Ceramics International 46 (2020) 21378–21387

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Systematic study of optoelectronic and transport properties of cesium lead T

halide (Cs2PbX6; X=Cl, Br, I) double perovskites for solar cell applications
Mujtaba Hussaina, Muhammad Rashidb,∗, Awais Alia, Muhammad Fahad Bhopala, A.S. Bhattia
a
Center for Micro and Nano Devices, Department of Physics, COMSATS University Islamabad, 44000, Islamabad, Pakistan
b
Department of Physics, COMSATS University Islamabad, 44000, Islamabad, Pakistan

A R T I C LE I N FO A B S T R A C T

Keywords: A systematic density functional theory investigation of Cs2PbX6 (X = Cl, Br, I) double perovskites is presented.
Double perovskites The lattice constants are computed after structure optimization and using Birch-Murnaghan equations, which
Solar cells agree to the experimental literature. The mechanical stability conditions satisfy Born criteria, and the ductile
Thermodynamic stability nature is evidenced by the calculated Poisson's (v) and Pugh's ratios (B0/G) because all three double perovskites
Optical properties
exhibit values higher than the respective critical values v = 0.26 and B0/G = 1.75. A detailed study of the
optoelectronic properties reveals these double perovskites as promising candidates for future optical devices due
to their direct band gaps (within 0.45–2.54 eV) and large absorption coefficients 5.95 × 105 cm−1, which are
suitable for solar cell applications. ZT calculations demonstrate minute variations within 200–800 K and com-
puted parameter values are quite favorable for thermoelectric applications of these materials in the future. A p-
type semiconducting nature is predicted by the computed thermoelectric properties. Additionally, computed
refractive indices show Cs2PbBr6 and Cs2PbI6 exhibiting super-luminescent properties in the UV range.
Therefore, the studied double perovskites provide further interest for future energy conversion and photonic
based technologies.

1. Introduction
Continuous technological advancement has made us dependent on
machines to save time, effort, and energy. Due to this, an ever-in-
creasing demand for efficient power generation is needed for operating
these machines. According to some careful estimates, non-renewable
and traditional energy resources e.g., coal, natural gas, and petroleum
will only last approximately for another 50 years. Therefore, the
growing need for having efficient energy materials for nano-devices in
modern technology has made the search essential, for alternative re-
newable energy resources. Amongst the various alternatives in this re-
gard, the use of solar energy is a leading choice, owing to low-opera-
tional costs and are also environment friendly. Being a limitless source,
the sun can provide solar energy more than required to power the entire
world. The only limitation to the large-scale use of solar power rests
solely on the energy conversion efficiency which also increases the net
initial cost. Hence, the main goal is to find effective ways to convert
most of the energy from the sun into electricity. The solar radiations are
composed of about 50%, 40%, and 10% infrared (IR), visible and ul-
traviolet (UV) radiations, respectively. Therefore, materials with band
gaps around 1.4 eV or lower are most suitable for photovoltaic (PV)
applications. Currently, Si (band gap 1.1 eV) based solar cells are the
most popular solar-powered energy sources commercially available in
the market because Si-based solar cells are cheap and provide a rea-
sonable conversion efficiency of around 24% [1,2].
Amongst various studied materials, hybrid organic-inorganic and
metal halide perovskite structures of the form ABX3 (where, A is or-
ganic/inorganic ion, B is a metal cation and X is a halide ion) have
received immense attention because of their novel material properties,
which are appropriate to develop future efficient solar cells. Although
halide perovskites have a long history of investigations, after the dis-
covery of MAPbI3 based photosensitizer for dye-sensitized solar cell
applications, they have received huge attention. Since then, perovskite
solar cells have exhibited a rapid improvement in power conversion
efficiency (PCE) from 3.81% to almost 20% [3–6]. Recent reports reveal
the efficiency of perovskite-based solar cells approaching 23.7% [7],
which is better than for some of its competing materials e.g., Cu(In,Ga)
(Se,S)2, and CdTe. Apart from photovoltaic applications, perovskites
exhibit novel optoelectronic properties making them applicable for a
variety of optical devices, such as light-emitting diodes (LEDs) [8–10],
lasers [11,12] and photodetectors [13], due to their capability to adjust
to varying wavelengths and high quantum yields [14–19]. In recently

∗
Corresponding author.
E-mail address: muhammad.rashid@comsats.edu.pk (M. Rashid).

https://doi.org/10.1016/j.ceramint.2020.05.235
Received 2 March 2020; Received in revised form 12 May 2020; Accepted 21 May 2020
Available online 27 May 2020
0272-8842/ © 2020 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
M. Hussain, et al. Ceramics International 46 (2020) 21378–21387

reported studies, inorganic CsPbX3 perovskites have gained immense

attention, especially for applications in the solar cells because they
exhibit direct band gaps, large absorption coefficients (up to
2.4 × 105 cm−1) in the UV range [20] and high charge carrier mobility
679 cm2/Vs [21]. The electronic and optical properties of such per-
ovskites have been performed by Burschka et al. [22]. For achieving
more versatility in the material properties, recently double perovskites
are also being explored both theoretically and experimentally. Double
perovskites generally have shown to be more suitable than their single
counterparts in the past literature [23,24]. CsPbX3 (X = Cl, Br, I) are
also relatively unstable. This is also one of the parts of our motivation
for a particular study. Apart from the higher stability of double per-
ovskite structures, the other motivation behind this study was that the
percentage molar composition of Pb in the double perovskites Cs2PbX6
(X = Cl, Br, I) would be reduced to 11% (nearly halved) from 20%
present within their single perovskite counterparts. In terms of the
percentage composition by mass of Pb in these perovskites, we get a
reduction of 16.1% from 46.2% to 30.2%, 14% from 35.7% to 21.7%
and 11.7% from 28% down to 16.3% for Cs2PbCl6, Cs2PbBr6, and
Cs2PbI6, respectively, when compared to the single perovskite coun-
terparts. This could play a vital role in limiting and minimizing the
toxicity effects of Pb in these compounds, while at the same time al-
lowing one to benefit from the useful features that are brought about by
the presence of Pb within these perovskite materials such as increased
stability [25] and higher absorption coefficients [26,27], compared to
Pb free perovskites.
To the best of our knowledge, no systematic first principle study of
the double perovskites Cs2PbX6 (X = Cl, Br, I) exists. In this work,
detailed DFT calculations for Cs2PbX6 (X = Cl, Br, I) have been per-
formed to expose electronic properties, which have been used to sug-
gest optical and thermoelectric commercial applications. Using volume
optimizations, cubic lattice parameters are found. The computed band
structures and density of states (DOS) are used to reveal the nature of
underlying interactions, which finally stabilize an effective band gap of
each compound. Optical studies are also conducted by computing and
analyzing energy-dependent complex dielectric constant, absorbance,
reflectivity, and complex refractive index. In the end, conclusions are
presented to show the viability and suitability of the studied double
perovskites for optical and thermoelectric devices.
2. Computational details
This work was carried out using WIEN2k code, based on the density
functional theory (DFT). It makes use of full potential linearized aug-
mented plane wave (FP-LAPW) method, which basically visualizes the
atoms as spheres consisting of atom like wave functions and the in-
terstitial regions between atoms as wave functions, expanded as a series
of plane waves. The value for Imax, which represented the maximum
number of partial waves used inside the atomic spheres is set at 4.
Rkmax is set at 7.0. The muffin tin radius (R) is the smallest atomic
radius used for the DFT calculations, chosen in a way as to ensure there
is no charge leakage from the core, whereas kmax is the cutoff wave-
number in the series of plane waves being used to describe the inter-
stitials. The corresponding cutoff energy is selected as −7.0 Ry. The
study is carried out for the simple cubic phase of the materials. The
lattice parameters are first optimized using Birch-Murnaghan's equation
of state [28]. For improving the accuracy of the band gap calculations
for these materials, modified Becke-Johnson (mBJ) exchange potential
scheme [29] along with generalized gradient approximation (GGA) is
utilized [30]. This method takes the core electrons inside the atom as
fully relativistic, while considering the valence electrons as semi-re-
lativistic. The number of k-points are set at k = 3000 cm−1, with the k-
mesh 12 × 12 × 12 in the first Brillouin zone. For uncovering the
material properties of these compounds and their potential for optoe-
lectronic applications, detailed computations were performed to study
their structural, mechanical, electronic, optical and thermoelectric
Fig. 1. Energy verses volume optimization curve for Cs2PbX6 (X = Cl, Br, I).
properties.
3. Results and discussion
3.1. Mechanical properties and thermodynamic stability
The volume optimization is carried out using Birch-Murnaghan's
equation of state [28]. The energy versus volume optimization curves is
presented in Fig. 1 for Cs2PbX6 (X = Cl, Br, I) in the cubic phase. The
stabilized crystal structure and first Brillouin zone for all three com-
pounds are shown in Fig. 2. As evident from Fig. 1, the minimum op-
timized unit cell volume increases from Cs2PbCl6 to Cs2PbI6, which is
due to the increase in the atomic radii of the halogen atoms from Cl to I.
It is well known that more negative minimum lattice energy will result
in the more stable structure. The calculated bond lengths and bond
angles determined using VESTA are given in Table 1.
For analysis of the mechanical properties of a material, it is fun-
damental to know the elastic constants which describe the material
characteristics under the application of stress. For a simple cubic
structure, there are just three independent elastic constants C11, C12,
and C44. The values of these parameters along with other mechanical
parameters are given in Table 2. It can be seen that Cs2PbCl6, Cs2PbBr6,
as well as Cs2PbI6, all fulfill the three conditions of the Born stability
criteria for cubic structures [31], C11–C12 > 0, C44 > 0, C11+2C12 > 0
and C12 < B0 < C11, thus ensuring their mechanical stability. The bulk
moduli were calculated using the relation B0=(C11+2C12)/3 [32]..
To analyze the mechanical properties further, we also investigated
few more important mechanical parameters including Young (Y) and
Shear moduli (G), Poisson's (v), and Pugh ratios (B0/G) (see Table 2).
The brittleness and ductility of the materials have been studied using
these ratios. The limiting values are v = 0.26 and B0/G = 1.75 [33,34].
Materials having values higher than these limits are ductile, otherwise,
they are brittle in nature. The values provided in Table 2, clearly show
that the studied double perovskites are ductile, which makes them
advantageous for device fabrication. The anisotropy factor calculated
using A = 2C44/C11–C12 [35] shows that all the materials are aniso-
tropic, with Cs2PbI6 being the most anisotropic among the studied
compounds having a factor of 0.49. Cs2PbCl6 is closest among the three
to having perfect isotropic nature, with an anisotropic factor of 0.86
[35].
Debye temperature is also calculated using the expression [36].

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Fig. 2. (a) Cubic optimized structures (b) First BZ of Cs2PbX6 (X = Cl, Br, I).

h ⎡ 3nNAρ ⎤1/3 Table 2

θD = vm
κB ⎣ 4πM ⎦ (1) The calculated mechanical and thermodynamic parameters of Cs2PbCl6,
Cs2PbBr6 and Cs2PbI6 in cubic phase.
where M is the molar mass, NA is the Avogadro constant, ρ is the ma-
Parameters Cs2PbCl6 Cs2PbBr6 Cs2PbI6
terial density and vm is the average of the transverse and longitudinal
sound velocities expressed as [37]: Bo (GPa) 28.63 22.16 17.01
C11 (GPa) 46.13 36.82 32.23
−1
1 2 1 3 C12 (GPa) 19.09 16.43 8.55
vm = ⎡ ⎛ 3 + 3 ⎞ ⎤ C44 (GPa) 11.21 7.70 5.75
⎣ 3 ⎝ vt vl ⎠ ⎦ (2)
B0/G 2.4 2.6 2.2
Υ (GPa) 31.7 23.0 20.0
where, vl and vt are the longitudinal and transverse sound velocities
A 0.83 0.76 0.49
and given as: υℓ (m/s) 3369.8 2759.9 2389.0
1 υt (m/s) 1761.6 1374.9 1283.2
G 2 υm (m/s) 1970.7 1542.7 1432.8
vt = ⎜⎛ ⎟⎞ 0.311 0.334 0.297
⎝ρ⎠ (3) V
θD (K) 183.9 135.9 116.8
1
3B + 4G ⎞ 2
vl = ⎜⎛ 0 ⎟

⎝ 3ρ ⎠ (4)
The velocity of sound is the highest in Cs2PbCl6 with vm = 1970 m/
s followed by Cs2PbBr6 and Cs2PbI6 (for values, see Table 2). The Debye
temperature, as dictated using relationship in Eq. (1), follows a similar
trend.
3.2. Electronic properties
The band structures of Cs2PbX6 (X = Cl, Br, I), presented in Fig. 3,
clearly show a direct band gap for all three double perovskites, with
valence band maximum (VBM) and conduction band minimum (CBM)
both coinciding at the same high symmetry point Γ. This fulfills one of
the main requirements to manufacture energy-efficient solar cells, as
the energy losses in the photo-excited electrons due to phonon scat-
tering events are minimized. The calculated band gaps for Cs2PbX6
(X = Cl, Br, I) are 2.542 eV, 1.542 eV and 0.449 eV, respectively. This
trend is owing to the increasing atomic radii of the different halogens in
these three different materials. As the atomic radius increases, the effect
of the electrostatic force of the nucleus on the valence shell electrons
diminishes, which contracts the band gap energy between the valence
and the conduction bands. Hence, for narrow band gaps, even a small
amount of incident energy can lead the bound electrons to move to the
conduction band to attain a free conducting state. The band gap tran-
sitions for all three compounds take place from X-p orbital in the va-
lence band to a mixture of Pb-s and X-p state in the conduction band. In
comparison, the band gap energies calculated for the corresponding
single perovskites CsPbX3 (X = Cl, Br, I) were higher at 3.1 eV in
X = Cl, 2.36 eV in X = Br and 1.75 eV in X = I [38]. This is because of
stronger double bonds present in the double perovskite structures,
which bring the atoms closer to each other in the structures, thereby
shifting the valence states farther away from the Fermi level. It is in-
teresting to note that amongst the single perovskites, CsPbI3 proved to
be most promising for solar cell applications with a band gap of 1.7 eV,
whereas amongst the double perovskite structures, Cs2PbBr6 took the

Table 1
The calculated structural parameters of Cs2PbCl6, Cs2PbBr6 and Cs2PbI6 in cubic phase using mBJ potential in WIEN2k and VESTA.
Parameters Cs2PbCl6 Other Cs2PbBr6 Other Cs2PbI6 Other

a (Å) 10.54 10.82 [35] 11.15 11.33 [35] 12.05 12.07 [35]
10.42 [36] 10.87 [35] 11.55 [35]
Bond Lengths (Å)
Cs-X 3.703 3.945 4.395
Pb-X 2.484 2.691 2.998
Cs–Pb 4.533 4.830 5.381
Bond Angles (Deg)
Pb-X-Cs 92.06 91.42 91.42
X1-Cs-X2 56.62 57.68 57.68
X1-Pb-X2 90.00 90.00 90.00

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Fig. 3. Energy band structure and total density of states, of (a) Cs2PbCl6, (b) Cs2PbBr6(c) Cs2PbI6.

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M. Hussain, et al.
Fig. 4. Partial DOS plotted for (a) Cs2PbCl6, (b) Cs2PbBr6,(c) Cs2PbI6.
lead with a band gap of 1.542 eV, which is closest to Shockley Queisser
limit [34]. The other two perovskites, however, could prove quite sui-
table to be used in photodetectors and light-emitting diodes.
Further analysis of the electronic properties was carried out by
studying the density of states (DOS). The total density of states (TDOS)
plots shown in Fig. 3 (a), (b), and (c) clearly show that all three ma-
terials exhibit semiconducting nature as the TDOS from the valence
band does not cross over the Fermi level. The partial density of states
(PDOS) presented in Fig. 4 (a), (b), and (c) provides information about
the contributions of the individual atoms in the stabilized structure. It is
seen that Cs-p orbital for all materials sits back quite deep in the va-
lence band. For X = Cl, three major bands can be seen in the PDOS
plots. In the range from −6 eV to −5 eV, the major orbitals present are
Cs-p and Pb-s. In addition, sp2 hybridization between the Cl-s and Cl-p
orbitals can also be seen. The large contributions of p-states (Pb-p and
Cl-p) and a small contribution of d-states (Pb-d) occur in PDOS plots.
When the Cl atom is replaced by the Br atom, we see similar patterns in
the PDOS plots except for a few differences. Firstly, the PDOS move
towards the lower energy, deeper into the valence band. An additional
band for Cs2PbBr6 is seen at about 6.5 eV, which is mainly constituted
by Pb-p orbital. When the Br atom in the double perovskite structure is
replaced by X = I atom, I-p has a comparable contribution to the Pb-p
orbital within this band. The Cs-p orbital, which plays a significant part
in the previously discussed perovskites, almost vanishes away for
Cs2PbI6. The calculated electronic band gaps for these double per-
ovskites are given in Table 3.
3.3. Optical properties
The optical parameters that are mostly studied to determine the
usefulness of the compounds include complex dielectric functions ε(ω),
absorption coefficients α(ω), optical conductivities σ(ω), complex re-
fractive indices η(ω) and reflectivity R(ω) [40–45]. The complex di-
electric function is described as ε(ω) = ε1(ω) +iε2(ω). The graphs for
complex dielectric functions are plotted in the energy range 0–6 eV in
Fig. 5. The real part ε1(ω) is plotted in Fig. 5 (a). The most important
parameter in these spectra is the zero-frequency limit ε1(0), which
Table 3
The calculated electronic and optical parameters of Cs2PbCl6, Cs2PbBr6 and
Cs2PbI6.
Properties Cs2PbCl6 Cs2PbBr6 Cs2PbI6
Eg (eV), 2.542 1.524 0.449
ε1 (0) 2.44 3.98 4.38
n(0) 1.56 1.75 2.09
R (0) 0.05 0.07 0.12
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Ceramics International 46 (2020) 21378–21387
represents the electronic part of the dielectric function. An increase in
ε1(0) from Cs2PbCl6 to Cs2PbI6 was observed, as the values increased
from 2.44 for X = Cl, 3.06 for X = Br and 4.38 for X = I. These values
are much higher in comparison to Cs2SnX6 (X = Cl, Br, I) compounds,
which have recently been gaining popularity for solar cell applications.
The ε1(0) values for Cs2SnCl6, Cs2SnBr6 and Cs2SnI6 are 2.17, 2.53 and
3.26 respectively, as computed in Refs. [27].
The peaks observed in the ε2(ω) plots are related to the various
possible inter-band transitions within the band structures of the mate-
rials. From the plots in Fig. 5 (b), it can be seen that for the visible and
the infrared (IR) regions, Cs2PbI6 exhibits the highest peak value, when
compared with the other two perovskite structures. This is because of
the lower band gap for Cs2PbI6 compared to the other two materials,
which makes it easier for the polarized electrons to extend into the
conduction band and enhance the photovoltaic effect. The spectra also
suggest that the critical energies for the three compounds shift to the
lower energy side, as we move from Cs2PbCl6 to Cs2PbI6, for the visible
to the IR range. The critical energies as observed from the plots are
2.50 eV for Cs2PbCl6, 1.49 eV for Cs2PbBr6 and 0.45 eV for Cs2PbI6,
corresponding to their band gap energies of 2.54 eV, 1.54 eV and
0.49 eV, respectively. The peaks after these critical energies express
other transitions within various atomic orbitals in the band structure.
The first peak for all materials is due to the transition from a combi-
nation of the Cl-p and Pb-p orbitals in the valence band to the Pb-s
orbital in the conduction band. The second peak that is seen only for the
Cs2PbI6 structure has its origin in the transition from the I-p orbital in
the valence band to the orbital combination of Pb-p and I-p in the
conduction band. An overall analysis of the ε1(ω) and ε2(ω) plots sug-
gests that Cs2PbI6 is most capable to absorb and retain the most energy
across a wide range of wavelengths, especially in the range from about
1 eV to 5 eV, making it suitable for PV applications. Hence, they are
most suited for solar energy applications. Nevertheless, the other two
perovskites are also quite suitable for various optoelectronic applica-
tions, and therefore, cannot be ignored.
The materials exhibit large absorption coefficients in the UV and
visible ranges as can be seen in Fig. 5 (c). In the UV range, the double
perovskite Cs2PbBr6 shows the largest absorption coefficient of
5.95×105 cm−1 at 4.53 eV, followed by Cs2PbI6 with an absorption
coefficient of 4.17×105 cm−1 at 3.71 eV and Cs2PbCl6 with an ab-
sorption coefficient of 1.45×105 cm−1 at 3.42 eV. Whereas, in the
visible range Cs2PbBr6 shows a peak absorption coefficient of 1.1×105
cm−1 at 2.54 eV and Cs2PbI6 with a maximum absorption coefficient of
7.7×104 cm−1 at 1.56 eV. A comparison with some of the recent
studies on perovskites reveals that our computed numbers are quite
high. The organic-inorganic perovskite MAPbI3, which is one of the
most promising perovskites for future solar cells has a maximum re-
ported absorption coefficient of 5.2×104 cm−1 in the visible range at
2.8 eV [41]. Also, the double perovskites in this study prove to have
larger absorption coefficients compared with their single perovskite
counterparts. In this regard, the single perovskite CsPbBr3 has a re-
ported maximum absorption coefficient of 2.4×105 cm−1 in the UV
range, which is the highest in this series of cesium lead halide per-
ovskites CsPbX3 (X=Cl, Br, I) [20]. A detailed study on eighteen dif-
ferent double perovskites was undertaken and presented in Ref. [42].
The study revealed a maximum absorption coefficient of 1.1×105
cm−1 in the UV range at 3.8 eV for (FA)2BiCuI6. For the visible range,
Cs2BiCuI6 exhibited an absorption coefficient of 5.8×104 cm−1 at
2.7 eV. Also, compared with Cs2SnX6 (X=Cl, Br, I), the Cs2PbX6 (X=Cl,
Br, I) perovskites in this study exhibit higher absorption coefficients,
especially in the ultraviolet (UV) range. For the case of X=I, Cs2SnI6
has a peak absorption coefficient of 1.5×105 cm−1 in the UV range
[26], significantly lower than the value calculated here (5.95×105) for
Cs2PbI6.
All three perovskite structures exhibit high optical conductivities in
the region from 1-6 eV. In particular, within the energy range most
suitable for solar cells (about 1–3.5 eV), Cs2PbCl6 shows highest optical
M. Hussain, et al.
Fig. 5. (a) Real part of dielectric constant ε1(ω), (b) Imaginary part of dielectric function ε2(ω), (c) Absorption coefficient ‘α(ω)’, (d) Optical conductivity σ(ω) for
Cs2PbCl6, Cs2PbBr6 and Cs2PbI6 double perovskites.
conductivity, of around 618.9 Ω-1cm-1 at 3.36 eV. It is followed by the
compound with X = Br with an optical conductivity 510.1 Ω-1cm-1 at
2.52 eV and X = I with 392.2 Ω-1cm-1 at 1.51 eV. Even though Cs2PbI6
exhibits the least optical conductivity, it presents its peak value at a
much lower energy, closer to the Schockley Queisser limit [39], which
is suited to construct solar cell applications.
The information about the refractive index and the reflectivity
coefficients for optical materials is essential in designing photonic de-
vices. In fact, the high refractive index of Si is one of the major factors
that limits the output efficiency of Si solar cells [43,44]. Si solar cells
exhibit huge reflectance losses as a result of high refractive index va-
lues, as these two parameters are connected to each other through the
following mathematical relationship [45]:
[n − 1]2 + k 2
R (ω) =
[n + 1]2 + k 2
The refractive index and reflectivity plots for Cs2PbX6(X=Cl, Br, I)
are provided in Fig. 6 (a) and (b). From the graphs, it is seen that the
values of the refractive index n (0) at 0 eV for Cs2PbCl6, Cs2PbBr6 and
Cs2PbI6 are 1.56, 1.75 and 2.09, respectively. These values are lower
than their single counterparts, which are equal to 1.75, 1.99 and 2.1 for
CsPbCl3, CsPbBr3 and CsPbI3 [38], respectively and are also quite
Fig. 6. (a) Refractive index n(ω), (b)Energy dependent reflectivity spectra R(ω) for Cs2Pb (Cl,Br,I)6.
Ceramics International 46 (2020) 21378–21387
comparable to the values reported for Cs2SnX6 (X=Cl, Br, I) structures
at 1.47, 1.59 and 1.81 for X=Cl, X=Br and X=I, respectively [27].
The maximum refractive index observed for the Cs2PbI6 perovskites
is n(ω) = 2.51, which is observed at the ultraviolet (UV) photon energy
of 3.38 eV. The maximum refractive indices decrease to 2.38 at 4.20 eV
and 2.31 at 4.88 eV, when the I atom is replaced by Br and Cl, re-
spectively. The other peak for X = I can be seen in the IR range, which
shows a high refractive index of 2.26. In the visible range, two peaks
occur at 1.96 for X = Br and 1.82 for X = Cl. The refractive index
values of these structures are much lower than that of Si. In the visible
range at 2.25 eV, the refractive index of Cs2PbCl6 is 1.66, followed by
Cs2PbBr6 and Cs2PbI6 with refractive indices of 1.83 and 1.92, respec-
tively. In comparison to the refractive index of Si (n = 3.4 [46]) at the
same energy, the double perovskite structures in this study hold a huge
advantage over Si for solar cell applications. In terms of the refractive
(5)
index, they also hold an advantage over MAPbI3, which has a reported
refractive index of 2.86 at 2.38 eV in the visible range, compared to the
refractive indices of 1.68 for Cs2PbCl6 and about 1.89 for both Cs2PbBr6
and Cs2PbI6, at the same photon energy value. From Fig. 6(b) the values
of total reflection R(0) at 0 eV for X = Cl, Br, I are 0.05,0.07, and 0.12
respectively. These values are also comparable to the values reported
for Cs2SnX6 (X = Cl, Br, I) at 0.03, 0.05 and 0.08 for X = Cl, X = Br
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and X = I, respectively [27].
In addition to that, it can also be seen that the refractive index for
X = Br and Cl falls below 1 in the UV range. According to the Paul
Drude's model [47], this implies that for light waves in the UV range,
these two compounds may become superluminal. This means that the
group velocity of light in this range can even exceed the speed of light
in a vacuum. Hence, these materials can also be explored further for fast
light experiments. The computed optical parameters reveal that the
studied double perovskites exhibit effective optical responses. Hence, it
is suggested that these materials may be grown experimentally for de-
signing attractive novel optical devices.
3.4. Thermoelectric properties
The solar thermoelectric generation that makes use of the heat
provided by the solar energy, has been receiving a lot of attention re-
cently, as it can improve the output efficiency of solar cells even further
[48–50]. They are even considered as replacements for thermoelectric
devices [51]. However, for practical device fabrication, materials with
suitable thermoelectric properties at room temperature (300 K) are
required. The thermoelectric figure of merit (ZT) is usually used to
indicate the overall thermoelectric performance of a material.
The value of the figure of merit can be calculated in terms of
Seebeck coefficient (S), electrical conductivity (σ/τ), and thermal con-
ductivity (κ/τ) employing the expression:
ZT  =  σ S2T/κ (6)
The net thermal conductivity is due to the contribution from elec-
trons as well as phonons/lattice vibration. There has been an intense
search for materials exhibiting high values of ZT at room temperature.
As a general criterion, a ZT = 1 is considered sufficient and advanta-
geous for practical applications [52]. Keeping this in view, we were also
interested in finding out and calculating the thermoelectric properties
of Cs2PbX6 (X = Cl, Br, I) to see if they could meet these requirements.
For evaluation of the transport properties, the BoltzTrap code based
on the Boltzmann transport theory was utilized [46]. Fig. 7 (a–f) and
Fig. 8 (a–d) represent the thermoelectric characteristics of the Cs2PbX6
(X = Cl, Br, I), plotted against chemical potential (μ) and temperature
(T). The BoltzTrap code can be used to find the electronic part of the
thermal conductivity, while for the calculation of the phononic part,
ShengBTE code is usually used [53]. In the present study, only the
electronic part was computed due to such computational limitations.
The calculation of ZT based on its electronic part has been adopted in
numerous previous studies [54,55].
In Fig. 7 (a), σ/τ is plotted against chemical potential (μ). The free
carriers are responsible for the conduction of current in any compound.
The amount of energy needed to overcome the repulsion of existing
electrons and to cast the electrons into the setup is referred to as the
chemical potential. Various materials have different chemical poten-
tials. Its value is positive for n-type materials, and for p-type materials
its value is negative. The σ/τ rises with increasing temperature for all
three compounds, as shown in Fig. 7 (b). The σ/τ in semiconductors
depends on two parameters, the carrier concentrations and the carrier
mobilities, mathematically described as σ = neμe + nhμh [56]. The
electrical conductivities at room temperature (300 K) are 5.87 × 1018
(Ωms)−1, 5.14 × 1018 (Ωms)−1, and 5.56 × 1018 (Ωms)−1 for the
compounds with the halogen atoms X = Cl, X = Br and X = I, re-
spectively. The high electrical conductivity for Cs2PbI6 can be asso-
ciated with its extremely low band gap of 0.449 eV.
The plots for thermal conductivity against the chemical potential (μ)
and temperature are shown in Fig. 7 (c, d). The basic expression for the
thermal conductivity is composed of two parts, namely the electronic
part, which is due to the electrons and holes in the material and the
lattice part, which is constituted by phonons. Mathematically this is
expressed as κ = κe+κph [57,58]. The electronic part of the thermal
conductivity is related to the electrical conductivity by the Wiedemann-
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Ceramics International 46 (2020) 21378–21387
Franz law κe = LσT [59]. The thermal conductivities for all three ma-
terials increase and remain almost equal, within the temperature range
from 200-400 K. At higher temperatures (T > 400 K), the thermal
conductivity for Cs2PbI6 exhibits a sharper increase when compared
with the other two perovskites. This rate of increase with temperature is
lowest for Cs2PbCl6. At room temperature, the thermal conductivity for
the compounds is around 9.13 × 1013 Wm−1K−1s−1. Our calculated
values of S against μ and T are shown in Fig. 7 (e, f). In Fig. 7 (c), it can
be seen that the value of S for all perovskites follows a similar trend, i.e.
it decreases with an increase in temperature. The values for the S are all
positive which indicates that the majority charge carriers in these
materials are holes. At room temperatures, the value of S for the
compounds with X = Cl, Br, and I is computed to be 197.10 μVK−1,
208.53 μVK−1, and 203.70 μVK−1, respectively.
The thermal efficiency can be explained in two ways, first one is the
power factor (σS2), while the other is the figure of merit (ZT) and both
of them can be distinguished based on thermal contributions (see
Fig. 8(a-d)). In the expression for power factor (σS2), we do not take the
thermal contribution into account and only consider the combined
impact of electrical conductivity and the Seebeck coefficient [28]. For
the other factor, i.e. the figure of merit (ZT), the thermal contribution is
taken into account. The graphs of the power factor (σS2) against the
chemical potential and temperature are presented in Fig. 8 (a) and (b),
respectively. At the Fermi level, both the materials under observation
have a maximum value of S. A region from −0.5 eV to −1.5 eV re-
presents the increased value of σS2 that is caused by the surplus addi-
tion of carriers at high chemical potential resulting from the maximum
peaks. Growing electrical conductivity causes the power factor values
(σS2) to reach the values of 3.0 × 1011 W/mK2s, 3.2 × 1011 W/mK2s
and 3.0 × 1011 W/mK2s at 600 K for Cs2PbCl6, Cs2PbBr6 and Cs2PbI6,
respectively. Lastly, Fig. 8 (c) and (d) present graphs for the figure of
merit (ZT) plotted against chemical potential and temperature, re-
spectively. Since the value of ZT increases with μ and reaches 1, this
highlights the importance of the studied compounds for applications in
thermoelectric devices. In the temperature range of 200–600 K, the
figure of merit is not strongly affected by the temperature. It is due to
the fact that the ratio between electrical to thermal conductivity re-
mains invariant at all temperatures. Referred to Fig. 8 (b), it is found
that at room temperature, ZT for the double perovskites with X = Cl,
X = Br, and X = I is 0.740, 0.765 and 0.745, respectively. Therefore,
our findings can be helpful to facilitate the fabrication of high-perfor-
mance thermoelectric devices based on these materials. The thorough
investigation of the optical characteristics of the selected double per-
ovskites enhances their reliability for optical uses in solar cell and op-
toelectronic applications, due to possible adjustments to the light in the
visible region. Also, investigation of thermoelectric characteristics
suggests that these perovskites are promising for high efficiency solar
powered thermoelectric generator and other thermoelectric device ap-
plications.
4. Conclusions
In this work, a comprehensive analysis of the optoelectronic and
thermoelectric properties of Cs2PbX6 (X = Cl, Br, I) is performed,
which reveals that these double perovskites are quite suitable for solar
cells and other optoelectronic applications, owing to their direct band
gaps being smaller than their respective single perovskite structures. In
particular, Cs2PbBr6 and Cs2PbI6 having band gaps of around 1.54 eV
and 0.44 eV, respectively, appear as very worthy contenders for future
solar cell devices. In terms of the computed optical properties, they
exhibit high absorption coefficients and dielectric constants in the UV
and visible energy ranges. Higher optical conductivities in comparison
to their respective single perovskites is also found to be quite suitable
for applications in solar cell structures. Furthermore, the superluminal
properties exhibited by Cs2PbBr6 and Cs2PbI6 in the UV range in-
creases the importance of these materials because they can be explored
M. Hussain, et al. Ceramics International 46 (2020) 21378–21387

Fig. 7. The calculated electrical, thermal conductivities and See-beck coefficients of Cs2Pb(Cl, Br, I)6 against (a, c, e) chemical potential and (b, d, f) temperature
respectively.

Fig. 8. The calculated power factors and figure of merit of Cs2Pb(Cl, Br, I)6 against (a, c) chemical potential and (b, d) temperature.

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and exploited for diverse future photonic devices. Additionally, since
the figure of merit ZT for these compounds also reach as high as 1, it
adds to their potential for solar cell applications, as these materials can
also efficiently convert the heat energy from the solar radiation to
electric power, increasing their efficiency further. The ductile nature of
the studied double perovskites suggests that the fabrication of solar
cells and photonic devices is quite feasible and practical. The complete
analysis reveals that they are potentially significant candidates for fu-
ture solar cells and energy harvesting devices.
Declaration of competing interest statement
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
We would like to thank Higher Education Commission (HEC),
Pakistan for supporting this work through fund No:7294/Balochistan/
NRPU/R&D/HEC/2017. Also, we would like to acknowledge DAAD for
their funding under the project titled “EXCIPLAS: Time resolved studies
of bound exciton-plasmon coupling in wide band gap semiconductor
nanostructure-metallic nanoparticle composites.”
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ceramint.2020.05.235.
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