Journal of Physics and Chemistry of Solids 182 (2023) 111548

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Journal of Physics and Chemistry of Solids

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

Ab initio insight into the structural, vibrational, electronic, optical,

magnetic, and thermal properties of lead-free perovskite Cs3Sb2Cl9 for solar
cell application
Zia ur Rehman a, *, M. Awais Rehman b, Hamna Chaudhry b, Muhammad Awais a
a
Department of Mathematics, Namal University, 30km Talagang Road, 42250, Mianwali, Pakistan
b
Department of Physics, Khwaja Fareed University of Engineering and Information Technology, Rahim Yar Khan, Pakistan

A R T I C L E I N F O A B S T R A C T

Keywords: In recent years, semiconducting lead (Pb) free perovskite materials have become more attractive materials due to
DFT their less toxicity. In this study, we have investigated structural, electronic, optical, magnetic, and thermal
CASTEP properties of Pb-free Cs3Sb2Cl9 perovskite material using density functional theory. We have calculated the
Electronic properties
Energy-Volume (E-V) curve to evaluate the structural stability. The estimated lattice parameters for the studied
Solar cells
Pb-free perovskite
material are a = b = 7.818 Å and c = 9.436 Å. Electronic properties suggest that Cs3Sb2Cl9 is a semiconductor
material with a suitable energy band gap (Eg = 3.214 eV) for solar cell applications. Optical properties like high
absorption, high optical conductivity, and peak reflectivity value in the visible region suggest that Cs3Sb2Cl9 is
the most promising material for photovoltaic applications. Furthermore, the dynamic vibrational stability has
been investigated as a calculated phonon energy dispersion curve, which shows that Cs3Sb2Cl9 is a dynamically
stable compound. The spin-polarized calculations show that the material as a whole and even at the elemental
bands level has zero resultant magnetic moments. We have also calculated thermodynamic properties, including
enthalpy, free energy, and entropy. Therefore, the calculated results suggest that Cs3Sb2Cl9 is a potential
candidate for solar cell applications.

1. Introduction
In recent years, organic and inorganic lead halide perovskites have
attracted much attention from the scientific community due to their
outstanding performance in photovoltaic and optoelectronics applica­
tions, i.e., solar cells, light-emitting diodes, lasers, and photocatalysis.
The Pb-based halide perovskites of the type CH3NH3PbX3 have received
the most attention in the perovskite family because of their good carrier
mobility, high absorption coefficient, long carrier diffusion length, and
low exciton binding energy [1–3]. The power conversion efficiency of
perovskite solar cells is equivalent to standard photovoltaic materials
like CdTe (22.1%), Si (26.1%), and GaAs (27.8%), having grown rapidly
from 3.8% in 2009 to 25.2% recently [4]. Despite being toxic to the
human body, Pb constitutes a major part of the structure of MAPbX3,
with X = Cl, Br, I. Due to this, it is essential to find an alternative halide
perovskite material for Pb that is also stable and less toxic [5]. According
to the literature, there are primarily three types of metal ions that can
substitute Pb2+: bivalent metal ions of the IIA-group, IVA-group, or
transition group (like Ge2+ and Sn2+); non-bivalent metal ions with a
corresponding atomic number to Pb (like Sb3+ and Bi3+); and one-valent
and three-valent metal ions that can make double perovskite structures
[6–9]. In this perspective, 2-dimensional Pb-free perovskites have been
investigated extensively because of their high absorption coefficient,
outstanding carrier mobility, and tunable energy band gap [10,11]. To
make non-toxic halide perovskite for solar cells and optoelectronics, it is
the natural way to combine the two types of substitution, i.e., Ge2+ and
Sn2+, Sb3+ and Bi3+, and Ag+ and Bi3+. As a result, several of the Cs
containing halide perovskites without Pb have been synthesized and
used in solar cells [12]. In general, there are two distinct types of Pb-free
Cs-containing perovskite material. One type is known as single structure
perovskite material with the general formula CsGeX3, CsBrX3, CsSbX3,
and Cs3Bi2X9 and Cs3Sb2X9 (where X = Cl, Br, I). The second type is
double-structure perovskite material with the general formula Cs2TiX6,
Cs2SbX6, and Cs2AgBiX6 (where X = Cl, Br, I) [9,13]. Cs3Sb2X9 (where X
= Cl, Br, I) is a two-dimensional layer structure perovskite material that
is less toxic and has excellent stability relative to lead-based perovskite

* Corresponding author.
E-mail address: zia545@gmail.com (Z. Rehman).

https://doi.org/10.1016/j.jpcs.2023.111548
Received 28 February 2023; Received in revised form 24 June 2023; Accepted 9 July 2023
Available online 23 July 2023
0022-3697/© 2023 Published by Elsevier Ltd.
 Z. Rehman et al.
materials. Compared to normal perovskites, carefully developed
two-dimensional perovskites generally exhibit higher levels of stability
in addition to improved photovoltaic and optoelectronic performance
[14,15]. New two-dimensional perovskites have recently attracted much
attention because of their unique structure and higher structural sta­
bility than the three-dimensional equivalents resulting from lower for­
mation energy [16]. There are two distinct crystal structures for the
perovskite Cs3A2B9 (A = Bi, Sb; B = Cl, Br, I), a trigonal crystal structure
and an orthorhombic crystal structure [17]. In the trigonal phase of
these Pb-free halide perovskites, AB6 polyhedra create a layered struc­
ture in the ab plane [18,19]. In contrast, in the orthorhombic phase, they
form zigzag double chains in the b direction due to corner sharing.
Pradhan et al. has recently produced Cs3Sb2Cl9 nanoparticles with
trigonal and orthorhombic phases by adjusting the precursors and sol­
vents [20]. A3B2M9 (where A = Rb, Cs, and CH3NH3; B = Bi, Sb; M = Cl,
Br, I) nanomaterials of perovskite with a Bi substitution at the Sb site
have been synthesized by Yao et al. [21]. Based on this concept, by using
the first principles calculations, Zhao et al. conducted an exhaustive
investigation of the structural, electronic, and optical properties of the
double perovskites Cs2InXCl6 (X = Sb, Bi) [22]. Both these perovskites
include lone pairs of s electrons. Wu et al. reported that two-dimensional
layered Ruddlesden proper type perovskite compounds Cs2Cu1/2
Bi1/2Cl4, Cs4In3/2Sb3/2Cl0, and Cs4In3/2Sb3,/2I10 show an attractive
lead-free solid-state-lighting and solar cell absorbers materials [23]. Wu
et al. developed a high-quality double perovskite (Cs2AgBiBr6) with
1.44% power conversion efficiency [24]. Using a 2D ultrathin approach,
Sarkar et al. produced lead-free, Cs3Bi2I9 perovskites with excellent
photostability [25]. The power conversion efficiency of Bi-based and
Sb-based perovskites is still fairly low, even though a high absorption
coefficient may be attained. Two-dimensional orientated layered pe­
rovskites with a general chemical formula An+1BnX3n+3 also attracted
researchers [26]. In this formula, A is a monovalent cation, B is a
trivalent cation, and X is a halogen anion. These two-dimensional pe­
rovskites have many remarkable properties, like a long carrier duration,
impressive defect tolerance, high carrier mobility, a highly suitable band
gap, and excellent photoluminescence quantum efficiency [27,28].
In the present study, we will investigate the Pb-free perovskite
Cs3Sb2Cl9 as potential substitutes to MAPbX3 by calculating structural,
electronic, optical, mechanical, and magnetic properties using the first
principle GGA-PBE and HSE06-based calculations as implemented in
CASTEP. According to previous literature, perovskite materials have
potential applications in various fields, including solar energy harvest­
ing; this fact led us to investigate the physical properties of Pb-free
perovskite for their potential applications [29]. Our calculations sug­
gest that Cs3Sb2Cl9 has excellent electronic properties, a suitable energy
band gap, and high absorption coefficient for optoelectronic and
photovoltaic applications. The current manuscript has four sections to
describe the present study fully. Section 1 describes the introduction and
motivation of the current research work. The methodology is given in
Section 2, whereas the results and discussions are presented in Section 3.
Finally, the article is concluded in Section 4.
2. Computational methodology
The investigations in this study are carried out using the Cambridge
Serial Total Energy Package (CASTEP) module of Materials Studio,
which is based on density functional theory (DFT) with the plane wave
pseudopotential method [30]. The generalized gradient approximation
(GGA) and Perdew-Burke-Ernzerhof (PBE) techniques were applied. A
supercell k-mesh with 6 × 6 × 6 point was performed to optimize ge­
ometry, and the plane wave cutoff energy was adjusted to 517 eV. The
geometry optimization of Cs3Sb2Cl9 was performed to get a stable
electronic crystal structure. The atomic calculation for Cs 4s2 4p6 4 d10
4f14, Sb 4 d10 5s2 5p3, and Cl 3s2 3p5 were employed. The finite strain
theory was utilized to investigate the values of elastic constants.
Vanderbilt-type ultrasoft pseudopotentials were used to examine the
2
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Journal of Physics and Chemistry of Solids 182 (2023) 111548
electrostatic interaction between the valence electron and the ionic core.
Ultrasoft pseudopotentials of the Vanderbilt type are used to explain the
electron-ion interaction [31]. A much finer separation grid, 0.015 Å, was
used for phonon and electronic band structure calculations. The crystal
structure was optimized using a Broyden-Fletcher-Goldfarb-Shanno
(BFGS) relaxation technique. The electronic, optical, thermodynamic,
phonon, and magnetic properties were investigated after the geometry
optimization. These values were used for convergence parameters:
maximum atomic displacement was 1.0 × 10− 3, the maximum force was
0.03 eV/nm, maximum stress was 0.05 GPa, and maximum energy was
5 × 10− 6 eV/atom. All the computations were done using the
High-performance computing facility [32].
3. Result and discussion
3.1. Structural properties
To study the physical properties of a material, it is essential to
investigate the structural parameters of CS3Sb2Cl.9 Table 1 shows the
experimental, calculated, and previously reported lattice parameters.
The calculated geometry optimization values are close to previously
reported theoretical structural data and compared to experimental
values. Furthermore, the calculated band gap is less than reported in the
literature because GGA yields a lower bandgap [33]. The Cs3Sb2Cl9
perovskite belongs to P3m1 space group 164, having a trigonal crystal
structure and hexagonal lattice. There are a total of 14 atoms in a unit
cell of Cs3Sb2Cl9. The Wyckoff position of Cs (0, 0, 0), Cs (2/3, 1/3,
0.6670), Sb (2/3 1/3 0.1859), Cl (1/2 0 0) and Cl (0.8247 0.1752
0.3345). To unveil the ground state parameters, geometry optimization
was performed. To evaluate the structural stability of Cs3Sb2Cl9 perov­
skite, we have calculated the Energy-Volume (E-V) curve. The structure
was relaxed, and a final volume was achieved, as shown in Fig. 1. The
structural parameters with the lowest energy were selected and shown
in Table 1. The black dot represents the data points, whereas the red line
shows the Birch-Murnagahan equation of state-fitting data. The crystal
structure of Cs3Sb2Cl9 can be seen in Fig. 2. The calculated parameters a
= b = 7.8186 Å and c = 9.4361 Å are comparable to experimentally
observed parameters a = b = 7.6300 Å, c = 9.3450 Å [34]. The shorter
and longer bond length of Cl-Sb is 2.5100 Å and 2.8100 Å, respectively.
Geometry optimization was performed using the Generalized Gradient
approximation (GGA) algorithm to fully optimize the structure using
exchange and correlation potentials of Per-dew–Burke–Ernzerhof (PBE)
[34,35].
3.2. Electronic properties
Electronic properties such as band structure and DOS help under­
stand the bonding nature and its physical properties.
3.2.1. Band structure
In Fig. 3, the conduction band minima and valence band maxima are
located at A and G symmetry points, respectively. The band structure
provides the allowed energy values for the electrons. Since the DFT
calculations are performed at 0 K without considering temperature ef­
fects. The highest energy level in the valence band is labeled as the Fermi
level (EF). Hence, the bands above and below the Fermi level are called
conduction and valence bands, respectively. The band gap is calculated
through the difference in valence band maxima and conduction band
Table 1
Experimental and calculated Cs3Sb2X9 structural properties.
Compound a (Å) c (Å) V (Å3) c/a References
Cs3Sb2I9 7.818 9.436 576.830 1.207 Present Work
Cs3Sb2I9 8.420 10.386 736.330 1.233 Experimental [34]
Cs3Sb2I9 7.633 9.345 544.464 1.224 Theoretical [36]
Z. Rehman et al. Journal of Physics and Chemistry of Solids 182 (2023) 111548

10 eV. Fig. 3 shows the total density of states of Cs3Sb2Cl9 and TDOS of
individual crystal atoms. The calculated total densities of states at the
Fermi level EF are 1.42 states/eV, 0.05 states/eV, 0.87 states/eV, 2.98
states/eV for Cs3Sb2Cl9, Cs, Sb, and Cl respectively. The TDOS of the
compound gets a major part from the chlorine, as shown in Fig. 4. To

Fig. 1. Energy volume curve of Cs3Sb2Cl9.

minima. In our study, the crest of the valence bond and trough of the
conduction band are slightly unaligned, as shown in Fig. 3, which rep­
resents the electronic band structure showing an indirect band gap with
a bandgap value of 2.406 eV. The band gap value calculated using GGA
is lower than the experimental value because GGA always predicts a
bandgap lower than the actual value. However, the variation in the
bandgap related to atomic densities and types is considerably accurate
[37,38]. Further calculations using HSE06 functional technique yielded Fig. 3a. Electronic band structure of Cs3Sb2Cl9.
a bandgap of 3.214 eV, which is close to the experimental value of 3.09
eV. The band gap depicts the semiconductor nature of the material at 0
K. The solid’s full energy bands and bandgap were calculated for the
Brillion zone along the path (G-A-H-K-G-M-L-H). The calculations were
performed for crystals of a relaxed structure corresponding to minimum
energy. Band structure plots were drawn in the energy range − 5 eV–5 eV
and wave vectors k. Band structure depicts the atomic orbitals within a
unit cell. The energy of the highest occupied state EF is shown by a
dotted line in Fig. 3.

3.2.2. Density of states

DOS is an essential element of electronic properties. The total Den­
sity of States (TDOS) and Partial Density of States (PDOS) for CS3Sb2Cl9
were calculated to reveal the electronic properties and nature of the
∑
chemical bond. The overall DOS Nx(E) of x orbital is given as [39].
∑ ∑ ∫ dk
DOS = Nx (E) = δ(E − Ex (k))
4π3
Ex(k) represents the dispersion of the band through the first Brillion
zone. It is observed that EF has low DOS and is a stable crystal con­
cerning the free electron model. DOS and PDOS of Cs3Sb2Cl9 are drawn
from − 10 eV to 10 eV and − 10 to 15 eV, respectively. The valance band
ranges from − 10 eV to 0 eV, and the conduction band starts from 0 eV to Fig. 3b. Electronic band structure of Cs3Sb2Cl9.

Fig. 2. Crystal structure of Cs3Sb2Cl9.

3
Z. Rehman et al.
study the contribution of individual orbitals of atoms in a crystal, PDOS
results were examined. Fig. 5 represents the PDOS of the Cs3Sb2Cl9 and
constituent atoms. The figure shows that the major contribution to the
valence band of the compound comes from the p orbital of Cs (Cs-p) and
chlorine (Cl-p), respectively. The most prominent peak at the Fermi level
3.03 states/eV was obtained due to the contribution of Cl-p orbital [40].
3.2.3. Population analysis
To get detailed insight, a population analysis was done. Table 2
represents the atomic population, charge, population average, and
average bond lengths. Since Cs and Sb atoms have a positive charge
contribution to Cl. At the same time, Cl atoms have a negative charge. It
can be concluded that the charge transfer took place from Cs and Sb to Cl
atoms. The Cl-Sb bond population is 0.14, which is positive and greater
than zero, which depicts the formation of a covalent bond. The Sb-Cs
bond, the value is − 0.35 showing that the bond is ionic [41]. The
equation used is given below.
( )
|pc − p|
− p
fn = 1 − e
Fig. 4. TDOS of: (a) Cs3Sb2Cl9 (b) Cs (c) Sb (d) Cl.
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Journal of Physics and Chemistry of Solids 182 (2023) 111548
3.3. Optical properties
Optical properties were calculated for a wide photon energy range,
but here, the energy range was from 0.7 eV to 4 eV with a Gaussian
smearing of 0.5 eV. Optical properties such as absorption coefficient,
transmission, reflectivity, relative permittivity, refractive index, and
energy loss function were calculated to further investigate the material’s
electronic structure. With these properties, it is possible to predict the
suitability of the material for its application in electronics and opto­
electronics [42].
Such properties of materials are investigated when the material is
probed using electromagnetic waves; hence, matter interaction takes
place. Optical properties are strongly related; therefore, a complex
function (dielectric function) is used, which is given below:
ε(ω) = ε1 (ω) + iε2 (ω)
Where,
ε1 (ω) is the real part and
ε2 (ω) is the imaginary part.
Z. Rehman et al. Journal of Physics and Chemistry of Solids 182 (2023) 111548

[ / { }1/2 / ]1/2
n(ω) = ε1 (ω) 2 + ε1 2 (ω) + ε1 2 (ω) 2

( ) /
L(ω) = − Im ε(ω)− 1 = ε2 (ω) ε1 (ω)2 + ε2 (ω)2

[{ }1/2 ]1/2
I(ω) = 21/2 ω ε1 2 (ω) + ε1 2 (ω) − ε1 (ω)

R(ω) = (n + ik – 1) / ((n + ik + 1)
The absorption spectrum in the visible region rises slowly and almost
linearly until the ultraviolet region, as shown in Fig. 6(a). In the visible
region, the absorption reaches the maximum value at the end of the
ultraviolet region, which means there will be a minimum transmission of
this energy because of the complete absorption of light. In contrast, light
absorption is almost absent at frequencies lower than the visible spec­
trum because no such electronic state exists which corresponds to this
range of energies. Hence the medium will be transparent to this range
due to complete transmission [44,45]. The peak value of the real part of
optical conductivity also occurs in the high-frequency region of the
visible spectrum, as shown in Fig. 6(b). Fig. 6(c) shows the dielectric
function calculates the refractive index and absorption coefficient. These
parameters help understand the physical properties and application of
these materials. To observe the energy lost by the electron while going
across the medium, the energy loss function was plotted in Fig. 6 (d).
Again, the peak value found in this curve was at the high-frequency
boundary of the visible spectrum. The surface response of any com­
pound is related to the reflectivity (frequency), as represented in Fig. 6
(e). The peak value of reflectivity in the visible region is 0.17. The
refractive index curve is shown in Fig. 6 (f). The static refractive index n
(ω) value was also calculated using a photon of zero electron volt energy;
the value of n(w) is 2.00. The refractive index has “n” and “k.” The value
“n” is highest at 2.30 at 2.48 eV, which lies in the visible region.

3.4. Magnetic properties

Fig. 5. PDOS of: (a) Cs3Sb2Cl9 (b) Cs (c) Sb (d) Cl.

Fig. 7 shows the results of the spin-polarized calculation for

Also, describe the relative permittivity of the compound under
investigation. Relative permittivity means how much a material allows
the electric field to set up inside its boundaries; therefore, good con­
ductors have zero relative permittivity.
Is the real part of the (dielectric) function related to the polarization
intensity, where the complex part ℇ2(w) affects the energy the material
dissipates? As shown in Fig. 6 (c).
It is frequency dependent and is given by the following equation,
which involves filled and empty states.
2e2 ∑⃒⃒ c ⃒2 ( ) partial density of states graphs, the spin-down curves mirror spin-up
ε2 (ω) = ψ |u.r|ψ vk ⃒ δ EKC − EKv − E
Ωε0 k,v,c k
Where uo is the polarization vector, w is the frequency of light, e is
the change of electrons, ψ ck and ψ vk represent the wave function of the
conduction band and valence band, respectively [43]. In addition to
these equations for dielectric constants, the equations used to calculate
the refractive index n, Absorption coefficient I, reflectivity R, and energy
loss L are given below,
Cs3Sb2Cl9. The calculations were performed using GGA with PBE
parameterization. Fig. 7(a) represents the spin-up (black) and spin-down
(red) band structures. Fig. 7(b) and (c) depict the density of states and
partial density of states, respectively. In the band structure graph, en­
ergy is plotted against the k-points, and it is observed that spin-up and
spin-down bands overlap each other, reflecting the magnetic nature of
the material [46]. The DOS graphs mirror each other for up and down
spin, and there is no shifting of DOS towards or away from the Fermi
level relative to each other for spin up and down states. Finally, in the
curves without any energy shifting. From these results, it can be
concluded that the material as a whole and even at the elemental bands
level, behavior is magnetic with zero resultant magnetic moments.
3.5. Phonon dispersion and phonon density of state
Fig. 8 represents the phonon dispersion, and Fig. 9 represents the
density of states of Cs3Sb2Cl9 crystal. In dispersion curves, phonons have
positive frequencies, and all the phonon frequencies are zero at the G
point within the Brillouin zone, which depicts that the material formed

Table 2
Mulliken population and charge analysis.
Species Mulliken atomic population Mulliken charge (e) Bond Population pμ Length dμ (Å)

s p d f Total

Cl 1.97 5.46 0 0 7.43 − 0.43 Cl-Sb 0.14 3.8038

Sb 2.04 2.02 0 0 4.06 0.94 Sb-Cs − 0.35 4.7196
Cs 2.08 6.01 0.19 0 8.27 0.73 – – –

5
Z. Rehman et al.
Fig. 6. Optical properties of Cs3Sb2Cl9: (a) Absorption (b) conductivity (c) dielectric function (d) loss function (e) reflectivity (f) refractive index.
Fig. 7. Spin Polarized electronic structure of Cs3Sb2Cl9: (a) Band Structure (b)
TDOS (c) PDOS.
is dynamically stable. The acoustic mode is responsible for the con­
duction of heat via lattice oscillations. In the dispersion curve, the op­
tical mode starts below the cutoff level of the acoustic mode; hence
mixing of optical and acoustic modes is prominent in the phonon
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Journal of Physics and Chemistry of Solids 182 (2023) 111548
Fig. 8. Ponon dispersion.
dispersion graph, which causes enhanced phonon scattering. The optical
mode curves are quasi-flat, depicting their low dispersion and will cause
fewer group velocities. Most of the phonons with positive frequency
showed complete convergence. Fig. 9 shows the phonon density of states
concerning the phonon frequency. The DOS was also zero for both
positive and negative frequencies near the zero-frequency region. The
first peak belongs to 0.34 states (1/THz) at 0.85 (THz), whereas the
highest DOS was 0.39 states at 3.4 (THz) in the positive frequency re­
gion. The phonon DOS peaks were observed due to acoustic and optical
bands in the vicinity. Since the phonon bands are observed only in the
positive frequency region and have the minimum value at the center of
the Brillion zone (gamma point) represents the fact that the crystal
lattice is resistant to small displacements that would increase the energy
of the system.
Z. Rehman et al.
Fig. 9. Density of phonon states.
3.6. Thermodynamic properties
The balance of a framework can be evaluated through its thermo­
dynamic functions, such as Entropy, Enthalpy, Helmholtz Free Energy,
and Specific heat capacity. Fig. 10 depicts these properties calculated
using phonon data in the temperature range from 5 to 1000 K. Enthalpy
of the system increases perfectly linearly as a function of temperature. In
contrast, the entropy and free energy vary non-linearly with tempera­
ture. The entropy and free energy curves followed the fit algorithm of
exponential growth and decay, respectively. Our results show that as the
temperature of the system rises, there is a steady decrease in free energy,
which is due to the effect of the framework’s entropy (S). The thermal
agitation causes an increase in disorder, leading to increased entropy
with increasing temperature. Conversely, the free energy decreases with
an increase in temperature. Additionally, the enthalpy of the system
increased with temperature.
The behavior of a material subjected to thermodynamic conditions
can be accessed using specific heat capacity (Cv), which means the
material’s ability to store thermal energy. The results indicate the
phonon contribution in the temperature dependence of Cv, as shown in
Fig. 10. The results clearly show the temperature dependence of specific
heat capacity as it rapidly increases at low temperatures. These results
illustrate the thermal behavior of the material.
3.7. Applications
Cs3Sb2Cl9 can be used for various applications, such as a semi­
conductor material due to its greater bandgap and solar light absorption
material due to its high absorption coefficient. Furthermore, its tunable
electronic and optical properties can also be used for photon detection.
In addition to these properties, another interesting application is as a
hole transport layer. Based on its magnetic and optical properties, it is
also suitable for spintronic, magneto-optical devices, and qubit material
for quantum computation.
4. Conclusion
In this work, DFT simulations were successfully performed to eval­
uate the material properties. The crystal structure, electronic parame­
ters, mechanical properties, and optical and magnetic properties were
probed using a plane wave basis set, GGA-PBE. The band gap and other
properties were calculated using HSE06; the material bandgap was
3.214 eV. The TDOS of the compound showed that it gets a major part
from chlorine. The contribution of Cs and Cl was found to be maximum
in the conduction and valence bands of the compound, respectively.
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Journal of Physics and Chemistry of Solids 182 (2023) 111548
Fig. 10. Thermodynamic properties.
Furthermore, Cl-p and Cs-p contributed to the compound’s p orbital in
the valence band. Likewise, Cs-s,p, and d orbitals replicated to the
conduction band of the compound. In addition, bond population anal­
ysis showed that ionic Sb-Cs and covalent Cl-Sb bonds were detected.
Cs3Sb2Cl9 has a high refractive index (2.30) and high absorption in the
visible region, which shows that the material can effectively trap and
absorb light for high conversion efficiency. The low frequencies are
transmitted due to the absence of corresponding electronic states. The
peak reflectivity value in the visible spectrum also indicates the ability
of the material to reduce light reflection and increase absorption. These
properties make it suitable for solar cell applications. The spin-polarized
calculation revealed the material’s behavior as a whole and at an
elemental level. The highest phonon density of states was observed at
0.0141 eV, whereas the DOS was zero at zero frequency. This study helps
understand the optical, electronic, structural, vibrational, and thermal
properties of the material under investigation and its use in various
applications.
Author statement
All authors certify that they have participated sufficiently in the
work to take public responsibility for the content, including participa­
tion in the concept, design, analysis, writing, or revision of the
manuscript.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Z. Rehman et al.
Data availability
No data was used for the research described in the article.
Acknowledgment
The author wishes to express their acknowledgment to Namal
University.
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