Solid State Sciences 26 (2013) 65e71

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Solid State Sciences

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First principles calculations of electronic and optical properties of Ag2S

T. Ben Nasr a, *, H. Maghraoui-Meherzi b, H. Ben Abdallah a, R. Bennaceur a
a
Laboratoire LPMC, Dpartement de Physique, Facult des Sciences, Universit Tunis El-Manar, Tunis 2092, Tunisia
b
Laboratoire LCAE, Dpartement de Chimie, Facult des Sciences, Universit Tunis El-Manar, 2092, Tunisia

a r t i c l e i n f o a b s t r a c t

Article history: A theoretical study of structural, electronic and optical properties of Ag2S is presented using the full
Received 13 August 2012 potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). In
Received in revised form this approach, the modied Becke Johnson (MBJ) potential coupled with Local Density Approximation
15 September 2013
(LDA) was used for the exchange-correlation potential calculation. Ground state properties are deter-
Accepted 24 September 2013
Available online 15 October 2013
mined for the bulk material in monoclinic phase. Band structure reveals that this compound is a direct
energy band gap semiconductor. MBJLDA results for the band gap of this compound are much better than
those obtained using LDA, PerdeweBurkeeErnzerhof generalized gradient approximation (PBE-GGA)
Keywords:
Chalcogenides
and EngeleVoskos GGA (EV-GGA). A very good agreement is observed between MBJLDA band gap and
Ab initio calculations corresponding experimental values as compared to other calculations. Optical constants including the
Electronic properties dielectric function, refractive index, extinction coefcient, electron energy loss function, reectivity and
Optical properties absorption coefcient are obtained and discussed.
2013 Elsevier Masson SAS. All rights reserved.

1. Introduction to those obtained from PBE-GGA, LDA, EngeleVoskos GGA and

Silver sulde (Ag2S) belongs to IeVI semiconductor materials
with monoclinic crystal structure. Thin lms of Ag2S have appli-
cations in photo conducting cells [1], IR detectors [2], solar selective
coating [3], photovoltaic and photochemical cells [4,5]. Thus, Ag2S
is a promising material for conversion of solar energy into elec-
tricity as its band gap is between 1 and 2 eV [6]. Electronic structure
of Ag2S was investigated experimentally using photoelectron
spectroscopy, and theoretically using the full-potential LMTO cal-
culations [7]. Chemical bonding in silver sulde was studied using
local approximation of density functional theory [8]. Since calcu-
lations performed using the local density approximation (LDA) and
the generalized gradient approximation (PBE-GGA) give unsatis-
factory electronic properties such as band gaps, some further ap-
proximations are usually needed to make the rst principles
electronic gaps and optical properties comparable with experi-
mental results. Recently Tran and Blaha [9] proposed a modied
BeckeeJohnson exchange plus local density approximation corre-
lation potential (MBJLDA), which can be used to produce accurate
semiconductor gaps. In this paper, we use the MBJLDA approach
within density functional theory (DFT) to investigate electronic and
optical properties of Ag2S. The calculated energy gap was compared
* Corresponding author. Tel.: 216 95822549; fax: 216 71885073.
E-mail address: tarek.ben-nasr@laposte.net (T. Ben Nasr).
with experiments to test accuracy. We will give computational
details in the next section. Our main results will be presented in the
third section. In the fourth section, we will give our principal
conclusion.
2. Computational method
Silver sulde Ag2S compound crystallizes in a monoclinic
structure with space group P21/c (No. 14). There are four formula
units in the unit cell (Fig. 1). The lattice constants and atomic po-
sitions were reported [10]. The FPLAPW method, which is based on
density functional theory (DFT) [11,12] and is implemented in
WIEN2k code [13], was used. The exchange and correlation (XC)
effects were taken into account using four approximations: LDA
[14], PBE-GGA [15], EV-GGA [16] and MBJLDA [9]. In order to ach-
ieve energy eigenvalues convergence, the wave functions in the
interstitial region are expanded in plane-waves with a cut-off
kmax 7/RMT, where RMT denotes smallest mufn-tin (MT) radii
in the unit cell and kmax gives the magnitude of largest k vector in
the plane-wave expansion. RMT values for Ag and S atom were
chosen to be 2.5 and 2.0 a.u., respectively. The valence wave func-
tions inside MT spheres are expanded up to Gmax 14 (a.u)1. Self-
consistent calculations are converged up to an accuracy of 104Ry
in the total energy using a special mesh (17  9  8) of 486 k points
in the rst Brillouin zone (BZ).

1293-2558/$ e see front matter 2013 Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.solidstatesciences.2013.09.017
66 T. Ben Nasr et al. / Solid State Sciences 26 (2013) 65e71

Fig. 1. Crystal structure of Ag2S.

3. Results and discussion

3.1. Structural properties

Structural properties of Ag2S are calculated solely using the LDA

and PBE-GGA functional. Indeed, since there is no exchange and
correlation term from which the MBJLDA potential can be deduced
as shown in Refs. [17,18], this potential cannot be used for the
calculation of forces which act on the nuclei as required for ge-
ometry optimization. Therefore, Tran and Blaha [9] recommend to
use rst a modern GGA functional for the structural properties and
then the MBJLDA potential for the calculation of the band structure.
Fig. 2, shows calculated total energies at different volumes around
the experimental one and tted by the Murnaghan equation of
state [19] in order to obtain the equilibrium lattice constant, the
bulk modulus and its pressure derivative. In the case of the MBJLDA
procedure (no correlation and exchange energy term) the t is
quite uncertain since the data do not follow Murnaghans curve in
sharp contrast with the LDA and the PBE-GGA. The calculated and
experimental lattice parameters are given in Table 1. It is clearly
seen that PBE-GGA over-estimates the lattice parameters while LDA
underestimates them. Moreover, the optimized b angle is found to Fig. 2. Total energyevolume curve for Ag2S within PBE-GGA, LDA and MBJLDA
be 117.35 . We can see that the calculated lattice constants agree approximations.
well with the experimental values [10]. Furthermore, calculated
bulk modulus for LDA is larger than the obtained value for PBE-
GGA. This is largely accounted for by the fact that LDA un- gives an energy band gap larger than LDA, PBE-GGA, EV-GGA which
derestimates the volume and overestimates bulk modulus [20]. is in better agreement with the experimental value (Eg 1.1 eV [6]).
This is an expected result since both LDA and PBE-GGA underesti-
3.2. Band structure and density of states mate the energy gap [21]. On the other hand, EV-GGA band gap is
better than those obtained from LDA and PBE-GGA but still there
LDA, PBE-GGA, EV-GGA and MBJLA calculated electronic band exists discrepancy from corresponding experimental value. One can
structures are shown in Fig. 3. Band structures show similar shape, notice that MBJLDA gap is better than other theoretical results
however, the gap values are different. The top of valence bands and (0.63 eV in Ref. [7] and 0.5 eV in Ref. [8]) and slightly larger than the
the bottom of conduction bands are located at G point. Following experimental one. This could be explained by the fact that MBJ
these calculations the crystal possesses direct energy gap equal to potential was designed to reproduce the shape of the exact ex-
about 0.79 eV (LDA), 0.83 eV (PBE-GGA), 0.97 eV (EV-GGA), and change optimized effective potential of atoms [22]. Calculated
1.20 eV (MBJLDA). It should be emphasized that MBJLDA approach MBJLDA partial densities of states in Ag2S are shown in Fig. 4b and c.
 T. Ben Nasr et al. / Solid State Sciences 26 (2013) 65e71 67

Table 1 can originate from a specic position of the conduction band

Calculated equilibrium lattice constants, bulk modulus (B0) and pressure derivative minimum, which is a mixture of S-3p and Ag-5s states. In the
of bulk modulus B00 of Ag2S.
conduction bands, a shift of Ag-s and S-p states has a strong effect
GGA LDA Exp.a on energy gap increase, while the valence bands remain almost
a (
A) 4.363 4.208 4.231 unchanged. Hence, within a framework of EV-GGA and MBJLDA
b (
A) 7.054 6.804 6.930 approaches, the spectral energy shift of Ag-s and S-p states have
c (
A) 8.790 8.477 9.526 strong effect in opening the gap keeping the valence bands un-

b 117.350 117.350 125.480
changed (Fig. 4a).
B0 (GPa) 65.348 98.261 e
B00 5.414 5.977 e
a
Ref. [10]. 3.3. Optical properties

The optical properties of matter can be described by the com-

In lower part of the valence band, the sharp peak around 12.5 eV
corresponds mainly to S-3s states. The valence states
between 5.6 eV and Fermi level are dominated by Ag-4d states,
while the contribution of Ag-5p states is practically zero. However,
Ag-5s states show a small contribution to the valence band. The
only contribution of S atoms comes from 3p states, while the s-state
and d-state contributions are negligible. The energy gap increase
plex dielectric function 3 (u), which represents linear response of
the system to an external electromagnetic eld. Real and imaginary
parts of the corresponding dielectric function are 3 1(u) and 3 2(u),
respectively. Real part 3 1(u) is related to the electronic polarizability
of the material, and imaginary part 3 2(u) is associated with elec-
tronic absorption of the material. Calculations of these dielectric
functions involve the energy eigenvalues and electron wave

Fig. 3. Band structures of Ag2S within PBE-GGA, LDA, EV-GGA and MBJLDA (The bands are shown in different colors). (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of this article.)
68 T. Ben Nasr et al. / Solid State Sciences 26 (2013) 65e71

functions. On the basis of calculated band structure of silver sulde, Optical constants such as refractive index n(u) and extinction
imaginary part of the dielectric function 3 2(u) is given by [23,24] coefcient k(u), are calculated in terms of the real and imaginary
part of the complex dielectric function as follows [26,27]
Z  
4pe2 X 
32 u hijMjji 2
fi 1  fi d E f  Ei  u d3 k (1)  2
1=2 1=2
m2 u2 i;j 31 3
1 3 22
n p (2)
2
where M is the dipole matrix, i and j the initial and nal states,
respectively. fi the Fermi distribution function for the ith state and
  1=2 1=2
Ei is the electron energy in the ith state. The real part 3 1(u) of the  31 3
2 3 22
1
dielectric function can be extracted from the imaginary part using k p (3)
KramerseKroning relation [25]. 2
Furthermore, the electron energy loss function L(u), reectivity
R(u) and the absorption coefcient a(u) can be calculated using the
dielectric function, through following relations [28]

3 2 u
Lu 2 u 3 2 u
(4)
3
1 2

p 
 3 u  12
 
Ru p  (5)
 3 u 1

p h i1=2 1=2
au 2u 3 21 u 3 22 u  3 1 u (6)

To perform optical calculations MBJLDA was used since it yields

better band gaps than LDA, PBE-GGA and EV-GGA. For the calcu-
lations of optical properties, a denser sampling of the BZ was
needed, where we used 1456 k-points.
Due to monoclinic symmetry of Ag2S, the dielectric tensor is not
diagonal in the arbitrary Cartesian coordinate system {x, y, z}.
However, the dielectric tensor can be reduced to its diagonal form
by transforming this coordinate system into another one which is
also orthogonal and usually called the principal axes system [29].
This transformation is illustrated below,

0 1 0 0 1
3 11 3 12 0 3
11 0 0
Im3 u @ 3 21 3 22 0 A0Im3 0 u @ 0 3
0
22 0 A
0 0 0
0 0 3 33 3
33
(7)

where 3 ij and 3 0ij stand for Im3 ij and Im3 0ij . The eigenvalues 3 0ij are
expressed in terms of the calculated 3 ij components by formulas:

 q 9
3
0 3 11 3 22 3 11  3 22 2 43 212 >
1
11 2 >
>
>
=
 q
0 1 2 (8)
3 2 3 11 3 22  3 11  3 22 43 12 > 2
>
22 >
>
;
3
0 3 33
33

Reducing the dielectric tensor to its diagonal form, we could

!
!
!
determine the three main optical axes in the crystal n1 ; n2 ; n3
[29]:

9

! ! !>
n1 xuex ey >
=

! ! !
n2 yuex ey (9)

! ! >
>
n3 ez ;

! ! !
ex , ey and ez denote the orts of the x, y and z directions of the
Fig. 4. Total and partial densities of states for Ag2S. original coordinate system, and:
 T. Ben Nasr et al. / Solid State Sciences 26 (2013) 65e71 69

Fig. 5. The monoclinic unit cell of Ag2S.

q
3 11 3 11  3 22 2 43 212
 3 22  23 12
xu q (10)
3 11  3 22 23 12  3 11  3 22 2 43 212

q
3 11 3 11  3 22 2 43 212
 3 22  23 12 
yu q (11)
3 11  3 22 23 12 3 11  3 22 2 43 212

From Fig. 5, a connection between the original coordinate sys- Fig. 6. Real and imaginary parts of the dielectric function of Ag2S within MBJLDA.
! ! ! ! ! !
tem ex ; ey ; ez and the system of crystallographic axes ea ; eb ; ec
can be easily established:
9 (Gv  Gc), which gives the threshold for direct optical transitions.
! ! > Beyond this point the curve increases rapidly. The rst peak at
ex ea >
>
>
= w1.8 eV is caused by transitions from the upper valence band to
! !
ey eb (12)
> the lower conduction band. These correspond either to transitions
! >
>
! ec  cotb! >
; from S 3p valence states to conduction band, or from occupied Ag
ez sin ea
b 4d to unoccupied S 3p. The next two peaks at w3.6 eV and 5.2 eV
involve mainly transitions from Ag 4d to S 3p, or from S 3p to Ag 5s
Combining this result with the Formula (9) one can determine
orbitals. At still higher energy, the spectrum is without structure
the orientation of the principal optical axes of Ag2S in terms of its
and decays very rapidly with photon energy. Fig. 6a shows the
crystallographic directions:
calculated real part of the dielectric function 3 1(u). It is evident that
9 3 1(u) increases with increasing energy and reaches a maximum

! ! !
n1 xuea eb >
>
> value at around 1.7 eV, then decreases to reach a negative mini-
>

! ! ! =
n2 yuea eb (13) mum value at 6.1 eV. The negative values of 3 1(u) show that, in this
! >
> energy region, the incident electromagnetic waves are mostly re-

! !>>
n3 ec  cot bea ;
sin b
Calculated real and imaginary parts of the dielectric function
3(u) for Ag2S are represented in this coordinate system as a func-
tion of the photon energy. The imaginary part 3 2(u) of the
dielectric function shown in Fig. 6b is slightly anisotropic and
highly isotropic in low and higher energy regions, respectively. The
weak anisotropy could be explained by the Ag2S crystalline
structure which can be considered as pseudocubic with slightly
distorted body-centered cubic arrangement of sulfur anions [30].
The fundamental absorption edge occurs at 1.07 eV. This point is
the valence band and conduction band splitting at G point
ected from the medium, hence the material exhibits a metallic
behavior and can be used for a shielding purpose from radiations
in this specic energy range. The local maxima of reectivity as
shown in Fig. 8b correspond to the negative values of 3 1(u). With a
further increase in energy, 31(u) increases and shows a steady
behavior at high energy limits.
The roots of 3 1(u) indicate plasma oscillations but it is not an
enough condition and we have to consider the energy loss function.
Fig. 8a shows the energy loss function of Ag2S compound in terms
of photon energy. There is just one outstanding peak at 11.80 eV.
This peak is in agreement with the last root of 3 1(u). Therefore, the
energy of Plasmon oscillation would be about 11.80 eV.
70 T. Ben Nasr et al. / Solid State Sciences 26 (2013) 65e71

than c, vg is found to be less than c [26]. The static refractive index

n(0) and static dielectric function 3 1(0) are summarized in Table 2.
The calculated refractive index is in good agreement with experi-
mental results [3].
A relationship between the calculated extinction coefcient k(u)
and energy is shown in Fig. 7b. The response of k(u) and 3 2(u) is
very close to each other. This result is in good agreement with
literature [26].
Frequency dependent reectivity R(u) versus energy is shown in
Fig. 8b. It is clear from the gure that at zero frequency the

Fig. 7. Refractive index (a) and extinction coefcient (b) of Ag2S within MBLDA.

The calculated refractive index of Ag2S is shown in Fig. 7a. A

broad spectrum for n(u) over a wide energy range is noted for the
compound. The index n(u) closely follows 3 1(u) [26]. The refractive
index spectrum shows two different features. First, n(u) reaches a
maximum value of around 2.9 at around 2.5 eV. Afterward, n(u)
falls down at intermediate energies and then the curve vanish at
higher energies, because beyond certain energy the considered
material absorb high energy photons and cannot behave as trans-
parent material. Fig. 7a shows that the refractive index is less than 1
over a number of frequencies, indicating a lower value of light
celerity c than the light phase velocity in disagreement with the
relativity. The signal propagates in a dispersive medium with the
group velocity vg, (vg du/dk) rather than at phase velocity (v u/
k c/n). The equation relating vg and v is given by:
 
k dn
vg v 1  (14)
n dk
The above equation suggests that vg is always smaller than v.
When a signal is transmitted in a spectral region, where v is greater

Table 2
Calculated static dielectric constant 3 1(0) and static refractive index n(0) at zero
frequency for Ag2S within MBJLDA.

!
!
!
n1 n2 n3

3 1(0) 6.24 5.08 5.41

n(0) 2.50 2.25 2.36 Fig. 8. Electron energy loss function (a), reectivity spectra (b) and absorption coef-
cient (c) of Ag2S within MBJLDA.
 T. Ben Nasr et al. / Solid State Sciences 26 (2013) 65e71
magnitude of the coefcient of reectivity (R(0)) is 0.16. The
reectivity which arises from the interband transition reaches a
maximum value at 11.21 eV. The energy dependence of the ab-
sorption spectrum is given in Fig. 8c. The absorption edge starts
from 1.07 eV, which corresponds to the energy gap. This originates
from the transition in S-3p states located at the top of valence band
to the empty Ag-5s states located at the bottom of conduction
bands.
4. Conclusion
Ab initio calculations have been performed on the electronic and
optical properties of Ag2S using rst-principles FP-LAPW method.
Structural parameters are found to be comparable to available data
in the literature. Calculated electronic structure and energy band
structure show a direct band gap at the G point in the Brillouin
zone. Our results for band structure and density of states have
shown that the use of LDA, PBE-GGA, EV-GGA and MBJLDA ap-
proaches can enhance the value of the energy band gap when we
move from LDA to GGA, EVGGA then MBJLDA. Optical parametric
quantities (dielectric constant, refractive index, extinction coef-
cient, electron energy loss function, reectivity and absorption
coefcient), which strongly depend on the band structure results
were also presented. Using projected densities and band structure,
the interband contributions to optical properties of Ag2S were
analyzed.
Acknowledgments
The authors are very grateful to Prof. P. Blaha and his team
(Vienna University of Technology, Austria) for providing the wien2k
package used in performing this calculation.
71
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