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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
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
52
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:
B:
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)
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
Table 3
Band gap energy of AgGaX2 (X S, Se, Te).
Compound
Ex
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
0.22
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).
54
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().
55
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
b
c
Ref. [17].
Ref. [8].
Ref. [9].
12 + 22 ) /2,
n=
(1 +
k=
( 1 +
2
12 + 22 ) /2,
(2)
56
n = A + B/(1 (c / )2) D2
(3)
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
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