.
carrier concentration, electrical resistivity, hole mobility
p-type samples
1018 cm 3
2 5 106 cm
20 cm2 V 1 s 1
p
p
T = 300 K
T = 300 K
n-type samples
106
cm
activation energies
EA
0.11 eV
0.58 eV
T <220 K
T >220 K
||c
c
0.36 W cm
0.35 W cm
1K 1
1K 1
RT
RT
94B
Optical properties
refractive indices
coefficients in the formula n2 = A + B/(1 C/ 2) + D/(1 E/ 2)
no
ne
no
ne
no
ne
no
ne
no
ne
no
ne
no
ne
12 m2 ]
C [10
4.6171
4.6791
4.5654
4.6732
4.5209
4.6559
4.4492
4.5717
4.4733
4.6332
4.3761
4.5801
4.2889
4.5285
5.4709
5.6826
5.3382
5.4842
5.2917
5.4001
5.3338
5.4513
5.2658
5.3422
5.2540
5.2747
5.2688
5.2463
0.1495
0.1567
0.1419
0.1499
0.1376
0.1460
0.1353
0.1435
0.1338
0.1426
0.1275
0.1368
0.1228
0.1326
12 m2]
E [10
1.4912
1.4577
1.4913
1.4581
1.4911
1.4580
1.4736
1.4262
1.4909
1.4580
1.4903
1.4576
1.4898
1.4572
662.55
662.55
662.55
662.55
662.55
662.55
662.55
662.55
662.55
662.55
662.55
662.55
662.55
662.55
T [K]
670
80B
470
370
320
79B
270
170
80B
90
References to 7.5
58P
74B
74V
75A
75B
75G1
75G2
75M
75S
79B
80B
84B
87B
87H
90X
93H
94B
96Z
Pfister, H.: Acta Cryst. 11 (1958) 221.

Bettini, M., Miller, A.: Phys. Status Solidi (b) 66 (1974) 579.
Varea de Alvarez, C., Cohen, M. L., Kohn, S. F., Petroff, Y., Shen, YR.: Phys. Rev. B10 (1974) 5175.
Averkieva, G. K., Prochukhan, V. D., Rud', Yu. V., Tashtanova, M.: Izv. Akad. Nauk SSSR, Neorg.
Mater. 11 (1975) 607.
Bettini, M.: Phys. Status Solidi (b) 69 (1975) 201.
Gorban', I. S., Gorynya, V. A., Lugovoi, V. I., Tychina, I. I.: Fiz. Tverd. Tela 17 (1975) 2631; Sov.
Phys. Solid State (English Transl.) 17 (1976) 1749.
Grigor'eva, V. S., Markov, Yu. F., Rybakova, T. V.: Fiz. Tverd. Tela 17 (1975) 1993.
Bhar, G. C., Ghosh, G. C.: J. Opt. Soc. Am. 69 (1979) 730.
Bhar, G. C., Ghosh, G. C.: IEEE J. Quant Elec. 16 (1980) 838.
Boudriot, H., Grundler, R., Deus, K., Stockert, T., Schneider, H.A.: Phys. Status Solidi B 126 (1984)
K149.
Boudriot, H., Deus, K., Grundler, R., Schneider, H.A., Stockert, T.: Phys. Status Solidi B 143 (1987)
K125.
He-Sheng Shen, Guang-Qing Yao, Kershaw, R., Dwight, K., Wold, A.: J. Solid State Chem. 71 (1987)
176.
Xing, G.C., Bachmann, K.J., Posthill, J.B.: Appl. Phys. Lett. 56 (1990) 271.
Hobgood, H.M., Henningsen, T., Thomas, R.N., Hopkins, R.H., Ohmer, M.C., Mitchel, W.C., Fischer,
D.W., Hegde, S.M., Hopkins, F.K.: J. Appl. Phys. 73 (1993) 4030.
Beasley, J.D.: Appl. Opt. 33 (1994) 1000.
Zapol, P., Pandey, R., Ohmer, M., Gale, J.: J. Appl. Phys. 79 (1996) 671.
Figures to 7.5
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.6
Band structure of ZnGeP2.
Fig. 7.5.1
ZnGeP2. Conductivity, Hall coefficient and hole mobility vs. (reciprocal) temperature for a p-type sample with p
1013 cm 3 [75S].
7.6 Zinc germanium arsenide (ZnGeAs2)

Crystal structure
ZnGeAs2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
energy gaps
thin film data
Eg,dir
1.15 eV
Eg,dir (A)
(B)
(C)
Eg,th
1.15 eV
1.19 eV
1.48 eV
1.16 eV
epilayer, optical transmission
89S
T = 300 K
electroreflectance
75S
T=0K
conductivity
75A
splitting energies
0.06 eV
0.31 eV
cf
so
T = 300 K
75S
effective masses
mn,
mn,``
mn,ds
mn,c
mp1,
mp1,``
mp1,ds
0.060 m0
0.058 m0
0.059 m0
0.059 m0
0.82 m0
0.084 m0
0.38 m0
theoretical
75S
(mds: density of states mass;

mc: conductivity mass)
Lattice properties
lattice parameters
a
c
c/a
5.671(1)
11.153
1.966(1)
RT
75S
5.26 g cmn3
RT
58P
density
d
melting temperature
Tm
1120...1145 K
75S
References to 7.6
58P
75A
75S
89S
Pfister, H.: Acta Cryst. 11 (1958) 221.

Mater. 11 (1975) 607.
Sharma, S., Hong, K.S., Speyer, R.F.: J. Mater. Sci. Lett.8 (1989) 950.
Figures to 7.6
Fig. 7.0.1
7.7 Zinc tin phosphide (ZnSnP2)

Crystal structure
ZnSnP2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
energy gap
Eg,dir (A,B)
(C)
1.66 eV
1.75 eV
T = 300 K
electroreflectance
75S
T = 300 K
(c/a = 2)
75S
RT
75S
peritectic
75S
disordered structure
75S,
75B
75S
ZnSnP2, epilayer
89S
splitting energies
cf
so
0
0.09 eV
Lattice properties
lattice parameters
a
c
c/a
5.652(1)
11.305(3)
2.000
melting temperature
Tperit
1200 K
wavenumbers of infrared active phonons

LO
327...330 cm
368 cm 1
322 cm 1
Symmetry
T = 300 K
4
T = 300 K
5
T = 300 K
p-type samples
p
35g47 cm2 V 1 s
1016g1018 cm 3
5 cm
T = 300 K
The temperature dependence of resistivity, mobility, Hall coefficient, and carrier concentration of ZnSnP 2 are
given in Figs. 7.7.1 and 7.7.2 [89S].
activation energies
EA
0.046 eV
0.03 0.07 eV
0.11 eV
ZnSnP2, thin film

ZnSnP2, single crystals
89S
85A
75S
T = 300 K
chalcopyrite
75S
T = 300 K
disordered zincblende
Optical properties
(0)
( )
(0)
( )
10.0
8.08
10.8
8.3
References to 7.7
75B
75S
89S
Bettini, M.: Phys. Status Solidi (b) 69 (1975) 201.

Sharma, S., Hong, K.S., Speyer, R.F.: J. Mater. Sci. Lett.8 (1989) 950.
Figures to 7.7
Fig. 7.0.1
Fig. 7.7.1
ZnSnP2. Resistivity and mobility as a function of temperature above room temperature [89S].
Fig. 7.7.2
ZnSnP2. Hall coefficient and carrier concentration as a function of temperature above room temperature [89S].
7.8 Zinc tin arsenide (ZnSnAs2)

Crystal structure
ZnSnAs2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
energy gap
Eg,dir (A,B)
(C)
dEg/dT
0.745 eV
1.185 eV
0.63 eV
2.710 4 eV K
T = 300 K
electroreflectance
T = 300 K
epitaxial layers; absorption
T = 300 K
(c/a = 2)
75S
mc: free charge carrier

effective mass
90B
transport
80D
5.8515(5)
11.703(1)
2.000
RT
75S
5.53 g cmn3
RT
69B
71K,
75S
78B
71S
splitting energies
cf
so
0 eV
0.34 eV
effective masses
mc
mp(V1)
mp(V2)
mp(V3)
0.048 m0
0.65 m0
0.065 m0
0.16 m0
mp
0.35 m0
T = 5...200 K
Lattice properties
lattice parameters
a
c
c/a
density
d
Debye temperature
D
271.1(27) K
0K
65A
melting temperature
Tm
1048(3) K
75B

p-type samples
p
p
6.85 1018 cm 3
7.05 10 3 cm
129 cm2 V 1 s 1
RT
ZnSnAs2, single crystal
95M
dielectric constant
(0)
15.6
T = 300 K
80D
References to 7.8
65A
69B
71K
71S
75B
75S
78B
80D
90B
95M
Leroux-Hugon, P., Veyssie, J. J.: Phys. Status Solidi 8 (1965) 561.

Kriviate, G. Z., Korneev, E. F., Shileika, A. Yu.: Fiz. Tekh. Poluprovodn. 13 (1971) 2242; Sov. Phys.
Semicond. (English Transl.) 5 (1~72) 1961.
Shay, T. L., Buehler, F., Wernick, T. H.: Phys. Rev. B3 (1971) 2004.
Borshchevskii, A. S., Kotsyuruba, E. S.: Fiz. Tekh. Poluprovodn. 9 (1975) 2346; Sov. Phys. Semicond.
Bedair, S. M., Littlejohn, M. A.: J. Electrochem. Soc. 125 (1978) 952.
Duncan, W. M., Schreiner, A. F., Bedair, S. M., Littlejohn, M. A.: J. Lumin. 21 (1980) 137.
Brudnyi, V.N., Borisenko, S.I., Potapov, A.I.: Phys. Status Solidi A 118 (1990) 505.
Manimaran, M., Kalkura, S.N., Ramasamy, P.: J. Mater. Sci. Lett. 14 (1995) 1366.
Figures to 7.8
Fig. 7.0.1
7.9 Zinc tin antimonide (ZnSnSb2)

Crystal structure
ZnSnSb2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
The energy band structure of ZnSnSb2 was calculated by the pseudopotential method [89P].
energy gap
0.4 eV
0.7 eV
Eg
T = 77 K
T = 300 K
absorption
(unpolarized light)
73B
calculated
89P
splitting energies
0.03 eV
0.87 eV
cf
so
effective masses
0.025 m0
0.031 m0
0.25 m0
mn
mp2
mp3
T = 77 K, 300 K
73B

lattice parameters
a
6.273
c
12.546
c/a
2.000
RT
75S
hole concentration, hole mobility, Seebeck coefficient (at 300 K)

p-type sample
p
p
1020 cm 3
70 cm2 V 1 s
36 V K 1 ?
75S
1
References to 7.9
73B
75S
89P
Berger, L. I., Kradinova, L. V., Petrov, V. M., Prochukhan, V. D.: Izv. Akad. Nauk SSSR, Neorg.
Mater. 9 (1973) 1258; Inorg. Mater. (USSR) (English Transl.) 9 (1973) 1118.
Polygalov, Y.I., Basalaev, Y.M., Zolotarev, M.L., Poplavnoi, A.S.: Fiz. Tekh. Poluprovodn. 23 (1989)
279; Sov. Phys. Semicond. (Engl. Transl.) 23 (1989) 173.
Figures to 7.9
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.7
Band structure of ZnSnSb2.
7.10 Cadmium silicon phosphide (CdSiP2)

Crystal structure
CdSiP2 crystallizes in the chalcopyrite lattice (space group D 2d12 I 4 2d, Fig. 7.0.1).
CdSiP2 is the only chalcopyrite material with a positive crystal field splitting(i.e. E( 5) > E(
to the large anionic displacement. The energy gap is generally said to be pseudodirect.
4)).
This is related

energy gaps
Eg,pseu
2.2 eV
T = 300 K
absorption
Eg,dir (B)
(C)
(A)
dEg,dir/dT
2.71 eV
2.75 eV
2.945 eV
3.510 4 eV K
T = 90 K
thermoreflectance;
5v ( 15v)
1c (
4v
70G,
79C
77A
1c)
1c
refractive index
78A
n = 1;
T = 80 K
absorption
80G
T = 90 K
thermoabsorption
77A

Egx
2.085 eV
splitting energies
cf
so
0.20 eV
0.07 eV
effective masses
mn``
mn
1.068 m0
0.124 m0
70G
Lattice properties
lattice parameters
a
c
c/a
5.679(1)
10.431
1.836(1)
RT
75S
3.97 g cmn3
RT
69B
density
d
melting temperature
Tm
1390 K
75S

Symmetry
Wavenumber
E
B1
B2
E
E
E
B1
A1
E
B2(TO)-E(TO)
B2(LO)-E(LO)
66 cm 1
87 cm 1
109 cm 1
158 cm 1
263 cm 1
286 cm 1
314 cm 1
323 cm 1
453 cm 1
485 cm 1
508 cm 1
RT
88S

carrier concentration, electrical resistivity, electron mobilities
p-type samples
p
n
n
3 1012 cm 3
T=6K
T = 300 K
5 1014 cm 3
80g100 cm2 V 1s 1 T = 300 K
single crystals, Cu-doped

single crystals
single crystal
89G
89M
89M
75S
n-type samples (at 300 K)

n
n
1014...1015 cm 3
80...150 cm2V 1s
106 cm
refractive indices
no
ne
3.414
3.379
= 0.6328 m, T = 300 K
= 0.6328 m, T = 300 K
78I
References to 7.10
69B
70G
75S
77A
78A
78I
79C
80G
88S
89G
89M
Goryunova, N. A., Poplavnoi, A. S., Polygalov, Yu. I., Chaldyshev, V. A.: Phys. Status Solidi 39 (1970)
9.
Ambrazevicius, G. A., Babonas, G. A., Shileika, A. Yu.: Phys. Status Solidi (b) 82 (1977) K45.
Ambrazevicius, G. A., Babonas, G.: Litov. Fiz. Sb. 18 (1978) 765.
Iseler, G. W., Kildal, H., Menyuk, N.: J. Electron. Mater. 7 (1978) 737.
Cordts, W., Heinrich, A., Monecke, J.: Phys. Status Solidi (b) 96 (1979) 201.
Gorban, I. S., Krys'kov, Ts. A., Tennakun, M., Tychina, I. I., Chukichev, M. V.: Fiz. Tekh.
Poluprovodn. 14 (1980) 975; Sov. Phys. Semicond. (English Transl.) 14 (1980) 577.
Shirakata, S.: Jpn. J. Appl. Phys., Part 1, 27 (1988) 2113.
Gorban, I.S., Korets, N.S.,Kryskov, T.A., Chukichev, M.V.: Phys. Status Solidi A 115 (1989) 555.
Medvedkin, G.A., Rud, Y.V., Tairov, M.A.: Fiz. Tekh. Poluprovodn. 23 (1989) 1002; Sov. Phys.
Semicond. (Engl. Transl.) 23 (1989) 625.
Figures to 7.10
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.8
Band structure of CdSiP2.
7.11 Cadmium silicon arsenide (CdSiAs2)

Crystal structure
CdSiAs2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
The energy band structure of CdSiAs2 was calculated by the pseudopotential method including spin-orbit
interaction [90B].
energy gap
Eg,dir (A)
(B)
(C)
1.55 eV
1.74 eV
1.99 eV
1.635 eV
dEg/dT
2.310
eV K
T = 300 K
electroreflectance
75S,
75T
T = 1.7 K
photoluminescence
photoconductivity
75S,
76M
76L

89M
89M
calculated
(mds: density of states mass)
75S
RT
75S

cf
so
0.22 eV
0.32 eV
T = 300 K
T = 300 K
effective masses
mn,
mn,``
mn,ds
mp1,
mp1,``
mp1,ds
0.084 m0
0.074 m0
0.080 m0
(n3.6 m0)
0.090 m0
1.07 m0
Lattice properties
lattice parameters
a
c
c/a
5.885(1)
10.881(1)
1.849
melting temperature
Tm
> 1120 K
75S
carrier concentrations, electrical resistivity, hoel mobilitiy
p-type samples
1016 cm
p
p
10 100 cm
250 cm2 V 1 s 1
T = 300 K
single crystals
86R
RT
T = 300 K
single crystals
single crystals
89C
86R
epilayer
89R
n-type samples
n
1017 cm
The temperature dependence of resistance, free hole concentration, and Hall mobility is shown in Figs. 7.11.1,
7.11.2 [84A].
References to 7.11
75S
75T
76L
76M
84A
86R
89C
89M
90B
Lebedov, A. A., Ovezov, K., Prochukhan, V. D., Rud', Yu. V., Serginov, M.: Pis'ma Zh. Eksp. Teor.
Fiz. 2 (1976) 385.
Mal'tseva, I. A., Prochukhan, V. D., Rud', Yu. V., Serginov, M.: Fiz. Tekh. Poluprovodn. 10 (1976)
1222; Sov. Phys. Semicond. (English Transl.) 10 (1976) 727.
Avirovic, M., Lux-Steiner, M., Elrod, U., Honigschmid, J., Bucher, E.: J. Cryst. Growth 67 (1984) 185.
Rud, Y.V., Serginov, M.: Izv. Akad. Nauk SSSR, Neorg. Mater. 22 (1986) 1208; Inorg. Mater.
(Engl.Transl.) 22 (1986) 1056.
Cotting, T., von Knel, H., Leicht, G., Levy, F.: J. Electrochem. Soc. 136 (1989) 382.
Medvedkin, G.A., Rud, Y.V., Tairov, M.A.: Solid State Commun. 71 (1989) 307.
Basalaev, Y.M., Zolotarev, M.L., Polygalov, Y.I., Poplavnoi, A.S.: Fiz. Tekh. Poluprovodn. 24 (1990)
916; Sov. Phys. Semicond. (Engl. Transl.) 24 (1990) 574.
Figures to 7.11
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.9
Band structure of CdSiAs2.
Fig. 7.11.1
CdSiAs2. Temperature dependence of the resistance of crystals grown by CVT [84A].
Fig. 7.11.2
CdSiAs2. Temperature dependence of the Hall mobility of crystals grown by CVT [84A].
7.12 Cadmium germanium phosphide (CdGeP2)

Crystal structure
CdGeP2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
energy gap
Eg
dEg/dT
1.73 eV
3.8 10
eV K
T = 300 K
T = 80...300 K
90M
90M
T = 300 K, E `` c
E c
photoconductivity
75B
T = 300 K
electroreflectance
75S
calculated
(mds: density of states mass)
75S
RT
75S
a axis
c axis
volume
75M

Egx
1.686 eV
1.712 eV
splitting energies
0.2 eV
0.11 eV
cf
so
effective masses
mn,
mn,``
mn,ds
mp1,
mp1,``
mp1,ds
0.088 m0
0.088 m0
0.085 m0
( 1.3 m0)
0.099 m0
0.56 m0
Lattice properties
lattice parameters
a
c
c/a
5.740(1)
10.776(1)
1.878(1)

8.910 6 K 1
0.3710 6 K 1
1.810 6 K 1
T = 300...1030 K
T = 300...1030 K
Debye temperature
D
340 K
0K
75A
melting temperature
Tm
1073 K
75B

(in cm 1), between parantheses the LO frequencies are noted
4
5
3
5
Experiment
IR (20 K)
Raman (77 K)
399 (409.5)
380.5 (400.5)
377
356 (369)
398 (407)
387 (400)
353
358 (368)
1
4
5
299.5 (317)
289 (297.5)
3
5
5
4
181 (187)
118.5 (123)
91 (91)
3
5
63 (63)
322
295 (314)
295 (296)
228
184 (186)
123 (123)
91 (91)
88
64 (64)
91A
Theory
3 parameters
399
394
353
356
341
306
307
300
278
188
184
107
95
90
83
4 parameters
402
393
355
352
306
309
304
268
177
183
114
98
98
64

carrier concentrations, carrier mobilities, electrical resistivitiy
p-type samples
p
p
(1 4) 1012 cm
103 cm
5 cm2 V 1 s 1
T = 300 K
T = 300 K
T = 300 K

single crystal, Ga-doped
88L1
88L1
88L2
1013 cm 3
(1 3) 103 cm
800 cm2 V 1s 1
T = 300 K
T = 300 K
T = 300 K
single crystal
single crystals, In-doped
single crystal
86L
88L1
90M
n-type samples
n
n
0.11 W cm
1K 1
T = 300 K
75S
refractive indices
coefficients in the formula n2 = A + B/(1 C/ 2) + D/(1
A
B
C [10 12 m2]
no
5.9677
4.2286
0.2021
ne
6.1573
4.0970
0.2330
no
6.3737
3.9281
0.2069
ne
6.9280
3.4442
0.2803
E/ 2)
D
1.6351
1.4925
1.6686
1.5515
E [10 12 m2]
671.33
671.33
671.33
617.33
T [K]
293
293
391
391
79B
References to 7.12
75A
75B
75M
79B
86L
88L1
88L2
90M
91A
Mater. 11 (1975) 607.
Bhar, G. C., Ghosh, G. C.: J. Opt. Soc. Am. 69 (1979) 730.
Lunev, A.V., Rud, Y.V., Tairov, M.A., Undalov, Y.K., Filippova, A.V.: Zh. Prikl. Spektrosk. 44 (1986)
247; J. Appl. Spectrosc. (Engl. Transl.) 44 (1986) 167.
Lunev, A.V., Rud, Y.V., Tairov, M.A., Undalov, Y.K.: Zh. Tekh. Fiz. 58 (1988) 1415; Sov. Phys.Techn. Phys. (Engl. Transl.) 33 (1988) 843.
Lunev, A.V., Rud, Y.V., Tairov, M.A., Undalov, Y.K.: Fiz. Tekh. Poluprovodn. 22 (1988) 1115; Sov.
Phys. Semicond. (Engl. Transl.) 22 (1988) 703.
Medvedkin, G.A., Rud, Y.V., Tairov, M.A.: Fiz. Tekh. Poluprovodn. 24 (1990) 1306; Sov. Phys.
Semicond. (Engl. Transl.) 24 (1990) 821.
Artus, L., Pascual, J., Pujol, J., Camassel, J., Feigelson, R.S.: Phys. Rev. B 43 (1991) 2088.
Figures to 7.12
Fig. 7.0.1
7.13 Cadmium germanium arsenide (CdGeAs2)

Crystal structure
CdGeAs2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
The electronic energy band structure of CdGeAs 2 calculated by the empirical pseudopotential method is given in
Fig. 7.18 [91M].
energy gaps
Eg,dir (A)
(B)
(C)
Eg,th
dEg,th/dT
0.57 eV
0.73 eV
1.02 eV
0.673 eV
3.510 4 eV K
T = 300 K
electroreflectance
75S
T=0K
T = 0...300 K
Hall effect
78I
T = 300 K
electroreflectance
75S
splitting energies
0.21 eV
0.33 eV
cf
so
effective masses
A calculation of the dependence of the effective masses of the electrons of the first-three magnetic sub-bands in
CdGeAs2 on electron concentration in the presence of crossed electric and magnetic fields is given in Fig. 7.13.1
[88G].
mn
mp
0.26 m0
0.035 m0
Hall effect
78I
5.943(1)
11.220(3)
1.888(1)
RT
75S
5.6 g cmn3 (crystalline)

5.35 g cmn3 (amorphous)
RT
69B
T = 370...570 K
c axis
a axis
(large anisotropy)
78I
T 0K
T = 4.2 K
from heat capacity

from elastic moduli
81B
82H
Lattice properties
lattice parameters
a
c
c/a
density
d

110 6 K 1
8...910 6 K
Debye temperature
D
240.9(14) K
257(2) K
melting temperature
Tm
943 K
phonon dispersion : Fig. 7.13.2.
77S,
75B

Symmetry
I 4 2d
LO/
TO
280/272 cmn1
278/270 cmn1
258/255 cmn1
210/203 cmn1
206/200 cmn1
101/159 cmn1
98/95 cmn1
(F 4 3m)
( 15)
( 15)
(W4)
(W2)
(X3)
(W3)
(W4)
5
5
5
5
5
5
5
RT
77H

Symmetry
282 cmn1
280 cmn1
257 cmn1
254 cmn1
201 cmn1
205 cmn1
211 cmn1
182 cmn1
155 cmn1
162 cmn1
169 cmn1
80 cmn1
76 cmn1
75 cmn1
65 cmn1
calculated
4
5
5
3
2
5
4
1
5
3
2
5
4
3
5
88A
elastic moduli
calculated
c11
c33
c44
c66
c12
c13
92A
6.8
5.4
1.3
1.1
5.2
4.7
1011
1011
1011
1011
1011
1011
dyn cm
dyn cm
dyn cm
dyn cm
dyn cm
dyn cm
experimental
2
2
2
2
2
2
9.45 1011 dyn cm

8.34 1011 dyn cm
4.21 1011 dyn cm
4.08 1011 dyn cm
5.96 1011 dyn cm
5.97 1011 dyn cm
2
2
2
2
2
2

carrier concentrations and mobilities
p-type samples
p
p
(0.7...2)1016 cm 3 T = 300 K
140...400 cm2 V 1 s 1 T = 300 K
78I,
76B2
n-type samples (by vacuum anneal, or In, Al, Te doping) [76B2]

n
n
41016...1018 cm 3 T = 100...500 K
1000...
T = 100...500 K
4000 cm2 V 1 s 1
78I
0.42 W cm
1K 1
T = 300 K
75S
refractive indices
coefficients in the formula n2 = A + B/(1 C/ 2) + D/(1 E/ 2)
no
ne
12
C [10
10.1064
11.8018
2.2988
1.2152
1.0872
1.6971
m2] D
1.6247
1.6922
E [10
1370
1370
12
m2] T [K]
300
300
76B1
(0)
( )
18.40.5
14.00.3
RT
RT
crystalline
crystalline
90K
90K
References to 7.13
69B
75B
75S
76B1
76B2
77H
77S
78B
78I
81B
82H
88A
88G
90B
90K
91M
92A
Bhar, G. C.: Appl. Opt. 15 (1976) 305.
Borshchevskii, A. S., Dagina, N. E., Lebedov, A. A., Ovezov, K., Polushina, I. K., Rud', Yu. V.: Fiz.
Tekh. Poluprovodn. 10 (1976) 1571; Sov. Phys. Semicond. (English Transl.) 10 (1976) 934.
Holah, G. D., Miller, A., Dunnett, W. D., Iseler, G. W.: Solid State Commun. 23 (1977) 75.
Satow, T. Uemura, O., Watanabe, S.: Phys. Status Solidi (a) 44 (1977) 731.
Brudnyi, V. N., Krivov, M. A., Potapov, A. I., Polushina, I. K., Prochukhan, V. D., Rud', Yu. V.: Phys.
Status Solidi (a) 49 (1978) 761.
Iseler, G. W., Kildal, H., Menyuk, N.: J. Electron. Mater. 7 (1978) 737.
Hailing, T., Saunders, G. A., Lambson, W. A., Feigelson, R. S.: J. Phys. C15 (1982) 1399.
Antropova, E.V., Kopytov, A.V., Poplavnoi, A.S.: Opt. Spektrosk. 64 (1988) 1285; Opt. Spectrosc.
(Engl. Transl.) 64 (1988) 766.
Ghatak, K.P., Mondal, M.: Zeitschrift fr Physik B 69 (1988) 471.
Baumgartner, F.P., Lux-Steiner, M., Bucher, E.: J. Electron. Mater. 19 (1990) 777.
Kug Sun Hong, Speyer, R.F., Condrate, R.A.: J. Phys. Chem. Solids 51 (1990) 969.
Madelon, R., Paumier, E., Hairie, A.: Phys. Status Solidi B 165 (1991) 435.
Artus, L., Pascual, J.: J. Phys.: Condensed Matter 4 (1992) 5835.
Figures to 7.13
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.10
Fig. 7.13.1
CdGeAs2. Calculation of the dependence of the effective masses mz*(EF) of the electrons of the first-three
magnetic sub-bands in CdGeAs2 on electron concentration in the presence of crossed electric and magnetic
fields. The dashed curve shows the same dependence when spin orbit splitting parameter = 0.3 eV and crystal
field splitting parameter = 0 [88G].
Fig. 7.13.2
CdGeAs2. Calculated phonon spectrum and one-phonon frequency distribution function [88A].
Fig. 7.13.3
CdGeAs2. Conductivity (circles) and Hall coefficient (triangles) vs. irradiation with 2 MeV electrons at T =
300 K [78B]. (full symbols) initially n-type sample, (open symbols) initially p-type sample. Note the change of
type at =31017 electrons cm 2 (p n).
Fig. 7.13.4
CdGeAs2. (a) Variation of Hall mobility with T for as grown n-type sample (A) and (B), as grown p-type
sample (C) , and the vacuum heat treated samples (D) (500C for 45 min) and (E) (500C for 3 h). (b) Variation of
resistivity with temperature for the samples of (a). Arrows indicate the temperatures at RH = 0 [90B].
7.14 Cadmium tin phosphide (CdSnP 2)

Crystal structure
CdSnP2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
energy gap
Eg,dir (A)
(B)
(C)
dEg/dT
1.17 eV
1.25 eV
1.33 eV
2.810
T = 300 K
eV K
electroreflectance
70S
80Z,
78M

Egx (A)
(B)
(C)
1.2343 eV
1.2353 eV
1.2360 eV
T = 1.7 K
photoluminescence
75S
calculated
calculated
calculated
calculated
75S
75S
75S
75S
RT
75S
effective masses
0.060 m0
0.056 m0
( 6.6 m0)
0.69 m0
mn
mn``
mp1
mp1``
Lattice properties
lattice parameters
a
5.901(1)
c
11.514(4)
c/a
1.951(1)
melting temperature
840 K
Tm
75S
wavenumbers of Raman active phonons (in cm 1, at RT)

Symmetry
I 4 2d
LO/
TO
364/353
340/348
314/328
301
306/288
280/283
265
146/147
113
93/94
73/73
54/54
4
5
5
1
4
5
3
5
3
5
4
5
85I

Symmetry
I 4 2d
LO/
TO
353/ cmn1
/389 cmn1
327/318 cmn1
/295 cmn1
285/279 cmn1
(F 4 3m)
( 15)
( 15)
(W4)
(W2)
(X5)
4
5
5
4
5
RT
78B

carrier concentrations, electron mobilities
p-type samples
1015 cm
T = 300 K
single crystal
89M
RT
single crystal
85F
RT
single crystal
85F
76M
n-type samples
8 1017 cm
n
n
1100 cm2 V 1s
see also Fig. 7.14.1

absorption coefficient
5.6 104 cm
= 1050 nm
single crystal
85F
infrared, unpolarized
75S
(0)
( )
11.8
10.0
The dielectric constants 1(E) and

shown in Fig. 7.14.2 [84B].
T = 300 K
2(E)
of CdSnP2 derived from transmission electron energy loss spectra are
References to 7.14
70S
75S
76M
76P
78B
78M
80Z
84B
85F
85I
89M
Shay, T. L., Buehler, E., Wernick, T. H.: Phys. Rev. B2 (1970) 4104.
Medvedkin, G. A., Ovezov, K., Rud', Yu. V., Sokolova, V. I.: Fiz. Tekh. Poluprovodn. 10 (1976) 2081;
Sov. Phys. Semicond. (English Transl.) 10 (1976) 1239.
Podol'skii, W. V., Karpovich, I. A., Zvonkov, B. N.: Fiz. Tekh. Poluprovodn. 10 (1976) 1004; Sov.
Phys. Semicond. (English Transl.) 10 (1976) 594.
Brudnyi, V. N. Krivov, M. A., Potapov, A. I., Prochukhan, V. D., Rud', Yu. V.: Fiz. Tekh. Poluprovodn.
12 (1978) 1109; Sov. Phys. Semicond. (English Transl.) 12 (1978) 659.
Medvedkin. G. A. Rud', Yu. V., Valov, Yu. A., Sokolova, V. I.: Phys. Status Solidi (a) 45 (1978) K95.
Ziegler, F., Siegel, W., Khnel, G.: Phys. Status Solidi (a) 65 (1980) 625.
Boudriot, H., Grundler, R., Deus, K., Stockert, T., Schneider, H.A.: Phys. Status Solidi B 126 (1984)
K149.
Folmer, J.C.W., Tuttle, J.R., Turner, J.A., Parkinson, B.A.: J. Electrochem. Soc. 132 (1985) 1608.
Irmer, G., Heinrich, A., Monecke, J.: Phys. Status Solidi B 132 (1985) 93.
Medvedkin, G.A., Rud, Y.V., Tairov, M.A.: Fiz. Tverd. Tela 31 (1989) 108; Sov. Phys. Solid State
(Engl.Transl.) 31 (1989) 606.
Figures to 7.14
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.10
Fig. 7.14.1
CdSnP2. Electron concentration (curves 1, 4) and electron mobility (2, 3) vs. temperature in undoped (1, 2) and
Cu doped (3, 4) samples [76P].
Fig. 7.14.2
CdSnP2. The dielectric function (a) 1 and (b) 2 derived from transmission electron energy loss spectra: (curve a)
from TEL data: (b) from reflectivity measurements; (c) Drude model values. For comparison the values for InP (d) are
shown [84B].
7.15 Cadmium tin arsenide (CdSnAs 2)

Crystal structure
CdSnAs2 crystallizes in the chalcopyrite lattice (space group D2d12 I 4 2d, Fig. 7.0.1).
energy gap
Eg,dir (A)
(B)
(C)
dEg/dT
0.26 eV
0.30 eV
0.79 eV
2.210
2.310
4
4
eVK 1
eV K 1
T = 300 K
electroreflectance
75S
T = 0...300 K
T = 300 K
transport
photoconductivity
75D
81D
Faraday effect
78K,
75D
75D,
80D1
effective masses
mn,
mn,``
mp1,
mp1,``
mp1,ds
0.05 m0
0.048 m0
0.10 m0
0.018 m0
0.5 m0
calculated
calculated
transport
Lattice properties
lattice parameters
a
c
c/a
6.089(5)
11.925(10)
1.957(2)
RT
75S
5.71 g cmn3
RT
75S
a axis
c axis
80P
density
d

3.210 6 K
4.510 6 K
T = 300 K
Debye temperature
D
234.4(53) K
0K
65A
melting temperature
Tm
868(2) K
75S

carrier concentrations, electrical resistivity, carrier mobilities
n-type samples
n
n
1018 1019 cm
single crystals
87N
6300 cm2 V 1s
single crystals
87N
for T- and p-dependence, see also Fig. 7.15.1

n
n
1018 cm 3
T = 300 K
4.4110 4 ... 1.3510 3 cm T = 77...300 K
1.1...1.5104 cm2 V 1 s 1
T = 300 K
76S,
75A1
75D
p-type samples (values for T = 300 K)

p
p
1.91017...1.81019 cm
35...116 1 cm 1
42.6...36 cm2 V 1 s 1
546...510 cm2 V 1 s 1
heavy holes
light holes
75S, 75A2, 76D

80D1,
80D2
dielectric constant
(0)
12.1
T = 300 K
unpolarized
80P
References to 7.15
65A
75A1
75A2
75D
75S
76D
76S
78K
80D1
80D2
80P
81D
87N
Leroux-Hugon, P., Veyssie, J. J.: Phys. Status Solidi 8 (1965) 561.

Mater. 11 (1975) 607.
Amirkhanov, Kh. I., Daunov, M. I., Magomedov, A. B., Magomedov, Ya. B., Emirov, S. N.: High
Temp. - High Pressure 7 (1975) 690.
Daunov, M. I., Magdiev, B. N., Magomedov, A. B.: Fiz. Tekh. Poluprovodn. 9 (1975) 1747; Sov. Phys.
Semicond. (English Transl.) 9 (1976) 1147.
Daunov, M. I., Magomedov, A. B.: Fiz. Tekh. Poluprovodn. to (1976) 641; Sov. Phys. Semicond.
Siegel, W., Ziegler, F.: Exp. Tech. Phys. 24 (1976) 141.
Karavaev, G. F., Barisenko, S. I.: Izv. Vyssh. Uchebn. Zaved. Fiz. 6 (1978) 28.
Daunov, M. I., Magomedov, A. B.: Fiz. Tekh. Poluprovodn. 14 (1980) 341; Sov. Phys. Semicond.
Daunov, M. I., Magomedov, A. B., Ramazanova, A. E.: Phys. Status Solidi (a) 60 (1980) 651.
Popov, A. S., Trifonova, E. P.: Phys. Status Solidi (a) 58 (1980) 679.
Dovletmuradov, Ch., Lebedev, A. A., Rud', Yu. V., Serginaov, M., Skoryukin, V. E.: Sov. Phys.
Semicond. 15 (1981) 1369 (transl. from Fiz. Tekh. Poluprovodn. 15 (1981) 2357).
Nakashima, Y., Hamaguchi, C.: J Phys. Soc. Jpn. 56 (1987) 3248.
Figures to 7.15
Fig. 7.0.1
Fig. 7.0.2
Fig. 7.0.12
Band structure of CdSnAs2.
Fig. 7.15.1
CdSnAs2. (a) Conductivity and Hall coefficient vs. (reciprocal) temperature, (b) log electron mobility vs. log T
for an n-type sample with n = 61016 cm 3. T in K. in cm2 V 1 s 1 [75S].

Semiconductors: Data Handbook (Ch. 6 & 7) (Ed: O. Madelung)

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6 I-III-VI2 compounds

(included are I-Fe-VI2 compounds)

6.0 Crystal structures and electronic structure

0 into two bands:

) + ( 2/2m)(a (b2 + c2cos(4 ))1/2)(kx2 + ky2)

6.1 Copper aluminum sulfide (CuAlS2)

from modulated phase-shiftdifference spectroscopy

excitonic energy gap

excitonic energy gap fine structure (from photoluminescence)

calculated from plasmon energy

splitting energies (at

wavenumbers of infrared and Raman active phonons

all are Raman active;

Transport and optical properties

epitaxial layer, As-doped

epitaxial layer, As-doped

single crystals, annealed in Cd-, Al-,

activation energy of donors

from infrared reflection

from infrared reflection

6.2 Copper aluminum selenide (CuAlSe2)

from optical absorption

free exciton from photoreflectance

excitonic energy gap

splitting energies (at

Hall measurements, epilayers

single crystal, undoped

from Hall-measurements on single crystals 91C

6.3 Copper aluminum telluride (CuAlTe2)

excitonic energy gap

Temperature coefficient of the exciton energy:

wavelength derivative reflectance

splitting energies (at )

thermal expansion coefficient

polycrystalline thin films

activation energy of conductivity

6.4 Copper gallium sulfide (CuGaS2)

excitonic energy gap

from optical absorption

from photocurrent excitation spectra

no temperature or orientation given

exciton emissions from photoluminescence

valence band splitting energies (at )

linear thermal expansion coefficient

wavenumber of infrared and Raman active phonons

single crystals, as grown

p-type sample, annealed under

resistivity, carrier concentration and mobility

coefficients in the formula: n2 = A + B/(1 C/ 2) + D/(1 E/ 2)

linear electrooptic coefficient

6.5 Copper gallium selenide (CuGaSe2)

exciton binding energy

splitting energies (at

linear thermal expansion coefficient

wavenumbers of IR active phonons (at RT)

thin films, four probe method

activation energy of conductivity

6.6 Copper gallium telluride (CuGaTe2)

thin films, optical transmission