Materials Science in Semiconductor Processing 47 (2016) 5156

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Ab initio study of structural, electronic and optical properties

of ternary chalcopyrite semiconductors
H. Salehi, E. Gordanian n
Department of Physics, Faculty of Science, Shahid Chamran University (SCU), Golestan Avenue, Ahvaz, Iran

art ic l e i nf o

a b s t r a c t

Article history:
Received 6 February 2016
Accepted 21 February 2016

In this paper, structural, electrical and optical properties of AgGaX2 (X S, Se, Te) were studied by using
Full Potential Linear Augmented Plane Wave (FP-LAPW) based on density functional theory. Perdew
Becke Ernzerhof (GGA-PBE) and Wu Cohen Generalized gradient approximation (GGA-Wc), Engel Voskov
Generalized Gradient Approximation (EV) and modied Becke-Johnson exchange potential (MBJ) were
used for the exchange correlation potential. GGA-PBE was closed to the other and experimental data for
lattice constant, bulk modulus (B) and its rst derivative (B), and MBJ potential was in good agreement
with the experiment and other calculations for band gap energy and the optical properties. Band
structure, total and partial density of states were plotted to obtain electronic properties and the band gap
was direct for all components. By using imaginary and real part of dielectric functions, some optical
properties such as reection coefcient (R), refractive index (n), extinction coefcient (k) were obtained
and the role of X atoms (X S, Se, Te) in optical properties were investigated.
& 2016 Published by Elsevier Ltd.

Keywords:
Chalcopyrite
DFT
Ternary semiconductors
Band gap energy
Density functional theory
Optical properties

1. Introduction
I III VI
AB
C2 semiconductor compounds have attracted considerable
interest because of their fascinating electronic and optical properties and wide transparency band in visible and infrared regions [1].
I III VI
AB
C2 semiconductor compounds are good candidates for the
formation of pn hetero-junction with IIVI group semiconductors,
because both structures are similar [2]. In this paper AgGaS2,
AgGaSe2 and AgGaTe2 compounds were studied. These ternary
compounds belong to the tetragonal chalcopyrite structure, which
is considered as two zinc-blende super lattice along C-lattice constant. Chalcopyrite ternary compounds are divided into two groups,
silver (Ag-IIIVI2) and copper (Cu-IIIVI2) based compounds. For the
rst group, Ag-based attracts much attention due to their potential
usage in non-linear optical and photonic applications. Among the
Ag-based, the AgGaS2 and AgGaSe2 were studied extensively due to
their direct band gap of about 2.51 eV and 1.82 eV respectively and
good transparency in 5001200 nm wavelength [35]. For the
second group, Cu-based, following compounds Cu (In, Ga, Se) (CIGS)
were studied extensively due to their suitability for the construction
of thin lm solar cells and high absorption coefcient, suitable optic
band gap (1.04 eV) and ease of production [2]. Chalcopyrite compound is used as solar cell, Light Emitted Diode (LED), Non-Liner

Abbreviation: EV, Engel Voskov Generalized Gradient Approximation; MBJ,

Modied BeckeJohnson exchange potential
n
Corresponding author.
E-mail address: elham.gordanian@gmail.com (E. Gordanian).
http://dx.doi.org/10.1016/j.mssp.2016.02.015
1369-8001/& 2016 Published by Elsevier Ltd.

Optical devices (NLO) and photonic sensors. The chalcopyrite

composition with narrow band gap is suitable for infrared detector
used in photovoltaic solar cells as thin lms [6,7]. Mentioned
semiconductors can shift wavelength and can tune over wide
spectra range because of their Non-Liner Optical properties (NLO),
so they increase laser performance and can be used as mid- and farIR lasers [7,8]. In previous works with rst principle calculations,
Local Density Approximation (LDA) and the Generalized Gradient
Approximation (GGA) were used for exchange-correlation potential
and calculate the structural, optical and electronic properties [9]. On
the other hand, the BeckeJohnson exchange potential (MBJ) and
Engel Voskov Generalized Gradient Approximation prove better
performance than LDA and GGA in predicting band gap energy. That
is why in the present work the GGA approximation was used to
calculate lattice constants and MBJ potential and EV approximation
were used to calculate band gap energy and optical properties.

2. Computational details
All calculations were performed employing Density Functional
Theory (DFT) [10] as embodied in the Wien2k code [11]. Perdew
Becke Ernzerhof (GGA-PBE) [12] and Wu Cohen Generalized gradient approximation (GGA-WC), Engel Voskov Generalized Gradient Approximation (EV) [13], Local Density Approximation (LDA)
[14] and modied Becke-Johnson exchange potential (MBJ) [15]
were used for exchange-correlation potential. Full relaxation was
exerted on all atoms until the total force became smaller than

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H. Salehi, E. Gordanian / Materials Science in Semiconductor Processing 47 (2016) 5156

1 mRy/Bohr. The mufn-tin radii for Ag, Ga, S, Se and Te atoms

were chosen to be 2.5, 2.36, 2.03, 2.28 and 2.49 a.u. respectively.
The expansion of the wave functions and charge densities were cut
off by the RMTKMAX 7 and GMAX 12 parameters. We generated 40
special k-points in the rst Brillouin zone (1BZ) corresponding to
the shifted MonkhorstPack grids of 7  7  7 for all compounds.

Table 1
Lattice constant in angstrom (), bulk modulus and its rst derivative.
Compound

Exchange

a b

B (GPa)

AgGaS2

LDA
GGA
WC
Othera
Otherb
Expa

5.640
5.678
5.663
5.587
5.77
5.755

10.734
10.587
10.647
10.401
10.578
10.278

98.65
100.04
100
81.23
60.8
77.6

9.93
4.95
5
4.74
4.00
4.00

AgGaSe2

LDA
GGA
WC
Othera
Otherb
Expa

5.878
5.915
5.895
5.838
6.05
5.992

11.313
11.172
11.346
11.022
11.210
10.886

100.02
100.00
100.00
64.621
50.7
65

5.09
5.00
5.00
4.70
5.02
4

AgGaTe2

LDA
GGA
WC
Otherc
Expd

6.138
6.272
6.254
6.288
6.280

11.669
11.925
12.037
11.949
11.940

99.39
99.99
99.99

1.91
5.83
5.00

3. Structural properties
AgGaX2 (X S, Se, Te) composition has tetragonal chalcopyrite
, which is considered as two zincstructure, the space group is I42d
blende super lattice along C-lattice constant, both structures are
shown in Fig. 1. There are eight atoms in the chalcopyrite structure
and the positions are as follows:

A:

(0, 0, 0), (0, 1/2, 1/2)

B:

(1/2, 1/2, 0), (1/2, 0, 1/2)

C:

(u, 1/4, 1/8), (0, 1/2, 1/2), (3/4, u, 7/8), (1/4, u, 7/8)
u = 1/2 (c 2/32a2 1/16)

(1)

The calculated and experimental data of lattice constants, bulk

modulus (B) and its rst derivative ( B) are given in Table 1 for
AgGaX2 (X S, Se, Te). The results of GGA approximation are in
good agreement with the experiment and other calculations. The
bond lengths before and after relaxation are given in Table 2 which
indicates that AgX and GaX (X S, Se, Te) bond length decreases.

4. Electronic properties
The electronic properties of AgGaX2 (X S, Se, Te) composition
were computed by using GGA, LDA, EV approximation and MBJ

76.6

Ref. [17].
Ref. [16].
c
Ref. [8].
d
Ref. [18].
b

Table 2
Bond lengths of AgGaX2 (X S, Se, Te), before and after relaxation in angstrom ().
Type

Before

After

AgS
GaS
AgSe
GaSe
AgTe
GaTe

4.690
4.420
4.919
4.595
5.137
4.977

4.680
4.416
4.855
4.977
5.136
4.976

Fig. 1. (a) Chalcopyrite and (b) zincblende structure.

H. Salehi, E. Gordanian / Materials Science in Semiconductor Processing 47 (2016) 5156

Table 3
Band gap energy of AgGaX2 (X S, Se, Te).
Compound

Ex

Band gap (eV)

AgGaS2

EV
GGA
LDA
MBJ
Othera
Other
Exp

1.57
1.04
0.86
2.13
0.95
2.23b
2.51

EV
GGA
LDA
MBJ
Othera
Other
Exp

1.18
0.73
0.60
1.68
0.19
1.42b
1.18

EV
GGA
LDA
MBJ
Otherb
Exp

1.10
0.80
0.68
1.47
0.75
1.32

AgGaS2

AgGaTe2

a
b
c

Ref. [17].
Ref. [8].
Ref. [16].

Crystal-eld splitting CF

 0.27
 0.26
 0.26c
 0.28

 0.26
 0.23
 0.24c
 0.25

53

potential. Obtained and experimental data of band gap energy and

the crystal eld splitting are demonstrated in Table 3.
The band gap energy and the crystal eld splitting decreased
from AgGaS2 to AgGaSe2 and AgGaTe2 that is in good agreement
with other work which indicated that by increasing the lattice
constants, the band gap decreases in binary semiconductors and
other chalcopyrite [16]. MBJ potential results reach an agreement
with the experiment. So by using MBJ, total, partial density of
states (TDOS and PDOS) and band structure are presented in
Figs. 24 for all compositions. Total density of states for up and
down electron spin (Fig. 2) demonstrate that AgGaS2, AgGaSe2 and
AgGaTe2 are not magnetic materials.
4.1. Density of states

 0.22

Electron conguration of Ag, Ga, S, Se and Te are [Kr]4d105s1,

[Ar]3d104s24p1, [Ne]3s23p4, [Ar]3d104s24p4 and [Kr]4d105s25p4
respectively. As shown in Fig. 2, for all compounds the valence
band is divided into two sub-bands so we have labeled the starting
from the top (zero energy) as VB1 and VB2.
By X atom replacement in AgGaX2 from S to Se, the widths of
these sub-bands and the band-gap between VB1 and VB2 decreased and the gap disappears in AgGaTe2. Partial density of
states (PDOS) are plotted for s, p and d orbital of Ag, Ga, Se, Te and

Fig. 2. Total density of states by MBJ potential, red lines show down spins and black lines show up spins.

Fig. 3. Partial density of states by MBJ potential for AgGaX2 (X S, Se, Te).

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H. Salehi, E. Gordanian / Materials Science in Semiconductor Processing 47 (2016) 5156

Fig. 4. Band structure of AgGaX2 (X S, Se, Te) compound by MBJ potential.

Table 4
Interband transition of AgGaX2 (X S, Se, Te).
Compound

Peak

Transition

Energy(eV)

AgGaS2

A1

a4a8

3.35

A2

a1a8

5.30

A3

a7a5

6.44

AgGaSe2

AgGaTe2

A4

a a

23 Peak

Transition

8.15
Energy (eV)

B1

b b

3.07

B2

b1b2

4.80

B3

b6b5

5.55

B4

b12b7

6.24

B5

b b

7.35

B6

b10b11

9.98

Peak

Transition

Energy (eV)

C1

c5c6

3.47

C2

c 3c4

4.29

C3

c1c2

5.37

Fig. 5. The imaginary part of dielectric function 2 for AgGaX2 (X S, Se, Te) compound.

s and p orbital of Sulfur. PDOS shows that for VB1, 4d, 5s and 5p
orbitals of Ag overlapped with 4p orbital of Ga and 3p orbital of
Sulfur while VB2 formed by overlapping 5s and 5p orbitals of Ag,
4s orbital of Ga and 3s orbital of Sulfur, also, 4s, 4p and 3d orbitals
of Ga overlapped with 3s orbital of Sulfur for VB2 for AgGaS2,
AgGaSe2 and AgGaTe2. Clearly the orbitals of gallium atom contribute less in both valence and conduction bands than other
atoms for three compositions [8].
4.2. Band structure
As shown in Fig. 4, the top of the valence band maximum (VBM)
and bottom of the conduction band minimum (CBM) in -point indicate that all materials are semiconductors with direct band gap. Also,
existence of crystal-eld (CF) pair in -point near the VBM is obvious
and the splitting between them, CF , is shown in Table 3 for three
compounds. This behavior indicates the role of anion displacement
(u 1/4), tetragonal distortion ( = c /a 1) and two different cations
(Ag and Ga), which is in good agreement with other calculations [17].

5. Optical properties
Dielectric function () is an important optical characteristic in
solid material which is a complex function () = 1() + i2().

The real part 1 was obtained by using the KramersKronig

transform and the imaginary part 2 by using joint density of
states and momentum matrix elements.
5.1. The imaginary part of dielectric function
Transition in material include intraband (band-to-band) and
interband (between two bands) transitions. In semiconductors the
most inuential term in transition is interband and there is no
transition for photon with energy smaller than band gap. On the
other hand, the imaginary parts of dielectric function 2 are related
to the absorption spectra and in that range of energy (smaller than
band gap energy) the absorption is zero. By increasing the energy,
rst peak becomes visible in imaginary part diagram. In this paper,
GGA approximation and MBJ potential were used to calculate
optical properties. There are two parts for dielectric function of
chalcopyrite structure, 2xy and 2z, the rst term is the average of
spectra for polarizations along the x and y directions (Ec-axis)
and the second term is related to the z direction (Ec-axis). The
average function of imaginary part 2(), 2 = (2x + 2y + 2z )/3, is
plotted in Fig. 5. Existence of several pick in 2() diagram are
related to the band-to-band transitions. By using partial density of
states and the diagram of imaginary part 2(), interband transition is predicted and the results are shown in Table 4 for AgGaX2
(X S, Se, Te) compounds.

H. Salehi, E. Gordanian / Materials Science in Semiconductor Processing 47 (2016) 5156

55

Fig. 9. Calculated values of reectance factor R.

Fig. 10. Calculated values of loss function.

Fig. 6. The real part of dielectric function 1 for AgGaX2 (X S, Se, Te) compound.

Table 5
Constants of Sellmeyer equation for AgGaX2 (X S, Se, Te).
Type

D  10  9

AgGaS2
AgGaSe2
AgGaTe2

1.7
2.03
2.47

0.583
0.51
0.43

109.76
132.83
238.82

 5.292
 5.34
 8.03

Table 6
Static dielectric constants of AgGaX2 (X S, Se, Te).
Compound

Ex

AgGaS2

GGA
MBJ
Other
Exp

8.20
5.65
6.06a

8.28
5.74
6.11a

8
5.45
5.94a

 0.03
 0.02
 0.029a

2.86
2.38
2.58b, 2.3c
2.46a

AgGaSe2

GGA
MBJ
Other
Exp

1.035
6.64
7.22a

10.58
6.66
7.23a

10.27
6.56
7.21a

 0.03
 0.02
 0.003a

3.21
2.58
2.98b
2.72a

AgGaTe2

GGA
MBJ
Other
Exp

12.91
8.87

12.90
8.93

12.72
8.79

 0.01
 0.02

3.58
2.97
3.27b
2.98b

Fig. 7. Calculated values of n for AgGaX2 (X S, Se, Te).

1 = (1x + 1y )/2, 1 = 1z , 345 = (1 1)/1.

a

Fig. 8. Calculated values of extinction coefcient k.

b
c

Ref. [17].
Ref. [8].
Ref. [9].

5.2. The real part of dielectric function

The average function of the real part 1(), 1 = (1x + 1y + 1z )/3,
is demonstrated in Fig. 6. There is a strong reection in the range
of energy where the real part of dielectric function is negative, for
example 720, 616 and 4.715.5 eV for AgGaS2, AgGaSe2 and
AgGaTe2 respectively. The important part of 1 is in zero energy,
1(0), which is equal to the square of the refractive index (n) and
known as static dielectric constant that depends on the band gap
energy. Our as well as other results are given in Table 6 for AgGaX2
(X S, Se, Te) component:

12 + 22 ) /2,

n=

(1 +

k=

( 1 +
2

12 + 22 ) /2,

R = ((n 1) + k 2)/((n + 1)2 + k 2)

(2)

Perpendicular and in-plane components of 1(0) shows the degree

of anisotropy of static dielectric constant which is small and negative for all materials and is close to other calculations. By using
Eq. (1) the other optical constant was obtained. Complex refractive
index (N) has two parts, real (n) and imaginary (k) parts that are

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H. Salehi, E. Gordanian / Materials Science in Semiconductor Processing 47 (2016) 5156

known as refractive index and extinction coefcient. The results of

n, k, reectance factor (R) and Loss function, are given in Figs. 7
10. Dependence of refractive index on the wavelength is presented by Sellmeyer equation, Eq. (2), where is the wavelength.
By tting refractive functions in Fig. 7 to Sellmeyer equation the
obtained constants are presented in Table 5. There is a similar
calculation for AgGaS2 and the constants are as follows: A  1.26,
B 3.49, C 132.62 nm and D  6.49  10  9 nm  2 which is in
good agreement with our calculation [9]

n = A + B/(1 (c / )2) D2

(3)

As shown in Fig. 7, by changing X atom in AgGaX2 (X S, Se, Te),

refractive index n(0), extinction coefcient k(0), reectance factor
R(0), the imaginary part 1(0) and the real part of dielectric function 1(0) increase. By replacing X atom in AgGaX2 (X S, Se, Te), as
presented in Fig. 7, for wavelength under 111 nm, refractive index
decrease from S to Se and Te while for wavelength higher than
111 nm, it increases. Finally the refractive index attains the constant value in innite wavelength, for instance 2.38, 2.58 and 2.97
for AgGaS2, AgGaSe2 and AgGaTe2 respectively. The behavior of
extinction coefcient (k) and reectance factor (R) is similar to
refractive index but the wavelengths are 160 and 110 nm respectively. In innite wavelength reectance factor (R) reaches to 0.17,
0.2 and 0.25 for AgGaS2, AgGaSe2 and AgGaTe2, and also extinction
coefcient (k) is zero for all components.

6. Conclusion
The electronic, structural and optical properties of ternary
compounds AgGaX2 (X S, Se, Te) were investigated by using
density functional theory (DFT) employing the augmented plane
waves plus local orbital method (APW lo). PBE-GGA, WC-GGA,
Engel Voskov generalized Gradient Approximation (EV) and
modied BeckeJohnson exchange potential (MBJ) were used for
the exchange-correlation functional. The investigation indicated
that AgGaX2 (X S, Se, Te) compounds crystallized in chalcopyrite
structure and they are nonmagnetic semiconductors with direct

band gap. Band structure diagrams demonstrated that valence

band is divided into two sub-bands, VB1 and VB2, and the widths
of these sub-bands and the band-gap between them decreased by
X atom replacement in AgGaX2 (X S, Se, Te) from S to Se and Te.
The results of real and imaginary parts of dielectric functions were
used to obtain optical constants. Refractive index n(0), extinction
coefcient k(0), reectance factor R(0), the imaginary part
2(0) and the real part of dielectric function 1(0) increased by
changing X atom in AgGaX2 (X S, Se, Te). Also some interband
transitions were given for AgGaS2, AgGaSe2 and AgGaTe2.

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