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Cs2TlBiI6: a new lead-free halide double perovskite with direct band gap
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 Journal of Physics: Condensed Matter

J. Phys.: Condens. Matter 31 (2019) 445902 (8pp) https://doi.org/10.1088/1361-648X/ab32a5

Cs2TlBiI6: a new lead-free halide double

perovskite with direct band gap
Shruthi Nair1, Mrinalini Deshpande2,5, Vaishali Shah3, Subhash Ghaisas4
and Sandesh Jadkar1,5
1
  Department of Physics, Savitribai Phule Pune University, Pune 411 007, India
2
  Department of Physics, H.P.T. Arts and R.Y.K. Science College, Nasik 422 005, India
3
  Interdisciplinary School of Scientific Computing, Savitribai Phule Pune University, Pune 411 007, India
4
  School of Energy studies, Savitribai Phule Pune University, Pune 411 007, India

E-mail: sandesh@physics.unipune.ac.in and d_mrinal@yahoo.com

Received 25 January 2019, revised 9 July 2019

Accepted for publication 16 July 2019
Published 7 August 2019

Abstract
The recent development of halide double perovskites A2B′BʺX6 with favorable band gaps have
provided a new search direction for stable Pb-free perovskite solar cells. Here, we propose a
new lead free double perovskite Cs2TlBiI6 as a potential candidate for perovskite solar cell
absorber. We probe the structural, electronic and optical properties of this material through
density functional theory calculations. Our calculations on this material show that Cs2TlBiI6
adopt cubic double perovskite structure with space group Fm-3m. Using PBE exchange-
correlation functional we obtain direct band gap of about 1.37 eV at the centre of Brillouin
zone. The direct band gap and strong optical absorption of this material in the visible energy
range of solar spectrum implies that Cs2TlBiI6 can be a potential candidate for perovskite
based solar cell. Our fundamental calculations on this material would open up further
possibility of experimental studies on TlBi based perovskite.

Keywords: double perovskites, Cs2TlBiI6, DFT, optical properties

(Some figures may appear in colour only in the online journal)

1. Introduction Trivalent cations such as Bi3+, alongwith monovalent cation

Lead (Pb) halide perovskites have attracted tremendous atten-
tion in recent years due to their rich opto-electronic proper-
ties, which have resulted in more than 22% power conversion
efficient photovoltaics (PV) [1–4]. Nevertheless, the chemical
instability and Pb-metal toxicity remains a huge hurdle for
extensive applications of these compounds. Thus, alterna-
tive compounds with similar opto-electronic properties need
to be developed. On the front of Pb replacement, several
lead-free perovskites and perovskite-derivatives including
vacancy-ordered double perovskites, cation-ordered double
perovskites (elpasolites), and 2D perovskites have been pro-
posed during the past two years as potential substitutes for
MAPbI3 (MA  =  CH3NH3) [5–7].
Recently, trivalent Bi3+ and Sb3+ also have been used to
replace Pb to form 2D layered Pb-free halide perovskites [6].
5
Author to whom any correspondence should be addressed.
such as Ag1+, have concurrently been introduced into the
B-sites of halide perovskites, leading to B-cation double per-
ovskites with the general chemical formula A2B′BʺX6. Among
this class of compounds, Cs2AgBiBr6 and Cs2AgBiCl6 have
been reported to have promising photovoltaic properties with
good stability [8–10]. The band gaps obtained for these com-
pounds by optical measurements range from 2.2 eV [7] to
2.77 eV [10] for Cs2AgBiCl6 and from 1.83 eV [9] to 2.19 eV
[10] for Cs2AgBiBr6, while that calculated using DFT and
hybrid functionals is found to be 2.62 eV [10] to 3 eV [7] for
Cs2AgBiCl6 and 2.06 eV [10] to 2.3 eV [7] for Cs2AgBiBr6.
Although these Ag–Bi double perovskites exhibit band gaps
in the visible range, the gaps are indirect, which is not ideal
for thin film PV application. Zhang et al [11] have reported
that In1+ and Tl1+ are two viable candidates if used in com-
bination with Bi3+ give direct band gap. Recently, Zhao et al
[12] reported direct band gap of 0.91 eV for Cs2InBiCl6 using
HSE functional along with the effect of spin–orbit coupling

1361-648X/19/445902+8$33.00 1 © 2019 IOP Publishing Ltd  Printed in the UK

J. Phys.: Condens. Matter 31 (2019) 445902
(SOC). However, In1+ based compounds like Cs2InBiX6
suffer from stability issues due to oxidation of In1+ to In3+
[13]. Monovalent Tl1+ when used with Bi3+ may be a possible
combination which can satisfy the criteria of direct band gap
and hence requires detailed study in order to be incorporated
in perovskite solar cell absorbers.
The density functional theory has been playing signifi-
cant role in explaining the electronic and optical properties of
organic–inorganic hybrid perovskites [14]. Giacomo et al [15]
theoretically attempted to substitute Tl1+ and Bi3+ in place of
Pb2+ (into tetragonal MAPbI3 structure) and obtained direct
band gap of 1.68 eV using PBE functional. Later in 2016,
Deng et  al [16] through their computational studies on lead
free hybrid double perovskites (CH3NH3)2BIBIIIX6 reported
the variation in band gap with the variation in terminating
group (X) from Cl to Br to I. Theoretical calculations on
these materials show that the band gap of (CH3NH3)2TlBiX6
decreases from 1.23 eV to 0.72 eV to 0.28 eV as X changes
from Cl to Br to I. Single crystals of (CH3NH3)2TlBiBr6 were
synthesized by the same group by hydrothermal method and
an optical band gap of 2.16 eV was reported [16]. Similar
results have been reported by Savory et al [17] for inorganic
Cs2TlBiX6 (X  =  Cl, Br) using hybrid functionals. The com-
parative results of above two works on TlBi perovskites show
that band gaps of these double perovskites show very little
variation with A cation i.e. (CH3NH3)2TlBiBr6 has band gap
0.72 eV while replacement of CH3NH3 with Cs gives band
gap 0.71 eV for Cs2TlBiBr6. Based on these results, here we
have considered Cs as the A cation and I as X anion in the TlBi
based double perovskite A2TlBiX6 to start with. Motivated by
these results and since inorganic TlBi-iodide based double
perovskites have not been explored, we have initiated our
investigations on inorganic TlBi halide based double perovs-
kite, Cs2TlBiI6. We apply DFT calculations to this material to
probe its structural, electronic and optical properties. We pre-
sent the results of electronic band structure, density of states
(DOS) and frequency dependent dielectric properties for the
fully optimized crystal structure. Through our calculations,
we have shown that Cs2TlBiI6 can show favorable light har-
vesting properties in perovskite solar cell and thus will pro-
vide a step towards experimental synthesis of this material.
2.  Theoretical calculations
All the theoretical spin polarized calculations are based on
Density Functional Theory as implemented in the vienna
ab initio simulation package (VASP) [18] program. The all-
electron projector augmented wave (PAW) [19] method is
adopted for pseudopotentials with following electrons treated
explicitly: Cs (5s 5p 6s), Tl (5d 6s 6p), Bi (5d 6s 6p) and I (5s
5p). The calculations are performed using electron exchange-
correlation functional of Perdew–Burke–Ernzerhof (PBE)
[20]. The crystal structure of Cs2TlBiI6 is initially built using
scrap values of lattice parameters and atomic positions from
experimental data assuming cubic symmetry. Visualization
for electronic and structural analysis (VESTA) program has
been used to build and visualize the crystal structures after
optimization. All the calculations have been performed on
2
S Nair et al
a supercell that consists of 40 atoms i.e. four formula units
of I2-I-III-VII6. Both the primitive cell (10 atoms) as well as
supercell of Cs2TlBiI6 has been optimized and their energy
convergences with respect to different k-meshes and cut-
off energies have been tested. The atomic positions and cell
parameters are optimized using special Davidson block itera-
tion method. The structures are considered to be converged
when the force on each ion is less than 0.001 eV Å−1 with total
energy convergence of ~10−5 eV. After the convergence tests,
7  ×  7  ×  7 mesh and default kinetic energy plane wave cut-off
of 242.9 eV were chosen for the structural calculations. The k
points are sampled in the 1st Brillouin zone with Γ-centered
7  ×  7  ×  7 mesh for the electronic calculations, while a finer
11  ×  11  ×  11 mesh is used for density of states and optical
calculations. SOC calculations are performed on the optim­
ized structure inorder to check the relativistic effects of
heavier elements Tl and Bi on the electronic properties of the
material [21]. In the standard mode, VASP performs a fully
relativistic calculation for core electrons and treats valence
electrons in a scalar relativistic approximation. In VASP code,
the spin–orbit operator HS·O consists with l  =  3, l  =  2 and
l  =  1 orbitals [22]. The optical response of the material is
studied using frequency dependent dielectric function under
independent particle approximation [23].
3.  Results and discussions
A visualization of basic and double perovskite structure is
shown in figure 1 which shows that like the basic perovskite
structure (ABX3), double perovskite A2B′BʺX6 is a 3D frame-
work of corner connected octahedra with monovalent A cat-
ions (here, Cs+) occupying cubeoctahedral cavities in the
framework. From the direct comparison with CsPbI3, it is clear
that the double perovskite under investigation, Cs2TlBiI6, is
obtained by replacing divalent Pb+2 ions by monovalent Tl1+
and trivalent Bi3+ ions thus forming alternating Tl1+ and Bi3+
octahedra in the structure. Cs2TlBiI6 crystallizes in elpasolite
structure which corresponds to an ideal double perovskite
with space group Fm-3m. As discussed earlier, this structure
is a network of corner-sharing octahedra with Cs+ ions in the
middle of cuboctahedral cavity. Each Cs+ is coordinated to
12 I− ions while every Tl and Bi is coordinated to 6 I− ions.
The polyhedral model of Cs2TlBiI6 in figure  2 shows TlI6
and BiI6 octahedra which alternate along [1 0 0], [0 1 0] and
[0 0 1] directions. The centres of octahedra are occupied by Tl
or Bi alternating in a rock-salt configuration. The calculated
structural parameters of Cs2TlBiI6 are listed in table 1. Tl–I
and Bi–I bond lengths are found to be 3.292 Å and 3.089 Å,
respectively which when compared with the bond lengths for
(CH3NH3)2TlBiI6 (3.292 Å and 3.063 Å) [16] shows that Tl-I
bond length is not affected by A+ cation variation whereas
Bi–I length is slightly more for Cs based compound.
We qualitatively assess the crystallographic stability
of Cs2TlBiI6 using Goldschmidt empirical criteria [24].
According to this criteria, one can assign a perovskite, two
parameters, tolerance factor and octahedral factor. The tol-
erance factor is defined as t  =  (RA  +  RX)/√  2 (RB  +  RX),
with RA, RB and RX being the ionic radii of A, B and X ions,
J. Phys.: Condens. Matter 31 (2019) 445902 S Nair et al

Figure 2.  The optimized super cell of Cs2TlBiI6 double perovskite.

The Cs, Tl, Bi and I ions are shown in blue, gray, pink and green
colors, respectively.

Table 1.  The geometrical parameters of the optimized structure of

Cs2TlBiI6, the numbers in parenthesis under bond lengths indicate
coordination number of Cs, Tl, Bi with I.
Crystal system Cubic
Space group Fm-3m (# 225)
Lattice parameters a  =  12.853 Å
b  =  12.846 Å
c  =  12.846 Å
Figure 1.  Unit cell of CsPbI3 (top) and Cs2TlBiI6 (bottom) α  =  β  =  γ  =  90°
depicting structural comparison between basic and double
perovskite. Dark gray octahedra shows PbI6 while alternating Volume (Å)3 2121.2
light gray and violet octahedra shows TlI6 and BiI6 octahedra, Bond lengths (Å) Cs-I (×12)  =  4.544
respectively with Pb, Tl and Bi occupying the centres of octahedra. Tl-I (×6)  =  3.292
Violet spheres are iodine atoms.
Bi–I (×6)  =  3.089
respectively; stable structures usually have values in the range
0.75  <  t  <1.0 [24]. The octahedral factor which is a measure 
of BX6 octahedral stability, is defined as µ  =  RB/RX, and [ETotal − n Ea ]
(1) ∆E =
stable structures tend to have 0.414  <  µ  <  0.732 [24]. Since N
we have double perovskite with different radii at site B, we where Ea is the atomic energy for each atom (or ion) belonging
consider the average ionic radii of Tl and Bi as RB. Employing to the crystal unit cell, n is the number of atoms of that species
the Shannon ionic radii of Cs, Tl, Bi and effective radii of I and N is the total number of atoms in the unit cell.
[25], for Cs2TlBiI6, we obtain (µ, t)  =  (0.57, 0.83), which lies
within the range of standard halide perovskites. The tolerance [ETotal − (8ECs + 4ETI + 4EBi + 24EI )]
(2) ∆E = .
factor (t) for (CH3NH3)2TlBiI6 is found to be 0.8917 which 40
reveals that Cs2TlBiI6 is structurally slightly less stable as The energies of isolated atoms are calculated by placing
compared to (CH3NH3)2TlBiI6. For comparison, the tolerance them in a unit cell of optimized dimensions. The obtained
factors of Cs2B′BʺI6 compounds were computed and it was value  −2.21 eV suggests that the reaction is exothermic. This
found that among them In1+ based compounds i.e. Cs2InBʺI6 value is consistent with that reported for the organic-inor-
show highest structural stability in cubic phase (t  =  0.968 ganic counterpart MATl0.5Bi0.5I3 [16] (MA+ = CH3 NH+ 3)
and 0.926 for Bʺ  =  Sb, Bi, respectively). We suspect that the i.e.  −2.72 eV in which formation energy has been obtained
reduced crystal stability of Cs2TlBiI6 as compared to similar by calculating energies of pure MATlI3 and MABiI3 instead
compounds is due to the large ionic radii of Tl1+. of individual atoms. The stability of the structure can also be
We calculated the formation energy of Cs2TlBiI6 from estimated from the charge transfer between Cs and Tl/Bi–I
total energy of our system and that of its constituent parts units. The Bader charge analysis [38] provides a picture of
according to, ionic interaction between Cs and the metal iodide octahedra

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J. Phys.: Condens. Matter 31 (2019) 445902
Figure 3.  Electronic charge density contour plot in the [1 0 1]
crystallographic plane of Cs2TlBiI6 with scale showing highest
charge density in the red regions and lowest in the blue regions;
Bader charge on each atom (right).
Figure 4.  Calculated band structure of cubic Cs2TlBiI6 along
high symmetry lines in the first Brillouin zone. The Fermi level is
aligned to zero.
since the average charge per Cs and TlBiI6 units is  +1.72e
and  −1.73e respectively. More understanding of the nature
of charge transfer between the atoms and the bonding mech­
anism can be obtained from the charge density distribution
map in figure 3. The overlap of contours along Tl–I and Bi–I
bonds shows the existence of covalent bonding between Tl
and I and between Bi and I. The absence of charge along Cs–I
bond shows the ionic nature of bonding between Cs and I
atoms.
The electronic properties of this material are further
explained on the basis of its band structure and electronic
density of states. The calculated band structure of Cs2TlBiI6
is shown in figure 4. It is observed that the minima of valence
band (VBM) and the maxima of conduction band (CBM) are
located at the centre of the Brillouin zone (Γ point). Hence
this material has a fundamental direct band gap of 1.37 eV at
Γ point. From the band structure, it is seen that both valence
and conduction bands are dispersive in nature near the edges.
The overall electronic properties of double perovskites
(A2B1+B3+X6) depend strongly on the atomic orbitals and the
4
S Nair et al
site occupation of B1+ and B3+ cations. It has been reported
that the B site cations must possess lone pair ns2 states in order
to have direct band and allowed optical transitions [17, 26].
The obtained direct band gap of Cs2TlBiI6 is suspected due
to 6s lone pair states of Tl and Bi because both Tl1+ and Bi3+
have the same fully occupied s shells. The interaction of
this lone pair electron with halide atoms gives rise to unique
structural and electronic properties of halide perovskites
[17, 27, 28]. Here, the s contribution of Tl completely matches
the Bi-s contribution which in turn interacts symmetrically
with the iodine atoms. The completely symmetric interac-
tion and orbital matching between Tl and Bi is a reason for
VBM at the zone centre and direct band gap of 1.37 eV. The
band structure can be closely examined by calculating the
total density of states (TDOS) and partial density of states
(PDOS) shown in figure  5(a). The orbital contributions to
the electronic structure can in detail be understood from the
analysis of PDOS. Several sets of bands are found in the
band structure. As noted earlier, the valence bands ranging
from  −5.85 eV up to Fermi level (0 eV) is more flat and is
primarily a mixture of I-5p, Tl-6s and Bi-6s states whereas,
the dispersive conduction band ranging from 1.36 eV to 6 eV
is composed of empty Tl-6p and Bi-6p states with a small
contribution of I-5p states.
It is well established that in basic ABX3 perovskites the VBM
is formed by anti-bonding states of B-s and X-p orbitals, and the
CBM originates mainly from B-p orbitals [14]. It is noted from
the PDOS images in figure 5(a) that VBM is characterized by
mixed Tl-6s and I-5p orbitals with a minor contrib­ution of Bi-6s
state because Tl-s has larger energy than Bi-s while the CBM con-
sists of mainly Bi-6p and Tl-6p states with a minor contrib­ution
of I-5p states. This observation is well supported by the band
decomposed charge density plots in figure  5(b). In Cs2TlBiI6,
the two metal cations Tl and Bi make different contrib­utions to
the band edge states. Tl atoms contribute more to the valence
band edge than Bi atoms while Bi atoms contribute more to the
conduction band edge. The contribution of the metallic orbitals
to the band edges is consistent with that reported for organic TlBi
perovskite [16] and inorganic Cs2TlBiBr6 [29]. It is observed
that Cs cation has a very negligible contribution to valence and
conduction states around Fermi energy since its energy levels
lie deep below the band edges around -8 eV. This suggests that
Cs+ cations do not directly influence the electronic structure and
properties of the material. The PDOS (figure 5(a)) along with
the charge density plot (figure 3) also gives a picture of bonding
mech­anism between the atoms. Since the highest energy bands
of Cs are located at  −8.2 eV and  −21.4 eV, Cs orbitals show
negligible overlap with Tl, Bi and I orbitals which shows that
there is no covalent interaction between Cs and Tl/Bi–I frame-
work. The hybridization of Tl-6s and Bi-6s states with I-5p state
is responsible for the covalent bonding between Tl–I and Bi–I.
These results are consistent with that observed in charge density
plot in figure 3. Thus, the band gap of Cs2TlBiI6 is defined by
the orbital overlap between Tl–Bi and I ions whereas Cs+ ions
act only as charge donor in order to keep the perovskite structure
stable.
We calculate the effective masses of photo-generated elec-
trons and holes existing around the bottom of conduction band
J. Phys.: Condens. Matter 31 (2019) 445902 S Nair et al

Figure 5.  (a) The uppermost panel shows the total density of states (TDOS) of Cs2TlBiI6 followed by panels showing partial density of
states (PDOS) of Tl, Bi, I and Cs atoms respectively; s and p states are shown in black and red colors, respectively and in (b) the iso-surface
and partial charge density of the VBM and CBM are shown.

(electrons) and the top of valence band (holes) by parabolic 8  dSk

ˆ
2
fitting of bands according the approximation relation, ε 2
(5)(ω) = 2
(Pnn (k) )
2πω BZ ∇ωnn (k)
 nn
ï 2 ò−1
∂ ε(k) where |Pnn (k) | is the dipole matrix element between initial
(3) m = 2
∂k2 and final states, n and n′ are occupied (En (k)  ⩽  EF) and unoc-
where ε(k) are the band edge eigenvalues and k is the wave cupied (En′ (k)  ⩾  EF) energy levels (EF is Fermi energy), Sk is
vector. an energy surface with constant value, ωnn′ is the energy dif-
Halide perovskites are known to possess ambipolar conduc- ference between the two states En′ (k)  −  En (k).
tivity owing to balanced effective masses of electron and hole Kramers–Kronig relation is used to calculate the real part
[30]. The effective masses of electrons (m∗e ) and holes (m∗h) in of dielectric function from ε2(ω) [33],
Cs2TlBiI6 are calculated from the band structure (figure 4) to 2
ˆ ∞ 
ω s2 (ω  )
be 1.05 mo and 0.23 mo respectively (mo is electron rest mass). (6) ε1 (ω) = 1 + P
π 0 ω 2 − ω 2
It is observed that the hole mass is lighter than electron.
Halide perovskites are known for its unique optical prop- here, P indicates the principal part of the integral.
erties like strong absorption in the visible and UV region of Frequency dependent refractive index and extinction coef-
the solar spectrum, high optical absorption coefficient etc as ficient are calculated by the following relations,
compared to conventional solar absorbers. Hence, our major ï ò1/2
1 ¶ 2
©
2 1/2
interest is to calculate the optical properties of Cs2TlBiI6. (7) n(ω) = √ ε1 (ω) + ε2 (ω) + ε1 (ω)
The optical properties of a material like optical absorption 2
co-efficient, refractive index, reflectivity etc are explained by ï ò1/2
complex dielectric function as a function of frequency. The 1 ¶ 2
©
2 1/2
(8)
k(ω) = √ ε1 (ω) + ε2 (ω) − ε1 (ω) .
complex dielectric function describes the complete response 2
of a material to the perturbations caused by the electro­ Similarly, absorption co-efficient (α) is calculated by the
magnetic radiation [31]. This function is expressed as, equation,
ε(ω) = ε1 (ω) + iε2 (ω). 4πk(ω)
(4)
(9) α(ω) = .
The optical absorption of a material is proportional to the λ
imaginary part of this function ε2(ω) which can be calculated Figure 6(a) shows the real and imaginary parts of dielectric
by the following relation [32], function ε(ω) of Cs2TlBiI6. The imaginary part ε2(ω) is the

5
J. Phys.: Condens. Matter 31 (2019) 445902 S Nair et al

Figure 6.  Optical plots of Cs2TlBiI6 (a) complex dielectric function showing real part ε1(ω) (red) and imaginary part ε2(ω) (black),
(b) complex refractive index showing refractive index n(ω) (black) and extinction co-efficient k(ω) (red) and (c) optical absorption co-
efficient α(ω) as a function of energy.

absorptive spectrum that reflects the electronic transitions
from occupied valence bands to unoccupied conduction bands.
It shows absorption peak centered at approximately 2.5 eV.
The critical point (absorption onset) in the spectra is observed
at 1.35 eV i.e. at 918 nm. This point is closely related to the
electronic band gap of Cs2TlBiI6 which is 1.37 eV. The optical
absorption of a semiconductor is determined by its partial den-
sity of states. This is related to the density of states of valence
and conduction bands which depend on the atomic orbitals.
The absorption peak beyond the critical point in the spectra

6
J. Phys.: Condens. Matter 31 (2019) 445902
reflect the inter-band transitions which can hence, be identi-
fied by the PDOS of atoms shown in figure 5(a). This peak is
due to the electronic band edge transition from mixed states
of I-5p and Tl-6s in valence band to Tl and Bi-6p mixed states
in conduction band. This peak covers the entire visible region
of solar spectrum from 1.3 eV to 4 eV extending to ultraviolet
region. This suggests that photoelectrons in sp hybridized
orbital in valence band can be photo-excited to unoccupied
Bi-p orbitals in conduction band. It is suspected that this direct
p-p transition from valence band containing I-5p orbitals to
conduction band composed of Bi/Tl-6p orbitals could result
in strong optical absorption. This serves to be advantageous
than other reported double perovskites like Cs2AgBiX6 com-
pounds in which, such a p–p transition is not observed since
valence band in Cs2AgBiX6 consists of Ag-4d orbitals along
with X-p orbitals. The presence of Ag-d orbital in valence
band of Cs2AgBiX6 is partly responsible for indirect band gap
in these materials [17]. Figure 6(a) also shows the plot of fre-
quency dependent real part of dielectric function ε1(ω) versus
energy. The most important quantity in this spectra is the zero
frequency limit of the function ε1(0) i.e. static dielectric con-
stant. The value of ε1(0) is found to be 5.45 from the spectra.
Static dielectric constant of a material strongly depends on
its band gap according to relation ε1 (ω) = 1 + (ωp /Eg )2 , as
explained by the Penn model [31]. This value is similar to
the dielectric constant of 6.003 obtained for CsPbI3 [31]. This
value is also consistent with those reported for Cs2AgBiCl6
and Cs2AgBiBr6 [8, 21]. It can be observed from figure 6(a)
that ε1(ω) starts increasing from the zero frequency limit ε1(0),
reaches its maximum value, then drops down to zero at certain
energy and decreases to negative values around 3.93 eV. The
negative values of ε1(ω) show that in this energy region the
incident photons are totally reflected from the material [31].
Hence, the material exhibits metallic nature in these regions.
The knowledge of refractive index of a material is useful to
probe its application in optical devices. From figure 6(b) it can
be seen that the zero frequency limit of refractive index is 2.33.
The plot shows a value of 2.99 at 1.96 eV (631 nm) implying
that Cs2TlBiI6 can be used as an anti-reflective coating for
tandem solar cells [34]. From the extinction co-efficient
k(ω), optical absorption co-efficient α(ω) for the material is
obtained. The plot in figure  6(c) shows high absorption co-
efficient of the order of 105 cm−1 in the optical range of solar
spectrum. This result is obvious since halide perovskites are
known to possess high absorption co-efficient than conven-
tional absorbers like silicon. The strong optical absorption of
Cs2TlBiI6 in the entire visible region shows the usefulness of
this material in optoelectronic devices.
We, finally calculated the exciton binding energy of
Cs2TlBiI6 within the Mott-Wannier model [35], using the
equation,
me e4 mr 1 mr 1
Ebex =
(10) 2 2
≈ 13.56 .
2(4πε0 ) 2 me ε1 (0) me ε1 (0)2
Where mr is the reduced effective mass calculated by
mr  =  (me  ×  mh)/(me  +  mh) (me and mh are effective masses
of electrons and holes respectively) and ε1(0) is the static
7
S Nair et al
dielectric constant. Using the obtained values of effective
masses and static dielectric constant, the exciton binding
energy is estimated to be approximately 85.7 meV. This value
is comparable, although twice high, with that estimated for the
prototype CH3NH3PbI3 perovskite [36, 37].
Conclusions
To summarize, through DFT calculations we have theor­
etically studied the structural, electronic and optical prop-
erties of double halide perovskite Cs2TlBiI6. From the
structural calcul­ations we found that Cs2TlBiI6 is a cubic
double perovskite structure with Fm-3m symmetry. The
crystal stability of Cs2TlBiI6 has been qualitatively assessed
by calculating its geometrical tolerance factor and formation
energy. However, the thermodynamic stability of this material
still needs to be determined with respect to harmonic oscilla-
tions or by going beyond the harmonic approximation. The
Cs2TlBiI6 possess direct band gap of 1.37 eV at the center of
Brillouin zone. The completely symmetric interaction of lone
pair 6s states of Tl and Bi with I-p states results in valence
band edge at the Г symmetry point. The valence band edge
of Cs2TlBiI6 is a hybridized state of Tl–Bi 6s states with I-5p
states while conduction band edge is derived from 6p states
of Bi mainly. The effective masses of electron and hole in
Cs2TlBiI6 are estimated to be 1.05 mo and 0.23 mo respec-
tively. During light absorption, the Tl-6s/I-5p electrons can be
photoexcited to empty Bi-6p states. The optical studies show
that Cs2TlBiI6 shows strong absorption in the visible region
with peak centered ~2.6 eV. The strongest optical transition
originates from I-5p to metallic 6p states at the band edge. The
static di­electric constant is found to be 5.45 which is similar
to the value 6.00 obtained for CsPbI3. The Cs2TlBiI6 shows
high theoretical optical absorption co-efficient of the order
105 cm−1. Finally, exciton binding energy for this material
was estimated to be approximately 85.7 meV using Wannier–
Mott model. Our initial investigations on Cs2TlBiI6 would
pave way for further theoretical and experimental studies on
this double perovskite for its applicability in thin film photo-
voltaics and optoelectronics.
Acknowledgments
Shruthi Nair is thankful to the Ministry of New and Renewable
Energy (MNRE), Government of India for the financial sup-
port under National Renewable Energy Fellowship (NREF)
program. Sandesh Jadkar is thankful to University Grants
Commission (UPE program), New Delhi and Indo-French
Centre for the Promotion of Advanced Research-CEFIPRA,
Department of Science and Technology, New Delhi for spe-
cial financial support. The authors would like to acknowledge
Prof Dr Anjali Kshirsagar for providing high performance
computing (HPC) facility at Department of Physics, Savi-
tribai Phule Pune University, Pune. Vaishali Shah acknowl-
edges the computing facility in ISSC under the DST PURSE
program. Thanks to the Head, Department of Physics, H.P.T.
Arts and R.Y.K. Science College for providing computational
J. Phys.: Condens. Matter 31 (2019) 445902
laboratory. Thanks to Dr Ganesh Lonkar for fruitful discus-
sions on the selected material.
ORCID iDs
Sandesh Jadkar https://orcid.org/0000-0002-0610-7242
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