Vol. 19, No.

3 | March 2021

Optoelectronic and elastic properties of metal halides

double perovskites Cs2InBiX6 (X = F, Cl, Br, I)
Muhammad Saeed1,2, Izaz Ul Haq3, Shafiq Ur Rehman4, Akbar Ali3, Wajid Ali Shah3, Zahid Ali3, Qasim Khan5**, and Imad Khan3*
1 State Key Laboratory of Nuclear Resources and Environment, East China University of Technology, Nanchang 330013, China
2 College of Nuclear Science and Engineering, East China University of Technology, Nanchang 330013, China
3 Center for Computational Materials Science, Department of Physics, University of Malakand, Chakdara, Pakistan
4 College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China
5 College of Electronic Science and Technology, Shenzhen University, Shenzhen 518000, China

*Corresponding author: [email protected]

**Corresponding author: [email protected]
Received November 20, 2020 | Accepted January 19, 2021 | Posted Online March 12, 2021

Structural geometry, electronic band gaps, density of states, optical and mechanical properties of double perovskite halides
Cs2 InBiX6 (X = F, Cl, Br, I) are investigated using the density functional theory. These compounds possess genuine perovskite
stoichiometry, evaluated using various geometry-based indices like tolerance factor, octahedral factor, and formation
energy. The fundamental electronic band gaps are direct and valued in the range 0.80–2.79 eV. These compounds have
narrow band gaps (except Cs2 InBiF6 ) due to strong orbital coupling of the cations. The valence band maximum and con-
duction band minimum are confirmed to be essentially of In 5s and Bi 6p characters, respectively. The splitting of Bi 6p bands
due to strong spin-orbit coupling causes reduction in the band gaps. These compounds have large dispersion in their bands
and very low carrier effective masses. The substitution of halogen atoms has great influence on the optical properties. The
mechanical properties reveal that Cs2 InBiX6 (X = F, Cl, Br, I) satisfy the stability criteria in cubic structures.
Keywords: optical materials; metal halides; density functional theory; perovskite stoichiometry; spin-orbit coupling.
DOI: 10.3788/COL202119.030004

1. Introduction compounds containing high content of Pb are reported harmful

to health and the environment[24,25].
The appearance of lead (Pb) tri-halide perovskites APbX3 in Overcoming this toxicity and instability problem gives rise to
photovoltaic cells resulted in power conversion efficiency up research work committed to investigating Pb free perovskites
to 25.2% in 2020[1,2], which offers an extraordinary prospect free of intrinsic structure instability and poverty under external
for wider use of solar energy. Pb halide perovskites have excep- stimuli[24,26]. It is highly desirable to identify Pb free materials
tional properties such as high charge carrier mobilites, direct and
that have properties of the extensively studied MAPbX3
tunable band gaps, small effective masses of electrons and holes,
perovskites[3]. The effective replacement of Pb from perovskite
high absorption, balanced electron and hole transport, and long
halides leads us to adopt different structural designs. Pb can be
carrier diffusion length[3–9]. Due to the remarkable structural,
replaced by other group IV elements, e.g., Ge and Sn, as
electrical, optical, electronic, magnetic, catalytic, and supercon-
ducting properties, halide perovskites find many applications in CH3 NH3 SnI3 and CH3 NH3 GeI3 , but their use provides chemi-
new areas of technology[10–14]. They are widely used as optical cal instability due to the preferred poor
4 oxidation state and
functional materials in different devices like light emitting poor optoelectronic performance[27]. Inorganic perovskites
diodes (LEDs), solar cell absorbers, X-ray detectors, lasers, bat- CsPbX3 (X = F, Cl, Br, and I) are more thermally stable in
teries, photodetectors, and quantum dots[15–20]. Extensive contrast to organic–inorganic hybrid perovskites[28–30].
research has been carried out on photovoltaic hybrid organic– Alternatively, two Pb can be replaced by a pair of monovalent
inorganic perovskites (ABX3 ) using Pb as a B-site cation from and trivalent ions leading to the structure of organic/inorganic
the last 10 years[21–23]. However, Pb perovskites undergo intrin- double perovskites having the general formula AB
B3
X6
sic structure instability when exposed to moisture, light, air, and (A = organic or alkaline earth metal, B
= monovalent, B3
=
high temperatures. In addition, Pb is a most toxic element and trivalent, X = halogen)[18]. The crystal structure of double

© 2021 Chinese Optics Letters 030004-1 Chinese Optics Letters 19(3), 030004 (2021)
Vol. 19, No. 3 | March 2021 Chinese Optics Letters

perovskite is stable and the same as in most oxides. Moreover, state. This situation will lead to valence band maximum of the d
introducing different metal cations on site B, diverse organic and character and is not needed[26]. Group III elements have filled s
inorganic cations on site A, and a variation of halide composi- and d orbitals when they are in the
1 oxidation state; in this
tions on site X can fabricate highly efficient materials compa- configuration, d electrons are deeper than s electrons. The suit-
rable to MAPbI3 (MA = CH3 NH3 ) and CsPbI3 [26,31]. Double able elements from group III are In and Tl (the rest have low
perovskite halides are emerging efficient materials in numerous atomic numbers and cannot exist in the
1 oxidation state);
applications such as ferroelectrics, electrocatalysts, phosphors, as Tl is toxic, the sole option for us is In [48].
white light emitters, spintronics, magnetoresistive materials, Zhao et al.[49] proposed that In1
-based double perovskites
and solar absorbers[32,33]. The early synthesized organic double Cs2 InBiCl6 and Cs2 InSbCl6 are useful solar cell absorbers
perovskite methyl ammonium CH3 NH3 
and formamidinium because their band gaps are direct, having band gaps of
NH2 CHNH2 
are not stable and not suitable for the use of 1.02 eV and 0.91 eV, respectively. These predictions were pro-
photovoltaic cells[34–38]. Small amounts of inorganic cations vided by the relatively new hybrid functional, including spin-
like Cs
doping with methylammonium CH3 NH3 
and for- orbit coupling (SOC) [Heyd–Scuseria–Ernzerhof (HSE +
mamidinium NH2 CHNH2 
at the A site can raise the stability SOC)] calculations. These two perovskites are found to be
of perovskites[29,39–42]. Inorganic double perovskite halides thermodynamically stable against decomposition with small
AB
B3
X6 (with B3
= Sb, Bi; B
= Ag, Cu, Au, and X = Cl, effective masses of electrons and holes[50]. The In1
oxidation
Br, I) are useful for optoelectronic purposes when their band state is rare; however, InCl and In3 Ti2 Br9 are the compounds
gaps lie in the visible range of the electromagnetic spectrum[43]. in which the In1
oxidation state has been reported[51,52].
The successful candidates for solar cells are Cs2 AgBiCl6 and Although theoretical studies proposed that Cs2 InBiX6 and
Cs2 AgBiBr6 . These compounds are more stable and absorb light Cs2 InSbX6 (X = Cl, Br, I) have admirable optoelectronic proper-
in the visible range of the electromagnetic spectrum. The struc- ties including direct band gaps and small carrier effective
tures of these compounds are highly symmetric faces of center masses, they are unstable due to the favorable
3 oxidation state
cubic double perovskites. Cs2 AgBiCl6 and Cs2 AgBiBr6 are indi- of In [53]. To the best of our knowledge, successful synthesis of
rect band gap semiconductors, and Cs2 AgBiBr6 is s synthetically these double perovskites has not been reported. The replace-
stable and non-harmful perovskite having a band gap of 2.19 eV ment of the A-site cation in these compounds with a large sized
by diffuse reflectance spectroscopy and 1.95 eV by photolumi- mixed cation such as Cs=MA=FA2 InBiBr6 can passivate the
nescence[44,45]. It has limited applications in photo cells because oxidation process and might solve the stability problem[26,32,47].
of its low absorption of light[46]. Substitution of the A-site cations can provide stability to double
In metal halides perovskites, the A-site cation is not involved perovskites[29,39–42], but have no contribution in the formation
in the formation of the frontier band edges; on the other hand, of frontier bands and therefore have negligible effects on the
optoelectronic properties[2,47]. These compounds have been
anions at the X site (F, Cl, Br, I) modulate the size [in electron
studied theoretically, yet there is a lack of literature about their
volts (eV)] of the band gap but have nothing with the orbital
elastic and optoelectronic nature. In this article, an attempt has
character and direct/indirect nature of the band gap[47].
been made to study the stability and effect of anion substitution
Therefore, the efficiency of metal halide perovskites in solar cells
on the structural, chemical bonding, electronic, elastic, and
and LEDs can be tuned by smart choices of B
and B3
sites
optical properties of Cs2 InBiX6 (X = F, Cl, Br, I) using different
cations. Choices for the B3
site are (i) elements of group III
exchange-correlation approximations of the density functional
(In, Tl), (ii) pnictogens, and (iii) several transition metals (Cr,
theory (DFT). These compounds are direct band materials in
Mn). For the B
site, the possible candidates are (i) noble tran-
contrast to other inorganic double perovskites. The calculated
sition metals (Ag, Au), (ii) lanthanides, (iii) some actinides (Pu,
band gap of Cs2 InBiCl6 is 1.37 eV, close to the optimal band
Am, and Bk), (iv) elements of group III (In, Tl), and (v) alkaline gap (1.4 eV) for photovoltaic applications. The absorption edge
metals (Na, K). Among these, lanthanides, actinides, and tran- of these compounds is found to be similar to the best-identified
sition metals have partially f or d orbitals, so they would have material (MAPbI3 ) for solar cells. The present work will not only
band extremes of such states. Group III elements in the
3 oxi- to help us understand the optoelectronic and mechanical prop-
dation state have the highest occupied states of the d character at erties of Cs2 InBiX6 (X = F, Cl, Br , I), but will also motivate
the top of the valence band. The pnictogens such as N3
and P3
researchers to explore double perovskite halides for practical
are not stable in perovskite structures because of their small size, applications.
according to Goldschmidt’s rule. Arsenic is toxic, and the pos-
sible candidates to realize double perovskites from the pnictogen
family are Sb3
and Bi3
.
2. Details of Calculations
Potential contestants for the B
site in double perovskite hal-
ides are alkaline metals, elements of group III, and noble DFT is used to calculate the structural, electronic, optical,
transition metals. Out of these three, alkaline metals give and elastic properties of Pb free inorganic double perovskite
non-dispersive bands and hence are not suitable for photovoltaic halides Cs2 InBiX6 (X = F, Cl, Br , I). The calculations are done
perspectives. Cations of the noble transition metals occupy the using the full potential linearized augmented plane wave (FP-
highest orbital of the d character when it is in the
1 oxidation LAPW) method implemented in the Wein2k package[54].

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Chinese Optics Letters Vol. 19, No. 3 | March 2021

Exchange-correlation energy is dealt by generalized gradient

approximation (GGA) Perdew–Burke–Ernzerhof for solids
(PBEsol)[55], because it is more effective compared to other GGA
characteristics for the calculation of structure optimization[56].
For the calculations of electronic properties of GGA, modified
Becke–Johnson (mBJ) and mBJ with SOC (mBJ
SOC) are
used. GGA often gives much underestimated results as com-
pared to experiments[57,58]. The mBJ[59,60] exchange potential
in addition to GGA is known for its remarkable success in repro-
ducing experimental band gaps of semiconductors in general
and halide perovskites in particular[60]. These compounds con-
tain heavy elements like Bi; therefore, SOC calculations have
been carried out for better treatment of different orbital splitting
in electronic and optical properties. Self-consistent calculations
throughout the Brillouin zone were carried out using 2 × 106
Fig. 2. Energy versus volume optimization curves of Cs2 InBiX6 (X = F,
points.
Cl, Br, I).

Table 1. Calculated Tolerance Factor τ, Octahedral Factor μ, Lattice Constants

3. Results and Discussion a, Bond Lengths rij, Band Gap Eg, and Effective Masses of Electrons me and
Holes mh (mo) of Cs2InBiX6.
3.1. Structural Properties
The crystal structure of Cs2 InBiX6 is cubic and belongs to Parameters X=F X = Cl X = Br X=I
space group Fm-3m (225)[49]. The unit cell structure of
a (Å) 9.70 11.07 11.30 12.32
Cs2 InBiX6 (X = F, Cl, Br, and I) shown in Fig. 1 possesses
a a a a
10 atoms. The figure illustrates that, like the basic perovskite 9.80 11.44 11.93 12.69
structure (ABX3 ), double perovskite A2 B
B3
X6 is a three-
τ Eq. (1) 0.95 0.90 0.89 0.87
dimensional (3D) framework, in which the A cation (here
Cs
) occupies the cubic octahedral cavity formed by corner Eq. (3) 3.49 4.01 4.07 4.13
shearing of In and Bi octahedra. These octrahedra have fascinat-
μ 0.68 0.53 0.47 0.44
ing roles in the physical properties of perovskites.
In order to get ground state energies, unit cells of Cs2 InBiX6 rij (Å) Bi–X (x6) 2.25 2.73 2.79 2.82
(X = F, Cl, Br, and I) are optimized using the reported[49] lattice
In–X (x6) 2.60 3.00 3.09 3.15
parameters, symmetry of the space group, and atomic coordi-
nates. Total energy versus volume curves are plotted in Fig. 2 Cs–X (x12) 3.43 4.06 4.12 4.20
for Cs2 InBiX6 compounds, and the obtained values are then fit-
Eg (eV) GGA 2.01 0.38 0.25 0.12
ted to Birch Murnaghan’s equation of states[61]. The calculated
lattice constants are listed in Table 1. Halogen replacement mBJ 2.79 1.37 0.82 0.80

mBJ + SOC 1.87 0.87 0.32 0.23

HSE + SOC 2.22a 1.02a, 0.88b 0a, 0.33b 0a, 0.21b

me mBJ 0.73 0.52 0.37 0.28

mBJ + SOC 0.58 0.38 0.29 0.24
a a a
HSE + SOC 0.61 0.39 0.30 0.23a
MaPbI3 0.19c

mh mBJ 0.46 0.23 0.19 0.13

mBJ + SOC 0.37 0.19 0.14 0.09
a a a
HSE + SOC 0.39 0.17 0.11 0.08a
MaPbI3 0.25c
a
Reference [31].
b
Reference [53].
Fig. 1. Unit cell structure of Cs2 InBiX6 (X = F, Cl, Br, and I). c
Reference [62].

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Vol. 19, No. 3 | March 2021 Chinese Optics Letters

caused a systematic increase in the lattice constant; this increase (100) (110)
is due to the increase in size of anions from F to I. Bi X In X Bi X In X Bi
For structure stability of these double perovskites Cs2 InBiX6
(X = F, Cl, Br, I), a modified tolerance (τ) factor and an octahe-
X Cs X Cs X Cs Cs
dral factor (μ) are calculated from the ionic radii of the different
components given in the formulas[63]
In X Bi X In Bi X In X Bi
r
rX
τ = p


A , (1)
2r B
r X 
X Cs X Cs X Cs Cs
r
μ= B, (2)
rX Bi X In X Bi X In X Bi

where r B is the average radius of B
and B3
; rA and r X are the Fig. 3. Electronic charge density contours in the [100,110] planes.
radii of Cs and halogen atoms. The calculated values of tolerance
and octahedral factors are listed and compared with other theo- 3.2. Chemical Bonding
retical results in Table 1. A τ value in the range of 0.8 < τ < 1.0
and a μ value in the range of 0.44 < μ < 0.90 have been sug- For studying bonding aspects of these materials, we examine the
gested, X atoms in the (100)[49]. The tolerance factor varies electron charge densities of the understudy compounds. The
between 0.95 and 0.87, and the octahedral factor lies in the range electron charge densities for crystal planes (100) and (110)
of 0.68 to 0.44; the tolerance and octahedral factors reveal that are plotted in Fig. 3. The overlapping counters between Bi
Cs2 InBiX6 (X = F, Cl, Br, I) adopts an ideal perovskite structure. and X atoms in the (100) plane reveal a covalent bond and cor-
The accurate and probabilistic nature of the tolerance factor as respond to BiX6 octahedra. In plane (110), the counters In and X
well as its applicability over a broad range of perovskites creates overlap each other, which confirm covalent bonds and corre-
a new physical insight into the stability and the prediction of new spond to InX6 octahedra. The non-overlapping and spherical
stable organic, inorganic, and hybrid perovskites. A new toler- symmetric counters of Cs show ionic bonds between Cs and
ance factor formula is used for perovskite structure stability[32]: X. The calculated bond lengths are listed in Table 1. The table
reveals that the bond lengths increase from Cl to I, and this
  increase is related to the decreasing electronegativity and
rX r =r
τ= − nA nA − A B , (3) increasing size of the halogens. The electronegativities of Cs,
rB ln r A =r B  In, Bi, F, Cl, Br, and I are 0.79, 1.78, 2.02, 3.98, 3.16, 2.96, and
2.66, respectively, on a puling scale basis.
where nA is the oxidation state of the A atom. The calculated
values of τ using Eq. (3) are listed in Table 1, which clarifies that
the values are below 4.18 (stable perovskites are expected when 3.3. Electronic Properties
τ < 4.18)[32]. The tolerance and octahedral factors confirm the In order to examine the electronic nature, the band structure and
stability of Cs2 InBiX6 in cubic crystal structures, and, hence, density of states (DOS) are used to look at whether materials are
these compounds are investigated in elpasolite structures with insulators, conductors, or semiconductors. The band structure
space group Fm-3m, which corresponds to an ideal double and DOS calculations are performed using GGA, mBJ, and
perovskite. mBJ + SOC. Figure 4 reveals that Cs2 InBiX6 (X = F, Cl, Br, I)
Formation energies of Cs2 InBiX6 (X = F, Cl, Br, I) com- is direct band gap materials. The valence band maximum
pounds have been calculated in order to determine their stabil- (VBM) and conduction band minimum (CBM) both lie on
ity[64,65]: the same Γ symmetry line of the Brillouin zone. Direct band
P gap materials are more efficient for optoelectronic applications
Etotal − nEa as compared to indirect band gap because of phonon involve-
ΔE = , (4)
N ment, which make indirect band gap semiconductors bad emit-
ters of light[57,58]. Zhao et al.[49] and Xiao et al.[53] also reported
where Ea is the ground state energy of a single atom, n is the direct band gaps of Cs2 InBiX6 (X = F, Cl, Br, I) using the HSE

number of atoms of that species, and N represents the total SOC method. Figure 4 shows that SOC pushed the valence and
number of atoms in a unit cell. The energy of a single atom conduction bands toward the Fermi level that caused reduction
can be calculated by optimizing an isolated atom. The calculated of the band gaps in these compounds. SOC splits the Bi 6p in the
formation energies of Cs2 InBiF6 , Cs2 InBiCl6 , Cs2 InBiBr6 , and conduction band, pushing one of the orbitals toward the Fermi
Cs2 InBiI6 are −3.54 eV, −5.46 eV, −10.06 eV, and −15.12 eV, level and reducing the band gap. The band gap values are listed
respectively. The negative formation energies confirm the in Table 1. GGA underestimates band gaps of Cs2 InBiX6 (X = F,
thermodynamic stability of these compounds. Cl, Br, I). Our results calculated with mBJ
SOC are consistent

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Chinese Optics Letters Vol. 19, No. 3 | March 2021

Fig. 4. Electronic band structures of Cs2 InBiX6 (X = F, Cl, Br, I).

with the reported data[49,53]. MBJ is renowned for its excellent

band gap production near the experimental values. The calcu-
lated band gap value of Cs2 InBiCl6 is closer (the best solar cell
material MAPbI3 has a band gap of 1.55 eV) to the optimal value
Fig. 6. Partial density of states of Cs2 InBiX6 (X = F, Cl, Br, I).
for photovoltaic performance (1.4 eV)[66].
DOS is mostly used for physical properties of materials like
dielectric spectra, photoemission spectra, and transport proper- that SOC pushes the conduction band towards the Fermi level,
ties. It shows the role and location of different energy orbitals in which reduces band gaps of these metal halides. The partial DOS
the formation of a band structure. Total DOS and partial DOS of demonstrates that In 5s contributes to VBM. The halogen p
Cs2 InBiF6 , Cs2 InBiCl6 , Cs2 InBiBr6 , and Cs2 InBiI6 compounds orbitals have a dominant role in the formation of bands in
are given in Figs. 5 and 6, respectively. The Fermi level separates the energy range of −2 to −4 eV in the valence band. Bi 6p orbi-
the valence and conduction bands. From the total DOS, it is clear tals have contributed bands at energy of −4.5 eV in the
valence band.
The CBM is derived primarily from the Bi 6p orbitals, whereas
In 5p orbitals have significant contributions in the energy range
from 4 to 6 eV in the conduction band. The small band gaps of
Cs2 InBiX6 compared to other metal halide perovskites are due to
the fact that strong sp coupling between the 5s state of In and p
orbitals of halogen endorses the VBM to relatively high energy
with respect to the CBM[67]. Figure 6 also reveals that SOC splits
Bi 6p orbitals in the conduction bands and pushes one of the Bi
6p orbitals towards the Fermi level, which further reduces the
band gap of these compounds. The high energy In 5 s2 states,
which occupy VBM, are mainly responsible for the promising
photovoltaic properties of Cs2 InBiX6 (X = Cl, Br, I)[53]. Such
high energy states at the top of the valence band are stable with
respect to decomposition[49].
Band dispersion and carrier effective masses play a vital role
in the efficiency of solar cells and other optoelectronic materials.
The VBM and the CBM of Cs2 InBiX6 (X = F, Cl, Br, I) are
located at Γ symmetry of the Brillouin zone and have large band
dispersion. This large band dispersion results in the small carrier
effective masses[49]. The effective masses of electrons and holes
are calculated from the parabolic fitting of the band edges
Fig. 5. Total density of states of Cs2 InBiX6 (X = F, Cl, Br, I). according to the relation

030004-5
Vol. 19, No. 3 | March 2021 Chinese Optics Letters
 
∂2 εk −1 4.2 K[71]. The understudy compounds have larger values of
m = ℏ2 , (5)
∂k2 dielectric function than MAPbI3 in the visible spectral region.
The imaginary part of the dielectric function is the measure of
where εk and k represent band edge eigen values and wave vec- the extent of light absorption. It is a seed parameter and can be
tors, respectively. The effective masses of electrons me  and directly calculated from the Fermi–Golden rule; all other optical
holes mh  are listed and compared with the reported data in parameters including ε1 ω are calculated from ε2 ω. The first
Table 1. The table reveals that Cs2 InBiX6 has quit small carrier onsets of absorption (absorption edge) are observed roughly at
effective masses. Our calculated values of the carrier effective 2.75, 1.35, 0.80, and 0.80 eV for Cs2 InBiF6 , Cs2 InBiCl6 ,
masses are in good agreement with the reported work[48]. The Cs2 InBiBr6 , and Cs2 InBiI6 , respectively. These onsets are close
effective masses are also compared with MAPbI3 . It is evident to the fundamental band gaps of these compounds. The absorp-
from the table that SOC not only splits the band but also alters tion edge of Cs2 InBiCl6 is very close to that of MAPbI3 , which is
the values of the carrier effective masses. found at ∼1.55 eV[71]. Halogen substitution significantly
changes the positional occurrence of the transition peaks.
High absorption peaks are observed in the visible spectral region
3.4. Optical Properties at energy around 2–3 eV. Several weak peaks are observed in the
The interaction of light with the material medium is expressed in energy range of 3–15 eV.
terms of optical properties. Presently, we study optical proper- Knowledge of the refractive index nω is necessary for the
ties of metal halide double perovskites Cs2 InBiX6 (X = F, Cl, Br, effective use of a material in photonic and optical devices.
I) under the DFT scheme by measuring their different optical Refractive indices are inversely proportional to the band gap
parameters. of a material, i.e., wide band gap materials have small values
The study of polarization and absorption of electromagnetic of refractive indices and vice versa. The refractive indices for
radiation within the material medium is expressed in dielectric Cs2 InBiX6 X = F, Cl, Br, I compounds are shown in Fig. 7.
functions, which are mathematically presented by a relation The zero frequency limit of refractive index n0 values are listed
εω = ε1 ω
iε2 ω. In this relation, the first term represents in Table 2. The maximum peaks of the index of refraction for
the real part ε1 ω, which shows polarization of light, while the Cs2 InBiCl6 , Cs2 InBiBr6 , and Cs2 InBiI6 are observed in the
second term represents imaginary part ε2 ω of the dielectric energy range of 2–2.5 eV for these compounds. The peak values
function, which measures the extent of light absorption. The cal- are larger than the refractive index of MAPbI3 (2.61) in the
culated zero frequency limits (static dielectric constant) ε1 0 are
listed and compared in Table 2. This reveals that ε1 0 increases
10
as the band gap decreases from F to I, meaning that band gap A
A
A
A
A
A
A
A
A
A
AA
A

8 A
A
A
A
A A
A
A

energy has an inverse relation to ε1 0, which is consistent with

A
A A
A
A A
A
A
AA A
A
AA A
A

6 AA
A
AA
A
A
A
AA A

the Penn model[68]. These compounds have remarkable large

A
ε1 (ω)

4 A
A
A
A
A
A
A
A
A
A AA
A
A A
AAA
A
AAA
AA
A
AA
A
A

values of ε1 0 comparable with that of MAPbI3 and CsPbI3 .

A A
A
AA A
A
A A
AA
A
A A
A A A
A A
A A
A
A
A A
A A
A
A A
A
A A A A
A AA
A

2 A A AA A
A
A A A A A A
A
A A AA A
A
A A A
A A
AA AA
A
A AA
A
AA
A
A A A A AA A
AA
AAAA A
A A
A
AA
AA
A
A
A A A A
A
AA AAA
A A AA
A A

The maximum value of ε1 ω is observed in the visible energy

A AA A
A AA
A A AA
A A
AA
AA A AA
A
A A
A A A
AA A
A AA
A
AA
A
A A
A A
A A AA
AA AA
A A
A AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
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A
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A
AA
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A
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A
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AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
A
AA AA A A A A A A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA

0 A
A A
AA AA
A
AA
AA A A
AA
A
A AA
AA
A
AA
AA
A
AA
AA
A A A
A
AA
AA
A
AA
AA
A
AA A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
A A
A AA
A
AAAA
AA
A
A A
A AA
AA
A A
A A
AA
AA
A
AA
AA
A
AA
A AA
A
AA
AA
A
AA
AA
A
A
A A
A AA AA
A A
A
A A
AA AA
AA
A
AA A
AA
A
AA
AA
A
AA
AA
A
AA
AA
AA
AA
A A AA
A
A A
AA
AA
A
AA
AA
A
A
A
AAA
A
AA A
AA
AA

range (2–2.5 eV) and then rapidly decreases, and small humps -2 A
AA
AA
A

8 AA
AA Cs2InBiF6
are observed, which can be related to interband transitions AA
AA
A A
A

6
A A
A A Cs2InBiCl6
between valence and conduction bands. MAPbI3 has a dielectric A A
ε2 (ω)

A
A A
A A
A A
A A
Cs2InBiBr6
constant of 6.5 in the visible spectral range at the temperature of
A
A

4 A A
AA
A
A A
A A AA
A
A A A A
A A
A AA
A A A
A A
A A A
AA A
AA
A
A A A
A A
A AA
A A A A
A A A
A A
A A
A
A A A A A A

Cs2InBiI6
A A A A
A A
A A A
AA A A
A
A
A A AA A A
AA A
A
A AA AA
A A A
A A A A
A A A
A
A
A
A A
A AA
A
A A
AA
AAAA
A A
AA A A
A A A A A
A A
AA
A
AA A
A A A AAA
A

2 A A A AA A
AA A
A AA
A
A A
A A A A
A A AA AA
AA
A
A A
A A AA A AA A
A
A A
AAA
A
A AAA A A
A A
AAA
AA
A A
A A
A A
AA A
A A
AA
AA
A A
A AA A
AA
A
A A
A AA
A
A A AA AA
A
AA
AA
A
A A
A A
A A
A
A
A A
AA
A A
A A
A
A A
A AA
A
A AA A A
AA A
AA
A AA AA
A
AA
AA
A
A A
A A A
AA
AA
A
A AA
A A
A A
A
AA A
A
AA A
A A
A AA
A A
AA
A
AA
A
A AA A AA
AA
A
AA
AA
A AA
A
AA
AA
A
AA
A
A A
AA A
AA A
A
AA
AA
A
A AA
A
A
A AA
A
A A
AA
A
AA
AA
A
AA
A A
AA
AA
A A
A
AA
AA
A
AA

0
A A

4 A
AA
A A
A
AA
AA
A
AA
A A
A
AA
AA
A
AA
AA
A
AA
AA
A
AA

Table 2. The Zero-Frequency Values of the Real Part of the Dielectric Function A
A
AA
AA
A
AA
AA AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AAA
A
AAA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
A A
A
AA
AA
A
A A
AA
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
A
A

and Refractive Index.

3 A
A
A
A
A
A
A
A
A
AA
AA
A
A
A
A
n (ω)

A
A
A
AA
A A
AA
A A
AA
A
AA A
A
A
AA
AA
A
AA
A
A
A

ε1(0)
A

Compounds n(0) 2 A
A
A
A
A
A
AA
A
A
A
A
A
A
A
A
A
A
A
A
AA
AA
A
AA
AA
A
A
A
AA
A
A A
A
A
A
A
A
A
A
AA
AA
A
A
A
A
A
A
AA
AA
A
A
A
AA
A
AA
AA
A
AA
A
AA
AA A
AA
A
AA
A AA A
A AA A
AA
AA A
A A
A
A
A A
A A A A
AA
AA A
A
A
A A
A AA AA A
AA
AA A
A AA A
A AA
AA
A
AA
A
A
A A
AA
A A
AAA
AA
A
AA
AA A
A A
A
A
A A
AA
A A
A A A
A AA
AA A
A A A A

1 A
AAA A
AA
A
A A
A AA
AA A
A A
A A
A
A
A
A AA
AA
A A
AA
AA
A A
A A
AA
A
AA
A
AA
A AA
AA
A
AA
AA AA AA
AA A
A A AA
A
A
AA
A
AA
AA
A
AA
AA
A A
AA
AA
A
AAA
A A
A A
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
A A
AA
AA
AA
A
AA
AA
A
AA
AA
A
AA
A
A AA
AA A
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
A
AA
A
AA
AA
A A
AA
A

2.73 1.66
A AA

Cs2 InBiF6
A
A
AA
AA
A
AA AA
AA
A
AA
AA
A
AA A
A
AAA
AA
A
AA
AA
A
AA
A
AA
A A
AA
A AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
A
AA
AA
A
AA
AA
A
AA
AA
A
A A
AA
AA
A
AA
AA
A
A
A
AA
A
AA
AA

0
4
Cs2 InBiCl6 4.65 2.10
3 AA
A
AA
L (ω)

A
A
A AA
A
AAA
A A
AAA
A A
A A
A A

Cs2 InBiBr6 6.00 2.47 A

A
A
A
A
A
A A
AA
A

2 A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
AA
A
A
AA
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A AA
AA
A
A
AA
A
A
AA
A
A
A
AA
A
A
A
AA AAA
A A
A
A
A A A
A
A
A A
A

Cs2 InBiI6 6.10 2.49

A
A A
A
AA A
A
A A
A

1 A AA
AA
AA
AAA
A
AA
AA
A
A
A
A
A
A
A
A
A
A
A
AAA
A
A
AA
A
A
A
A
A
A
A
A
A A
A
A
A
A
AA
A
A
A
AA
A A
A
A
A
A
AA
A
A
A
A
A
A
A
A
A
A
AA AA
A
AA
A
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A
A
A
AA A
AA
AA
AA
A A
A A
A A
A
A
AAAA A
A
A A
A A
AA
AA
AA A
A
A
A AAA
A AA
AA
A
AA
A AA AA
AA AA A
AA
A

5.00a 2.1a
AA
A
A A
A
A A
A AA
AA
A
AA
AA
A
AA
AA
A AA
A
AA
AA
A
AA
AA
A
AA AA
AA
A A
A
AA A A
AA
A A A
AA
AA
A
AA
AA A
A AA
A AAA
AA
A
AA
AA

CsPbI3 A
A A A
AA A
AA AA
A
AA
AA A
AA
AA
A
AA
A A
A
AA
AA
A
A A AA A
AA
AA
A
AA
AA
A A
A A AA
A
AA
AA
A
A A A
A
AA
AA A
AA
AA
AA
A
A AA
A A
AA

0 AA
AA
A
A AA
A
AA AA
A AA
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
A A
AA
A
AA
AA
A
AA
AA
A
AA AA
A
AA
AA
A
AA
AA
A
AA
AA
A
A A
A
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
AA
A
AA
AA
A
AA
AA
A
AA
AA
A A
A
AA
AA
A
AA A
AA
A
AA
A AA
A
AA
AA
A
A
A
A
AA
AA
A
AA
AA
A
AA
AA
A

b b
0 5 10 15 20 25 30
MAPbI3 6.00 1.68 Energy (eV)
a
Reference [69]. Fig. 7. Frequency dependent optical parameters of Cs2 InBiX6 (X = F,
b
Reference [70]. Cl, Br, I).

030004-6
Chinese Optics Letters Vol. 19, No. 3 | March 2021

visible spectral range[71]. Appreciable values of nω below material; thus, G is calculated using two models Voigt
4.5 eV suggest that Cs2 InBiX6 is opaque against light. It explores (GV )[73] and Reuss (GR )[74]:
interactions of the incident photons and explains various fea-
1
tures of a semiconductor. The calculated Lω for Cs2 InBiX6 GV = 3C 44
C 11 − C 12 , (6)
is plotted in Fig. 7, in which no scattering happens when the 5
energy of the photon is less than the band gap energy. The high- 5C 11 − C12 C44
est peaks appear at the energy range of 17–20 eV. These peaks GR = : (7)
4C44
3C 11 − C12 
show plasma resonance, and their frequencies are called plasma
frequencies. However, Hill[75] (GH ) calculated the arithmetic mean of GV
and GR :
3.5. Mechanical Properties GV
GR
GH = : (8)
The mechanical properties of a material play an important role 2
in structure stability and strength of a material to an exterior The calculated values of GH show that Cs2 InBiI6 has the high-
force, and are associated with basic phenomena of solid state, est value (43.3 GPa) of shear modulus, which clarifies that it is
like inter-atomic bonding, phonon spectra, and equation of stiffer than the rest of the materials. The reaction of a material to
state. Mechanical properties are computed using independent linear deformation can be determined from Young’s modulus
elastic coefficients C ij calculated using the Charpin package (Y), i.e., the toughness of a material depends on the value of
embedded in Wien2k and listed in Table 3. Y. The higher the value of Y, the greater the toughness of a
The calculated results satisfy the Born mechanical stability material will be, which is calculated using the relation
criteria, i.e., C11
2C12 > 0, C 44 > 0, C 11 − C 12 > 0, and
C12 < C11 [72], which show that these compounds are a mechan- 9BGV
Y= : (9)
ically stable perovskite structure. Resistance of a material to 3B
GV
reversible deformation upon shear stress is calculated from shear
modulus (G), which gives information about the rigidity of a The larger value of Y (103.2 GPa) for Cs2 InBiF6 indicates
a high toughness among these compounds. Pugh’s ratio (B/G)
Table 3. Calculated Values of Elastic Constants Cij, Shear Modulus G, Young's can be used to examine the ductile/brittle nature of a
Modulus Y, Bulk Modulus B, Shear Constant C 0 , Cauchy Pressure C 00 , B/G Ratio, material[76]; material is ductile if the value of B/G is less than
ν, ζ, A, λ, and μ Parameters. 1.75, otherwise it represents a brittle nature. Pettifog and
Chen have established the brittle versus ductile transition in dif-
Parameters X=F X = Cl X = Br X=I ferent materials using first principles calculations[77,78]. Our cal-
culated results show that these compounds have lesser value of
C11 (GPa) 98 81 105 71 B/G than the critical value of 1.75, which confirm that these
C12 (GPa) 35 28 31 20 materials are brittle in nature. The bonding nature of a material
can be explained with the help of Cauchy pressure[78]. The
C44 (GPa) 57 44 41 62 value of Cauchy pressure is determined using the following
GV (GPa) 46.8 37.0 39.4 47.4 equation:

GR (GPa) 43.0 34.8 39.3 39.4 C 00 = C 12 − C44 : (10)

GH (GPa) 44.9 35.9 39.3 43.4 Lower values of Cauchy pressure show directional response in
Y (GPa) 103.2 87.3 95.6 99.6 bonding (covalent bonding), while higher values of Cauchy
pressure result in ionic bonding. The values of C 00 mentioned
B (GPa) 49.2 45.6 55.6 37.0 in Table 3 confirm that these compounds are brittle in nature.
B/G 1.09 1.27 1.41 0.85 The compressibility is measured with the help of Poisson’s ratio
ν, which is the ratio of adjacent longitudinal strain in non-axial
C 00 −22 −16 −10 −42 tensile stress:
ν 0.15 0.18 0.21 0.05
3B − Y
ν= : (11)
Z 0.61 0.59 0.52 0.50 6B
A 1.80 1.66 1.100 2.43 A material having ν < 0.5 is considered incompressible[79],
C0 31.5 26.5 37.00 25.5 and ν ≥ 0.5 has the tendency of compressibility, i.e., stretching
a sample causes no adjacent reduction, so its volume remains the
λ 19.1 21 29.4 5.4 same no matter how distorted it is. The values of Poisson’s ratio
μ 60.7 37 39.4 47.4 for compounds Cs2 InBiX6 (X = F, Cl, Br, I) lie in the range of
0.05–0.21, which show that these materials are incompressible.

030004-7
Vol. 19, No. 3 | March 2021 Chinese Optics Letters

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Chinese Optics Letters Vol. 19, No. 3 | March 2021

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