Materials Science in Semiconductor Processing 40 (2015) 727–736

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Materials Science in Semiconductor Processing

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

Structural, electronic, optical, elastic and thermal properties

of CdGeP2 with the application in solar cell devices
Ruchita Gautam a,b, Pravesh Singh a,b, Sheetal Sharma c, Sarita Kumari d, A.S. Verma b,n

D
a
Department of Electronics and Communication, K.I.E.T., Ghaziabad, U.P. 201206, India
b
Department of Physics, Banasthali Vidyapith, Rajasthan 304022, India
c
Department of Physics, Swami Premanand Mahavidyalaya, Mukerian, Punjab 144211, India
d
Department of Physics, University of Rajasthan, Jaipur 302004, India

TE
ar t ic l e i nf o a b s t r a c t

Article history: The ab initio calculations were performed for CdGeP2 chalcopyrite in the body centered tetragonal (BCT)
Received 23 May 2015 phase in an attempt to calculate the structural, electronic and optical properties by linearized augmented
Received in revised form plane wave (LAPW) method as implemented in the WIEN2K. Furthermore, optical features such as di-
2 July 2015
electric functions, refractive indices, extinction coefficient, optical reflectivity, absorption coefficients,
Accepted 6 July 2015
optical conductivities, were calculated for photon energies up to 40 eV. The six elastic constants (C11, C12,
Available online 31 July 2015

PACS:
31.15.A

46.70.
P
62.20.D

C
C13, C33, C44 and C66) and mechanical parameters were presented and compared with the available ex-
perimental data. The thermodynamic calculations within the quasi-harmonic approximation is used to
give an accurate description of the pressure–temperature dependence of the thermal-expansion coef-
ficient, bulk modulus, specific heat, Debye temperature, entropy and Grüneisen parameters. Based on the
semi-empirical relation, we have determined the hardness of the materials for the first time at different
A
62.20.de
65.40.De pressure (0–8 GPa) and temperature (0–1000 K). Further, CdGeP2 solar cell devices have been modeled;
65.40.
b device physics and performance parameters are analyzed for zinc chalcogenides (ZnX; X ¼ S, Se, Te)
65.60. þ a buffer layers. Simulation results for CdGeP2 thin layer solar cell show the maximum efficiency (22.6%)
71.20.
b with ZnSe as the buffer layer.
& 2015 Elsevier Ltd. All rights reserved.
R

Keywords:
Semiconductors
Optical properties
Mechanical properties
Thermodynamic properties
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1. Introduction
The physics of semiconductor materials used in photovoltaic
(PV) technology is governed by their energy band gaps, optical
properties, etc. Scientifically, recent studies suggest that chalco-
pyrites have truly unique properties not found in classical semi-
conductors and represent the most advanced technology for thin
R
Very recently, Zhang et al. [9] have been successfully grown the
single crystals with the dimension of 8 mm in diameter and
40 mm in length using vertical Bridgman method. Despite such
achievements very little is known about these materials in com-
parison with Si or binary compounds. The progress of Cd(SiGeSn)
P2-based technologies has mostly been attained using scientific
intuition rather than knowledge-based design: technology first

film photovoltics [1–4]. Cadmium chalcopyrites are currently of
technological interest since it shows promise for applications in
the areas of optical parametric oscillators and upconverters [5–8].
These semiconductors crystallize in the chalcopyrite structure
12
with I-42d (D2d ) space group and are deduced from that of the zinc
blende by the replacement of the cationic sublattice by two dif-
ferent atomic species. Important physical characteristics, including
transparency, birefringence, and thermo-mechanical properties
have already been measured and can be found in the literature [8].
n
Corresponding author.
E-mail address: ajay_phy@rediffmail.com (A.S. Verma).
and scientific explanation later. Nowadays with the development
of the robust computational techniques the complexities of ex-
periments can be eliminated, as in these methods only the atomic
numbers of the constituent atoms are required inputs.
In this work, we focus on CdGeP2 and present the results of first
principles calculations for their structural, electronic, optical,
elastic and thermal properties within the density functional the-
ory. The outline of the paper is as follows. In Section 2 we have
given a brief review of the computational scheme used. The cal-
culations of the structural, electronic and optical properties along
with the computed elastic and thermal properties are described in
Section 3; Section 4 included the device modeling and numerical

http://dx.doi.org/10.1016/j.mssp.2015.07.005
1369-8001/& 2015 Elsevier Ltd. All rights reserved.
728 R. Gautam et al. / Materials Science in Semiconductor Processing 40 (2015) 727–736
simulations of CdGeP2 thin layer cells, in order to analyze the ef-
fect of the different buffer layers (ZnS, ZnSe and ZnTe) on the
performance parameters of the cells; while the summary and
conclusions are drawn in Section 5.
2. Computational methods
The calculations were performed using FP-LAPW computa-
tional scheme [10,11] as implemented in the WIEN2K code [12]. In
this method, the space is divided into an interstitial region (IR) and
non-overlapping (MT) spheres centered at the atomic sites. In the
IR region, the basis set consists of plane waves. Inside the MT
spheres, the basis sets is described by radial solutions of the one-
particle Schrödinger equation (at fixed energy) and their energy
D
derivatives multiplied by spherical harmonics without spin–orbit
interactions. The FP-LAPW method expands the Kohn–Sham or-
bitals in atomic like orbitals inside the muffin-tin (MT) atomic
spheres and plane waves in the interstitial region. The Kohn–Sham
TE
equations were solved using the recently developed Wu-Cohen
generalized gradient approximation (WC-GGA) [13,14] for the
exchange-correlation (XC) potential. It has been shown that this
new functional is more accurate for solids than any existing GGA
and meta-GGA forms. For a variety of materials, it improves the
equilibrium lattice constants and bulk moduli significantly over
local-density approximation [15] and Perdew–Burke–Ernzerhof
(PBE) [16] and therefore is a better choice. For this reason we
adopted the new WC approximation for the XC potential in
studying the present systems. Further for electronic structure
calculations modified Becke–Johnson potential (mBJ) [17] as cou-
pled with WC-GGA is used.
The valence wave functions inside the atomic spheres were
C vs [V, c/a (V), u (V)] by FPLAPW calculations and Murnaghan
A
expanded up to l ¼10 partial waves. In the interstitial region, a
plane wave expansion with RMTKmax equal to seven was used for all
the investigated systems, where RMT is the minimum radius of the
muffin-tin spheres and Kmax gives the magnitude of the largest K
vector in the plane wave expansion. The potential and the charge
R
density were Fourier expanded up to Gmax ¼12. We carried out
convergence tests for the charge–density Fourier expansion using
higher Gmax values. The RMT (muffin-tin radii) are taken to be 2.32,
1.7 and 2.11 a.u. (atomic unit) for Cd, P and Ge respectively. The
modified tetrahedron method [18] was applied to integrate inside
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the Brillouin zone (BZ) with a dense mesh of 5000 uniformly
distributed k-points (equivalent to 405 in irreducible BZ) where
the total energy converges to less than 10
6 Ry.
The computer simulation tool AMPS-1D (Analysis of Micro
electronic and Photonic Structures) was employed by specifying
semiconductor parameters as input in each layer of the cell.
R
3. Results and discussion
3.1. Geometry and electronic structure
The ternary chalcopyrite semiconductor crystallizes in the
¯ d (D 12).The Cd
chalcopyrite structure with space group I − 42 2d
atoms are located at (0,0,0); (0,1/2,1/4), the Ge atom at (1/2,1/2,0);
(1/2,0,1/4) and P at (u,1/4,1/8); (
u,3/4,1/8); (3/4,u,7/8); (1/4,
u,7/
8). Two unequal bond lengths dCd–P and dGe–P result in two
structural deformations, first is characterized by u parameter de-
fined as u ¼0.25 þ(dCd–P2
dGe–P2)/a2 where a is the lattice para-
meter in x and y direction, and the second parameter η ¼c/a,
where c is lattice parameter in z direction which is generally dif-
ferent from 2a.
To determine the best energy as a function of volume, we have
minimized the total energy of the system with respect to the other
Table 1
Structural equilibrium parameters, a, c, u, B and B′ calculated in WC-GGA and
thermal properties at 300 K; isothermal bulk modulus (B in GPa), Hardness (H in
GPa), Gruneisen parameter (γ), Debye temperature (θD in K) and thermal expansion
coefficient (α in 10
5/K) of CdGeP2.
Structural analysis a (Å) c (Å) u B (GPa) B′
5.68, 5.73a 11.11, 10.77a 0.262 72.0, 83b 4.84
Thermal analysis B (GPa) H (GPa) γ θD (K) α (10
5/K)
71 5.07, 5.5c,exp 1.86 357, 340d 4.45
a
Reference [43].
b
Reference [42].
c
Reference [48].
d
Reference [49].
exp
Experimental.
geometrical parameters. The minimization is done in two steps,
first parameter u is minimized by the calculation of the internal
forces acting on the atoms within the unit cell until the forces
become negligible, for this MINI task is used which is included in
the WIEN2K code. Second, the total energy of crystal is calculated
for a grid of volume of the unit cell (V) and c/a values, where each
point in the grid involves the minimization with respect to u. Five
values of c/a are used for each volume and a polynomial is then
fitted to the calculated energies to calculate the best c/a ratio. The
result is an optimal curve (c/a, u) as a function of volume. Further a
final optimal curve of total energy is obtained by minimize energy
equation of state [19]. Table 1 present the lattice constants ob-
tained along with the bulk modulus and its pressure derivative.
The calculated total energy per CdGeP2 unit as a function of vo-
lume is shown in Fig. 1(a).
3.2. Electronic and optical properties
The band structure of CdGeP2 without spin–orbit interaction is
shown in Fig. 1(b). As clear from the energy band diagram that
CdGeP2 has a direct band gap at Γ (1.44 eV). To describe the
general features of bonding in more detail the partial and total
density for states (PDOS and DOS) for CdGeP2 is calculated using
the mBJ potential together with Wu-GGA for the correlation
(Fig. 2). The position of the Fermi level is at 0 eV. It can be seen
that in Fig. 2, the valence bands near Fermi level are composed of
mainly of P–p states with minor presence of Ge–p states. The in-
termediate valence band is essentially dominated by Cd–d states.
The other valence bands are essentially dominated by P–s states.
The conduction band consists essentially of Ge–s and P–p states
with a minor presence of Ge–p and P–s states. The comparison of
the theoretical band gaps with available experimental data shows
that mBJ correlation potential allows the prediction of band gap
values much closer to the experimental values. The mBJ potential
gives results in good agreement with experimental values that are
similar to those produced by more sophisticated methods but at
much lower computational costs [17,20].
The linear response to an external electromagnetic field with a
small wave vector is measured through the complex dielectric
function,
ε(ω) = ε1(ω) + iε2(ω) (1)
which is related to the interaction of photons with electrons [21].
The imaginary part ε2 (ω) of the dielectric function could be
obtained from the momentum matrix elements between the
occupied and unoccupied wave functions and is given by [22]
 R. Gautam et al. / Materials Science in Semiconductor Processing 40 (2015) 727–736 729

-33510.66

-33510.67
Energy (Hartree)

-33510.68

-33510.69

D
-33510.70

-33510.71
1050 1100 1150 1200 1250 1300 1350

Volume (bohr3)

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Fig. 1. (a) Calculated total energies as a function of volume and (b) band structure of CdGeP2.

2π 2e2 2 averages are listed in Table 2. The refractive index increases with
⟨Ψkc μ . r Ψkv⟩ δ⎡⎣Ekc − Ekv − ℏω⎤⎦.
∧
ε2(ω) = ∑ ∑ energy reaching a maximum value in the visible region for this
Ωε0 i∈ c .f ∈ v k (2)
compound. The peak value for CdGeP2 is 4.10 at 2.25 eV. Fig. 4
The real part ε1 (ω) can be evaluated from ε2 (ω) using the (b) show extinction coefficient k (ω) of CdGeP2. It is related to the
Kramer–Kronig relations and is given by [23] decay or damping of the oscillation amplitude of the incident
electric field, the extinction coefficient k (ω) decreases with in-
⎛2⎞
ε1(ω) = 1 + ⎜ ⎟
⎝π ⎠ ∫0
∞ ω‵2 ε2(ω‵)
ω‵2 − ω2
dω‵.

All of the other optical properties, including the absorption

C (3)
creasing the incident photon energy.
The calculated optical reflectivity (R (ω)), absorption coefficient
(α (ω)) and photoconductivity (s (ω)) are displayed in Fig. 5. The
maximum reflectivity occurs in region 4.5–11.6 eV for CdGeP2. The
coefficient α (x), the refractive index n (x), the extinction coeffi-
absorption coefficient α (ω) is a parameter, which indicates the
A
cient k (x), and the energy-loss spectrum L (x), can be directly
fraction of light lost by the electromagnetic wave when it passes
calculated from ε1 (ω) and ε2 (ω) [22,24].
through a unit thickness of the material. This has been plotted for
Fig. 3 displays the real and imaginary parts of the electronic
CdGeP2 in Fig. 5(b). It is clear that polarization has a minor influ-
dielectric function ε (ω) spectrum for the photon energy ranging ence on the spectrum. From the absorption spectrum, we can
up to 40 eV. The main peaks of real part of the electronic dielectric easily find the absorption edges of 1.36 eV for CdGeP2. When the
R

function ε1 (ω) which is mainly generated by electronic transition
from the top of the valence band to the bottom of conduction
band, occurs at 2.21 eV and ε1 (ω) spectra further decreases up to
7.21 eV. Optical spectra exhibit anisotropy in two directions (along
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photon energy is more than the absorption edge value, then ad-
sorption coefficient increases. The absorption coefficients further
decrease rapidly in the high energy region, which is the typical
characteristic of semiconductors. Optical conductivity parameters

basal-plane and z-axis) with a very small difference (0.2269) in the
static limit. The imaginary part of the dielectric constant ε2 (ω) is
the fundamental factor of the optical properties of a material.
Fig. 3 displays the imaginary (absorptive) part of the dielectric
function ε2 (ω) up to 40 eV. Our analysis shows that the critical
points of the ε2 (ω) occurs at 1.44 eV corresponding to the main
energy gap. Our onset values of energies have a small deviation
from the experimental band gap (Table 2).
Fig. 4 presents the refractive index n (ω) along with the ex-
R
are closely related to the photo-electric conversion efficiency and
mainly used to measure the change caused by the illumination.
Fig. 5(c) shows the optical conductivities of CdGeP2. It is clear that
this material has non-vanishing conductivity in the in the visible
light region (1.65–3.1 eV), hence has a strong absorption ability of
solar radiations. Therefore are important as solar cell materials.
3.3. Elastic properties

tinction coefficient k (ω). The refractive index spectrum shows an The elastic properties of a solid are among the most funda-
anisotropic behavior (Δn (0 eV)¼ 0.03588) [25], hence only the mental properties that can be predicted from the first-principles

Fig. 2. The calculated partial and total density of states (DOS) for CdGeP2.
730 R. Gautam et al. / Materials Science in Semiconductor Processing 40 (2015) 727–736

20 18

18 E⊥c 16
E⊥c
16 E || c E || c
CdGeP 14 CdGeP
14
12 12
10
10
8

ε2
ε1
6 8

4
6
2
0 4

-2 2
-4
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40

Energy (eV) Energy (eV)

D
Fig. 3. The calculated real ε1 (ω) and imaginary ε2 (ω) parts of complex dielectric constant for CdGeP2.

Table 2 In order to check the internal consistency of calculated elastic

The calculated minimum band gaps Eg (eV), refractive index (n) and dielectric constants we can compare the bulk modulus reported in Table 1
constant for CdGeP2 compared with other experimental and theoretical data.
with an equivalent combination of the Cij's. Bulk modulus should

TE
Eg (eV) this work n This work ε1 This work be bound from above by the Voigt approximation (uniform strain
assumption) [28,29]:
a b c b
1.44, 1.7 , 1.61 3.15, 3.3 , 4.2 9.93, 9.65d
1
BV = (2C11 + C33 + 2C12 + 4C13)
a
Experimental values derived from Reference [44]. 9 (4)
b
Theoretical values derived from Reference [45].
c
Experimental values derived from Reference [45]. Reuss found lower bounds for all lattices [30]
d
Theoretical values derived from Reference [46]. 2
(C11 + C12)C33 − 2C13
BR =
C11 + C12 + 2C33 − 4C13 (5)
ground-state total-energy calculations. The determination of the
elastic constants requires knowledge of the curvature of the en-
ergy curve as a function of strain for selected deformations of the
unit cell. The deformations [26,27] are shown in Table 3 and
C Voigt and Reuss approximations provide, in fact, an estimation
of the elastic behavior of an isotopic material, for instance a
polycrystalline sample. Such a medium would have a single shear
chosen such that the strained systems have the maximum possible constant, G, upper bounded by
A
symmetry. The system has been optimized for each deformed cell
geometry. The WIEN2K package [12] facilitates this task by pro- 1
GV = (M + 3C11 − 3C12 + 12C44 + 6C66)
30 (6)
viding a force-driven optimization of the internal cell geometry.
The elastic stiffness tensor of chalcopyrite compounds has six in- and lower bounded by
R

dependent components because of the symmetry properties of the −1

D212d space group, namely C11, C12, C13, C33, C44 and C66 in Young ⎧ 18B 6 6 3 ⎫
GR = 15⎨ 2 V + + + ⎬
notation. The calculated elastic constant for the tetragonal phase ⎩ C (C11 − C12) C44 C66 ⎭ (7)
of Cadmium chalcopyrite are listed in Table 4. In general, our re- 2 2
sults are in good agreement with the experimental data and the- where C = (C11 + C12)C33 − 2C13
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In the Voigt–Reuss–Hill approximation [31], the B and G of the

oretical data, in particular if we consider, shear constants (C44 and
polycrystalline material are approximated as the arithmetic mean
C66) appear to be no worse than the rest of the elastic constants,
of the Voigt and Reuss limits:
even though the inner strain component is particularly difficult in
those constants. The comparison with other theoretical calcula- BV + BR
B=
tions also shows an important dispersion of values. The calculated 2 (8)
elastic constants fulfill the mechanical stability criteria for the
tetragonal systems: GV + GR
G=
C11 > C12 , (C11 + C12)C33 > 2C132, C44 > 0, and C66 > 0 2 (9)
R

4.5 3.0

4.0 E⊥c E⊥c

E || c E || c
CdGeP2 2.5
3.5 CdGeP2
Extinction coefficient

3.0 2.0
Refractive index

2.5
1.5
2.0

1.5 1.0

1.0
0.5
0.5

0.0 0.0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Energy (eV) Energy (eV)

Fig. 4. The calculated refractive index and extinction coefficient for CdGeP2.
 R. Gautam et al. / Materials Science in Semiconductor Processing 40 (2015) 727–736 731

180

0.6
E⊥c 160 E⊥c
E || c E || c
CdGeP2 140 CdGeP2
0.5
120

α (ω) (10 /cm)

0.4

Reflectivity
100

0.3 80

60
0.2
40

0.1 20

0
0.0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Energy (eV)
Energy (eV)

D
12000
11000 E⊥c
10000 E || c
CdGeP2
9000

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8000
σ (ω) (1/Ohm.cm)

7000
6000
5000
4000
3000
2000
1000
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
C Energy (eV)

Fig. 5. The calculated (a) reflectivity (R (ω)), (b) absorption coefficient (α (ω)) and (c) photoconductivity (s (ω)) for CdGeP2.

Table 3
A
The lattice parameters of the deformed tetragonal unit cell, the expression relating the δ and ε variables, the finite Lagrangian
strain tensor (Voigt notation) and the value of the second derivative, (1/2 V) (dE2/dε2), in terms of the elastic constants (ε being
deformation coordinate and E the energy).

Strained cell ε Strain (η) dE2/dε2

R

c + cδ ε ε cε
(a + δ , a + δ , , 90, 90, 90) (a + δ )2 ( , , , 0, 0, 0) 1
(C + C12) +
1
C +
1
C
a −1 2 2 2a 4 11 8 33 2 13
a2
ε ε
(a + δ, a + δ, c, 90, 90, 90) (a + δ )2 ( , , 0, 0, 0, 0) 1
(C + C12)
−1 2 2 4 11
a2
c + cδ ε
(a , a , , 90, 90, 90) (c + δ )2 (0, 0, , 0, 0, 0) 1
C
a −1 2 8 33
c2
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ε
(a, a + δ, c, 90, 90, 90) (a + δ )2 (0, , 0, 0, 0, 0) 1
C
−1 2 8 11
a2
(a, a, c, 90, 90 + δ, 90) sin δ (0, 0, 0, 0, ε, 0) C44
(a, a, c, 90, 90, 90 + δ ) sin δ (0, 0, 0, 0, 0, ε ) C66

Table 4 tetragonal structure, the linear compressibilities κa and κc along

Elastic constants Cij (in GPa) of the CdGeP2 compared with available data. the a- and c-axis respectively are given in term of elastic constants
by the following relations;
R

C11 C12 C13 C33 C44 C66

107, 84a 61, 53a 63, 50a 102, 79a 47, 29a 48, 26a 1 ∂a C33 − C13
B (GPa) G (GPa) Y (GPa) ν κa (GPa
1) κc (GPa
1) κa = − = 2
76.63 34.43 89.84 0.30 0.0043 0.0045
a ∂p C33(C11 + C12) − 2C13 (12)
a
Reference [47]. 1 ∂c C11 + C12 − 2C13
κc = − = 2
c ∂p C33(C11 + C12) − 2C13 (13)
Finally the Poisson ratio and the Young modulus are obtained
as Pugh [32] proposed that the resistance to plastic deformation is
3B − 2G related to the product Gb, where ‘b’ is the Burgers vector, and that
υ= the fracture strength is proportional to the product Ba, where ‘a’
2(3B + G) (10)
corresponds to the lattice parameter. As b and a are constants for
specific materials, the Ba/Gb can be simplified into B/G. This for-
9BG
Y= mula was recently exploited in the study of brittle vs ductile
3B + G (11)
transition in intermetallic compounds from first-principles calcu-
Using the single crystal Cij data, one can evaluate the linear lations [33,34]. A high B/G ratio is associated with ductility,
compressibilities along the principles axis of the lattice. For the whereas a low value corresponds to the brittle nature. The critical
732 R. Gautam et al. / Materials Science in Semiconductor Processing 40 (2015) 727–736

1280 110
0 GPa 2 GPa
4 GPa 6 GPa 0 GPa 2 GPa
1260 105 4 GPa 6 GPa
8 GPa
100
8 GPa
1240
95
1220
90

V (bohr 3)
1200

B (GPa)
85
1180
80
1160 75

1140 70

1120 65

0 100 200 300 400 500 600 700 800 900 1000 60
0 100 200 300 400 500 600 700 800 900 1000
Temperature (K) Temperature (K)

Fig. 6. Volume vs temperature and Bulk modulus vs temperature at various pressures for CdGeP2.

D
value which separates ductile and brittle material is around 1.75, ⎡ ⎛θ ⎞ ⎤
i.e., if B/G4 1.75, the material behaves in a ductile manner other- S = nk⎢4D⎜ ⎟ − 3 ln 1 − e−θ / T ⎥
⎣ ⎝T ⎠ ⎦ ( ) (20)
wise the material behaves in a brittle manner. We have found that
B/G ratios 2.23 for CdGeP2, classifying this material as ductile. γCV

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Consequently, the Ba/Gb reflects the competition between the α=
BT V (21)
shear and cohesive strengths at the crack tip of fracture.
where γ is the Grüneisen parameter, which is defined as
3.4. Thermal properties d ln θ (V )
γ=−
d ln V (22)
To investigate the thermodynamic properties of Cd-chalcopyr-
ite, we have used Gibbs program. The obtained set of total energy Through the quasi-harmonic Debye model, one could calculate
vs primitive cell volume determined in previous section has been C the thermodynamic quantities of any temperatures and pressures
used to derive the macroscopic properties as a function of tem- of compounds from the calculated E–V data at T¼ 0 and P¼ 0.
perature and pressure from the standard thermodynamic rela- We can also provide a prediction of the hardness by using the
tions. Gibbs program is based on the quasi-harmonic Debye model semi-empirical equation developed by Verma et al. [41]
[35,36], in which the non-equilibrium Gibbs function G*(V; P, T)
H = K B K+1 (23)
can be written in the form of
A
where B and K are the bulk modulus and constant respectively.
G*(V ; P , T ) = E(V ) + PV + A vib [θD; T ] (14) The value of K is 0.59 for AIIBIVC2V.
where E(V) is the total energy per unit cell, PV corresponds to the Through the quasi-harmonic Debye model, the thermodynamic
constant hydrostatic pressure condition, θD is the Debye tem- properties are determined in the temperature range from 0 to
1000 K and pressure effects are studied in the 0–8 GPa range. Fig. 6
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perature, and Avib is the vibrational term, which can be written

using the Debye model of the phonon density of states as [37,38]: (a) presents relationships between the equilibrium volume V
(bohr3) and pressure at T ¼0–1000 K. Meanwhile, the equilibrium
⎡ 9θ ⎛ θ ⎞⎤
A vib [θD; T ] = nkT ⎢
⎣ 8T (
+ 3 ln 1 − e−θ / T − D⎜ ⎟⎥
⎝ T ⎠⎦ ) (15)
volume V decreases dramatically as the pressure P increases at a
given temperature. This account suggests that the CdGeP2 under
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loads turns to be more compressible with increasing pressure than

where n is the number of atoms per formula unit, D (θ/T) re-
presents the Debye integral, and for an isotropic solid, θ is ex- decreases temperature. Furthermore, It is also noted that the re-
pressed as [37]: lationship between the bulk modulus and temperature in Fig. 6(b).
The bulk modulus slightly decreases with increasing temperature
ℏ ⎡ 2 1/2 ⎤1/3 BS at a given pressure and increases with increasing pressure at a
θD = ⎣6π V n⎦ f (σ ) (16)
k M given temperature.
The variation of the Debye temperature θD (K) as a function of
M being the molecular mass per unit cell and BS the adiabatic
pressure and temperature illustrated by our results is displayed in
bulk modulus, approximated by the static compressibility [35]:
R

Fig. 7(a). With the applied pressure increasing, the Debye tem-
d2E(V ) peratures are almost linearly increasing. Fig. 7(b) shows the vo-
BS ≅ B(V ) = V
dV 2 (17) lume thermal expansion coefficient α (10
5 K
1) at various
pressures, from which it can be seen that the volume thermal
f (s) is given by Refs. [35,39]; s is the Poisson ratio [40].
expansion coefficient α increases quickly at a given temperature
Therefore, the non-equilibrium Gibbs function G*(V; P, T) as a
particularly at zero pressure below the temperature of 300 K. After
function of (V; P, T) can be minimized with respect to volume V,
a sharp increase, the volume thermal expansion coefficient is
⎛ ∂G*(V ; P , T ) ⎞ nearly insensitive to the temperature above 300 K due to the
⎜ ⎟ =0 electronic contributions.
⎝ ∂V ⎠P, T (18)
As very important parameters, the heat capacities of a sub-
By solving Eq. (18), one can obtain the thermal equation of state stance not only provide essential insight into the vibrational
(EOS) V(P, T). The heat capacity CV and the thermal expansion properties but are also mandatory for many applications. Our
coefficient α are given by [31], calculation of the heat capacities CP and CV of CdGeP2 vs tem-
perature at pressure range 0–8 GPa are shown in the following
⎡ ⎛θ ⎞ 3θ / T ⎤
CV = 3nk⎢4D⎜ ⎟ − θ / T ⎥ Fig. 8. From these figures, we can see that the constant volume
⎣ ⎝T ⎠ e − 1⎦ (19) heat capacity CV and the constant pressure capacity CP are very
 R. Gautam et al. / Materials Science in Semiconductor Processing 40 (2015) 727–736 733

6
430 0K 100 K 200 K 300 K
420
400 K 500 K 600 K
700 K 800 K 5
410 900 K 1000 K
400
4
390

α (10 /K)
θD (K)
380 3
370

360 2 0 GPa
350 2 GPa
4 GPa
340 1 6 GPa
330
8 GPa

0 1 2 3 4 5 6 7 8 0
0 100 200 300 400 500 600 700 800 900 1000
Pressure (GPa)
Temperature (K)

Fig. 7. Debye temperature (θD in K) vs pressure (GPa) and Thermal expansion coefficients (α in 105 K
1) vs temperature (in K) for CdGeP2.

D
similar in appearance and both of them are proportional to T3 at dimensional Poisson equation and the continuity equations for
low temperatures. At high temperatures, the anharmonic effect on free charge carriers. These equations are expressed as follows:
heat capacity is suppressed; which is called Dulong–Petit limit,
with the increasing of the temperature, whereas CP increases d ⎛ dψ ⎞
⎜ − ε(x) ⎟

TE
monotonically with the temperature. Fig. 9(a) shows the entropy dx ⎝ dx ⎠
vs temperature at various pressures. The entropies are variable by = q⎣p(x) − n(x) + ND+(x) − NA−(x) + pt (x) − nt (x)⎤⎦
⎡
(24)
power exponent with increasing temperature but the entropies
are higher at low pressure than that at high pressure at same
temperature. The Grüneisen parameter γ is another important dpn pn − pn0 dE dp dp 2
= Gp − − pn μ p − μ p E n + Dp n2
quantity for the material. In Fig. 9(b), we have shown the values of dt τp dx dx dx (25)
Grüneisen parameter γ at different temperatures and pressures. It
shows the value γ increases as the temperature increases at a gi- C dn p n p − n p0 dE dn p dnp2
ven pressure and decreases as the pressure increases at a given = Gn − + npμn + μn E + Dn
dt τn dx dx dx 2 (26)
temperature.
In Fig. 10, we have shown the values of hardness (H in GPa) at Where ε the permittivity, q the charge, Ψ the electrostatic poten-
different temperatures and pressures. It shows the hardness de- tial, n the free electron, p the free holes, ND+ the donor like doping,
creases as the temperature increases at a given pressure and in- NA− the acceptor like doping, E the electric field and G the gen-
A
creases as the pressure increases at a given temperature. The va- eration rate, D the diffusion coefficient, τ the lifetime and μ the
lues of hardness are reported for the first time at different pressure mobility of charge carriers. With the help of solution of these
and temperature. Table 1 also presents the thermal properties equations current/voltage (I/V) characteristics are determined and
such as isothermal bulk modulus, hardness, Grüneisen parameter, performance of solar cell with different buffer layers is compared.
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Debye temperature and thermal expansion coefficient at 300 K. In Table 5 we have presented description for the parameters;
which was used in the simulation. Simulated results are presented
in Table 6. These were base parameters; that were used through-
4. Cell structure, material parameters and cell performance out the study [50–54]. The schematic energy-band diagram for
modeled cell structure with ZnTe, ZnS and ZnSe buffer layers are
ET

The cell structure in the present study consists of the layers, Al shown in Fig. 12. The illumination has done by AM1.5G (Air Mass
doped ZnO, n type buffer layer (ZnS/ZnSe/ZnTe), p-CdGeP2 absor- 1.5 Global 1000 W/m2) photon flux. This figure clearly represents
ber and Mo on glass substrate. Fig. 11 illustrates the dimensions the energy band gap discontinuity in between valance and con-
and the different regions of the modeled cell. The device simula- duction band. This discontinuity arises as spikes in the energy
tion is based on the solution of a set of equations, which provides a band diagram. These dangling bonds work as potential wells and
mathematical model for device operation. Using this model, the behave as intermediate energy states. These states work as
influence of the modeling parameters over the efficiency of the recombination centers and minimize the performance of the cell.
device can be examined, which is a tedious task by experimental The more height of spikes represents higher losses by recombina-
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method. The simulation is based on the solution of one tion process. Fig. 13 shows the current/voltage (I/V) characteristics

250
200

200

150
C (J/mol.K)

150
C (J/mol.K)

100
100
0 GPa
0 GPa
2 GPa
2 GPa
50 4 GPa
4 GPa
50 6 GPa
6 GPa
8 GPa
8 GPa
0
0 0 100 200 300 400 500 600 700 800 900 1000
0 100 200 300 400 500 600 700 800 900 1000
Temperature (K) Temperature (K)

Fig. 8. Heat capacity vs temperature at various pressures for CdGeP2.

734 R. Gautam et al. / Materials Science in Semiconductor Processing 40 (2015) 727–736

1.96
500 1.94 0 GPa 2 GPa
1.92
4 GPa 6 GPa
8 GPa
1.90
400
1.88
1.86

S (J/mol.K)
300 1.84
1.82

γ
1.80
200 0 GPa 1.78
2 GPa
4 GPa 1.76
100 6 GPa 1.74
8 GPa 1.72

0 1.70
0 100 200 300 400 500 600 700 800 900 1000 0 100 200 300 400 500 600 700 800 900 1000
Temperature (K) Temperature (K)

Fig. 9. Entropy vs temperature and Gruneisen parameter vs temperature at various pressures for CdGeP2.

D
10
0 GPa 2 GPa The quantum efficiency curves for CdGeP2 solar cell with dif-
4 GPa 6 GPa
9 ferent buffer layers are shown in Fig. 14. The response of the cell is

TE
8 GPa
analyzed for solar spectrum from 500 nm to 1000 nm. The dif-
ferent buffer layers have differences in their band gaps. So the
Hardness (H in GPa)

different parts of spectrum are absorbed by the layers near the

7
junction. This difference arises as the layer with higher band gap
6 provides a wider window for radiation to get absorbed in ab-
sorption layer. Moreover, the quantum efficiency of CdGeP2/ZnS
5 heterojunction solar cell is least though the band gap for ZnS
C buffer layer is highest among the considered buffer layers. The
4
reason behind this contradictory result is that the quantum effi-
0 100 200 300 400 500 600 700 800 900 1000 ciency is not the measure of generation of photo-generated car-
Temperature (K) riers; but it is a measure of the effectiveness of separation of
Fig. 10. Hardness vs temperature at various pressures for CdGeP2. charge carriers in the depletion region [55]. The results show that
probability of recombination of charge carriers is more in CdGeP2/
A
ZnS heterojunction structure due to small diffusion length and
high recombination rate; whereas recombination is less in
CdGeP2/ZnSe heterojunction structure, showing higher quantum
efficiency. Hence CdGeP2 as absorption layer with ZnSe buffer has
R

been a promising solar cell model; which is not only beneficial on

the energy basis but also helps in overcoming the serious en-
vironmental related problems.
ET

5. Summary and conclusion

To conclude, results have been presented for the solid state

properties such as structural, electronic, optical, elastic and ther-
mal properties of the CdGeP2 using the first-principles calculation.
The structural properties in the chalcopyrite structure are obtained
using the total energy as a function of volume; the derived equi-
Fig. 11. The CdGeP2 based typical solar cell structure for different buffer layers.
librium parameters are compared with experimental data. We
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compared electronic and optical properties calculated with the

mBJ functional and spectroscopic ellipsometry data. We find that
of CdGeP2 solar cell with a variety of buffer layers. The short circuit the mBJ functional provides an accurate description of the elec-
current density and open circuit voltage are calculated with help tronic and optical properties. The CdGeP2 has a direct band gap.
of these I/V characteristics. The short circuit current density (Jsc We have also derived the static refractive index. Thermal proper-
(mA/cm2)) and open circuit voltage (Voc (mV)) are almost similar ties such as Grüneisen parameter, volume expansion coefficient,
for ZnS, ZnSe and ZnTe buffer layers. With these buffer layers the bulk modulus, specific heat, entropy, Debye temperature and
barrier generated at the interface of absorption layer and buffer hardness are calculated successfully at various temperatures and
layer are equal, thus creating same type of results. Here we have pressures, and trends are discussed. The ground state parameters
find good efficiency (η (%)) and fill factor (FF (%)) for CdGeP2 solar of interest were obtained and showed good agreement with
cell with both the buffer layers i.e. ZnS, ZnSe and ZnTe; but published experimental and theoretical data. An application of the
efficiency and fill factor are considerably higher for CdGeP2/ZnSe material in solar cell device has been presented; here we have
heterojunction solar cell. The good performance of this cell used AMPS-1D to investigate the dependence of the buffer layer
structure ensures the better lattice matching in between CdGeP2 for thin layer CdGeP2 solar cells. The performance parameters of
absorption layer and ZnSe buffer layer. solar cells as current/voltage (I/V) characteristics, quantum effi-
ciency, fill factor and the conversion efficiency have been
 R. Gautam et al. / Materials Science in Semiconductor Processing 40 (2015) 727–736 735

Table 5
The parameters for CdGeP2 solar cell structure.

Layers 1
nþ ZnO 2
n(i) ZnO 3
ZnS 3
ZnSe 3
ZnTe 4
CdGeP2

Parameters

Thickness (nm) 50 50 30 30 30 2500

ε (dielectric constant) 9a 9a 10a 10a 14b 9.93c
μn (electron mobility in cm2/Vs) 50d 50d 50a 50a 70b 100e
μp (hole mobility in 10 cm2/Vs) 5d 5d 20a 20a 50b 30–60e
n/p (carrier density in cm
3) 1.7  1019d 5  1016d 1  1017a 5.5  107a 7.5  1019b 3
4  109e
Eg (eV) (band gap) 3.3a 3.3a 3.5a 2.9a 2.25b 1.44c
Nc (electron density in cm
3) 1  1019d 1  1019d 1.5  1018a 1.5  1018a 1  1015b 3  1014
Nv (effective density in cm
3) 1  1019d 1  1019d 1.8  1018a 1.8  1019a 1.5  1019b 1  1016
χ electron affinity (eV) 3.9d 3.9d 4.5a 4.09a 3.65b 3.98f

a
Reference [50].

D
b
Reference [52].
c
This work.
d
Reference [51].
e
Reference [53].
f
Reference [54].

TE
Table 6 100

Simulated performance parameters of the CdGeP2 solar cell. 90

2 80
Buffer layer η (%) Voc (mV) Jsc (mA/cm ) FF (%)

Quantum Efficiency (%)

70
ZnS 12.4 978 27.6 46.1
60
ZnSe 22.6 979 30.5 75.8
ZnTe 15.4 981 29.9 52.5 50
C 40

30

20

10
ZnS ZnSe ZnTe

500 550 600 650 700 750 800 850 900 950 1000 1050
A
Wavelenght (nm)

Fig. 14. Quantum efficiency of CdGeP2 solar cell.

the best of our knowledge, most of the investigated parameters are

reported for the first time and will further stimulate the research
R

in the related field.

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ET

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