pubs.acs.

org/JPCC Article

Enhanced Visible Light Absorption in Layered Cs3Bi2Br9 Halide

Perovskites: Heterovalent Pb2+ Substitution-Induced Defect Band
Formation
Mrinmoy Roy, Supriti Ghorui, Bhawna, Jiban Kangsabanik, Rekha Yadav, Aftab Alam,* and M. Aslam*
Cite This: J. Phys. Chem. C 2020, 124, 19484−19491 Read Online

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ABSTRACT: We have successfully substituted trivalent Bi3+ with

divalent Pb2+ in Cs3Bi2Br9-layered perovskites. Controlled hetero-
valent Pb substitution in these Cs3Bi2Br9-layered perovskites
reduces the band gap because of the emergence of defect states
in between the bands. These heterovalent Pb-substituted Cs3Bi2Br9
bulk perovskite compounds are successfully synthesized for the first
time by chemical reprecipitation method. X-ray photoelectron
spectroscopy analysis indicate that lead substitution in the structure
is in Pb2+ form, which creates a charge imbalance in the compound
as it replaces Bi3+ from the layered perovskite structure. Such
charge imbalance is compensated either by bromine vacancies
(VBr) or interstitial cesium (Csi) additions. VBr or Csi in Cs3Bi2Br9
along with PbBi creates defect states in between the bands, which
results in redshift in the layered perovskite band. Band structure calculations indeed confirm the onset of such defect states,
responsible for the redshift. A more detailed defect physics simulation indicates that the defect complex PbBi + VBr is more probable
to form if Pb is rich in the environment, which consequently introduces a few deep level defects responsible for the reduction of the
band gap. Understanding of the electronic structure and defect physics of such heterovalent Pb-substituted Cs3Bi2Br9 will strengthen
the future photovoltaic and optoelectronic applications.

■ INTRODUCTION
Controlled doping in a semiconductor is one of the key aspects
alternative, as it has the same 3D crystal structure and
electronic dimensionality as MAPbI3, and Sn belongs to the
same group as Pb (group 14 in the periodic table). However,
for the semiconductor industry as doping can tune/change the
the tendency of change in the oxidation state from Sn2+ to Sn4+
optical and electrical properties of that material, which is the
in ambient conditions quickly disintegrates the 3D structure of
most desirable part for customized device fabrication. New
MASnI3 and makes it nonprofitable in a realistic device
electronic levels introduced by dopant elements are the main
platform.11,12 More recently, the quest for efficient, less-toxic
reason for a desired but functional device.1 As the doping
materials has led to the exploration of various types of
concentration increases, impurity levels in the band become
alternative perovskite structures. In this aspect, different
more influential and more prominent, and these bands start
nontoxic double perovskite [A2B(III)B′(I)X6] structures,
overlapping with conduction/valance bands of the n- or p-type
with elements of stable +3 and +1 oxidation states (B and
materials, rendering a smaller or narrower band gap. Such band
B′ site, respectively), are also getting examined, with little to no
engineering is routinely sought in various types of optoelec-
success regarding the device efficiency.13−17 Despite the
tronic applications.2−4 Hybrid/inorganic tri-halide lead perov-
extensive mobilization in the double perovskites, the inherently
skites are a class of the emerging semiconducting compounds indirect band gap or direct band gap with forbidden optical
for photovoltaic/optoelectrical applications. In 2009, Kojima et transition makes it impractical for photovoltaics or optoelec-
al. first introduced MAPbI3 (MA = CH3NH3+) as an absorber trical applications. A recent addition to alternative perovskites
material for photovoltaic applications.5 In a decade, these lead
halide perovskite solar cells have reached ∼25% photocurrent
efficiency.6−10 Though high photocurrent efficiency is well Received: June 28, 2020
established now, ambient stability and hazardous nature of lead Revised: July 15, 2020
are still a hot and existing research problem. A penchant has Published: July 16, 2020
shifted to find a less-toxic air-stable perovskite, with an
isostructural framework. To address these concerns, the tin-
based 3D perovskite (MASnI3) was suggested as a less-toxic

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.jpcc.0c05880

19484 J. Phys. Chem. C 2020, 124, 19484−19491
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Figure 1. (a) Powder XRD patterns of Cs3Bi2Br9 with various Pb alloying concentrations. The XRD data show a small lower angle shift in the
lattice planes, as Pb has higher ionic radius (1.19 Å) as compared to Bi (1.03 Å). (b) SEM images of various lead-substituted Cs3Bi2Br9 compounds.
(c) Digital image of different Pb-substituted Cs3Bi2Br9 powder samples. The systematic change of color indicates that Bi is replaced from the
structure.
is the A3B2X9 type of layered polymorphs of vacancy-ordered
triple perovskites (where A = MA+, Cs+; B = Bi3+, Sb3+, and X
= Cl−, Br−, I−). Though these compounds have been reported
a long time back, however, most of those studies are only
focused on the crystal structure, phase transition, and some
basic magnetic/optical properties of the pristine Cs3Bi2X9 (X =
Cl−, Br−, and I−) compound.18−21 Recently, few applications of
A3B2I9 are reported in optoelectronic and photovoltaic
applications, with very less power conversion efficiency
(∼1.64%).22−27 Therefore, it is necessary to further investigate
various bismuth-based compounds with lesser toxicity and
higher stability impact.
The layered perovskite, particularity, Cs3Bi2X9, is isostruc-
tural to the CsPbX3 perovskite as Bi3+ has a similar electronic
structure and ionic radius to Pb2+ but much lesser toxicity.
Although Cs3Bi2X9 crystallizes as an ordered perovskite
structure with only two-third of the lead position (as compared
to CsPbBr3) occupied by bismuth, the one-third unoccupied
lead site in octahedra remains vacant. Thus, Cs3Bi2Br9 makes a
corner-shared double-layered [BiBr63−] octahedral which leads
to low carrier mobility; which could be more beneficial for
various optoelectrical applications (e.g., photodiodes, photo-
detector, etc.) rather than photovoltaic utility.20,21,28,29
External doping in Cs3Bi2Br9 could lead to alteration in carrier
type, mobility of the carrier, and the band structure, which
could be useful for above-mentioned applications. Till now,
little efforts have been in place to modify the electronic
structure of this layered perovskite by putting pressure or
doping metal at the “Bi” position. Recently, Zhang et al.
showed that when pressure is applied, Bi−I bond contraction
and the bridging Bi−I−Bi angle decrease enhance the atomic
orbital coupling, leading to a reduction in the band gap of
Cs3Bi2I9.30 Similarly, Gu et al. showed that doping of Ru3+ in
Cs3Bi2I9 reduces the band gap value from 1.98 to 1.80 eV.31
The doping of Ru narrows the optical band gap by inducing
shallow defect states which create more radiative recombina-
tion centers. In yet another example, Eu3+ doping in Cs3Bi2Br9
increases the band gap because of a decrease in the lattice
constant of the doped compound.32 Hence, to further enhance
the performance of Cs3Bi2Br9 for optically relevant usages,
material engineering is essential to taper the optical band gaps,
modify the defect chemistry, and optimize the electronic
structure.
In this work, we have successfully substituted heterovalent
Pb in Cs3Bi2Br9 to obtain complete knowledge about how the
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optical properties and electronic configuration vary, as ionic
radius of Pb2+ (1.19 Å) is similar to Bi3+ (1.03 Å).33 It is
expected that Pb can easily replace Bi from the Cs3Bi2Br9
structure. Pb-substituted Cs3Bi2Br9 is synthesized by room
temperature reprecipitation method, which to the best of our
knowledge is the first and successful one for Pb-substituted
Cs3Bi2Br9. X-ray photoelectron spectroscopy (XPS) results
confirm lead replacement in Cs3Bi2Br9 perovskites; Pb is
present in +2 oxidation state, whereas Bi is in +3 oxidation
state; so replacement of Bi with Pb leads to charge imbalance
in the compound, which creates additional new states above
the valance band. As the concentration of Pb increases in the
structure, these additional states get more and more prominent
and overlap with the valance band, which gives an impression
of change in the band gap value from 2.62 to 2.23 eV. First-
principles density functional theory (DFT) calculations are
also performed to get a better insight into the electronic/
optical properties and the defect states of Pb-substituted
Cs3Bi2Br9 compounds. The simulated band structure and
density of states (DOS) indicate the presence of mid-band gap
states because of Pb s and Br p antibonding orbitals. The
simulated absorption coefficient for different Pb substitutions
(12.5 and 25% of Pb of substituted Cs3Bi2Br9) shows a new
red-shifted absorption peak as compared to the pristine
Cs3Bi2Br9, which is similar to the experimental optical
absorption studies. Simulations involving PbBi along with Br−
vacancies (VBr) or Cs+ interstitials (Csi) reveal a change in the
electronic structure by introducing new states above the
valence band where the defect complex PbBi + VBr is more
probable to form if Pb is rich in the environment. We believe,
such a combined experimental and theoretical study of
heterovalent Pb-substituted Cs3Bi2Br9 will serve as a reference
for enhanced understanding of future optoelectronic/photo-
voltaic properties of other heterovalent substitutions.
■ RESULTS AND DISCUSSION
Phase and crystal structures of a lead-substituted Cs3Bi2Br9
compound are investigated via X-ray diffraction (XRD)
studies. Figure 1a shows the XRD pattern of pristine and
lead-substituted Cs3Bi2Br9 perovskites. Cs3Bi2Br9 shows five
prominent diffraction peaks originating from (101), (201),
(022), (300), and (220)/(005) planes which match quite well
with standard JCPDS data (JCPDS:01-070-0493) shown in
Figure S1 of Supporting Information. This result also confirms
that Cs3Bi2Br9 belongs to the hexagonal phase with space
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group P3̅m1.34 The same XRD peak position of Pb-substituted Table 1. Pb to Bi Ratio in Various Lead-Substituted
Cs3Bi2Br9 as the pristine compound confirms the formation of Cs3Bi2Br9 Perovskites with the Estimated Compositiona
single-phase perovskite. As the pristine and Pb-substituted
percentage of
Cs3Bi2Br9 perovskite belongs to the hexagonal phase, lattice the Pb/Bi the Pb/Bi Pb substitution
parameters are calculated for the pristine perovskite using the in the fed ratio in the in Bi position estimated
h2 + hk + k 2 l2 compound solution compound (%) composition
formula
1
d2
=
4
3 ( a2 )+ c2
are a = b = 7.90 ± 0.04 Å Pb:0 0 Cs3Bi2Br9
and c = 9.85 ± 0.06 Å. In Pb:15−Pb:25 has a small impurity Pb:5 0.05 0.0094 0.9 Cs3Bi1.98Pb0.02Br9
peak in XRD was observed which is located at 21.27 in 2θ Pb:10 0.1 0.025 2.5 Cs3Bi1.94Pb0.06Br9
value. This peak can be identified as (101) lattice planes of Pb:15 0.15 0.0504 5.0 Cs3Bi1.90Pb0.1Br9
PbBr2 which belongs to the orthorhombic phase of space Pb:20 0.2 0.0844 8.4 Cs3Bi1.84Pb0.16Br9
group Pnma. XRD patterns of various Pb-substituted layered Pb:25 0.25 0.1609 16.0 Cs3Bi1.71Pb0.29Br9
a
perovskites also give an idea about the crystalline size of the The ratio is estimated from ICP−AES measurements.
coherently diffracting domains. Scherrer method is utilized to
estimate the crystal size by considering the formula Cs3Bi1.94Pb0.06Br9, Cs3Bi1.90Pb0.1Br9, Cs3Bi1.84Pb0.16Br9, and
kλ
D = β cos θ , where D is the crystalline size, λ is the wavelength Cs3Bi1.71Pb0.29Br9 for Pb:5, Pb:10, for Pb:15, Pb:20, and
D Pb:25 samples, respectively. XPS measurement of these Pb
of the incident X-ray, k is a constant equal to 0.94, βD is the substitution Cs3Bi2Br9 compounds is carried out to acquire an
peak width at the half-maximal intensity, and θ is the peak idea about the composition and the chemical state of various
position of the most intense peak. The average crystallite size elements. The spectrometer dispersion is adjusted to the
of the Pb-substituted Cs3Bi2Br9 perovskite increases from 52 to binding energy of 284.8 eV for the C 1s line of adventitious
115 nm with the increase in lead concentration. XRD pattern (aliphatic) carbon present in the chamber on the sample.
of lead-substituted Cs3Bi2Br9 perovskite shows a similar type of High-resolution XPS spectra of 2.5% Pb-substituted Cs3Bi2Br9
crystal structure as pristine Cs3Bi2Br9 because Pb (1.19 Å) has (Cs, Bi, Pb and Br element), as shown in Figure 2a−d,
nearly the same ionic radius as that of Bi (1.03 Å), and also, it
has the same isoelectronic configuration (6s2). In previous
reports, people have shown that in Cs3Bi2Br9, Bi makes
unprecedented regular chains with halogen ions, which forms a
regular array of [BiBr63−].35−37 In [BiBr63−] octahedra, the
bond length of Bi−Br is 2.92 Å (axial), 2.92 and 2.82 Å
(equatorial) which closely matches with the Pb−Br bond (2.95
Å). This result indicates that Pb can easily replace Bi from the
perovskite structure. Powder XRD measurements show a small
lower angle shift in the lattice planes, as Pb has a higher ionic
radius (1.19 Å) than Bi (1.03 Å). Scanning electron
microscopy (SEM) images of these lead-substituted Cs3Bi2Br9
powders are shown in Figure 1b. Cs3Bi2Br9 is a layered type of
perovskite; SEM images clearly hint the appearance of the
layered nature in these perovskites.38 Interestingly, with Pb
incorporation into the structure/compound, the shape of the
perovskite did not change. This indicates that with lead
substitution in Cs3Bi2Br9, the structure and phase remain Figure 2. High-resolution XPS spectra of 2.5% Pb-substituted
intact. Color of the compounds evolves from bright yellow to Cs3Bi2Br9 (a) Cs 3d, (b) Bi 4f, (c) Pb 4f and (d) Br 3d. XPS data
dark orange, via the continuous increase of Pb elements in the of Bi and Pb confirms that Bi belongs to +3 state and Pb belongs to
structure, which indicates that lead is possibly getting +2 state.
incorporated into the structure. A similar kind of change in
color of the compound is observed when Bi is doped in corresponds to the core levels of Cs 3d, Bi 4f, Pb 4f, and Br 3d,
APbBr3 (A = MA and Cs) perovskites.33,39,40 respectively. The binding energy of Cs 3d5/2 and 3d3/2
The compositional study of various lead substituted-layered appearing at 724.5 eV and 738.5 eV, respectively, (shown as
perovskites is performed using inductively coupled plasma Figure 2a) matches with the previously reported results.41 The
atomic emission spectroscopy (ICP−AES). The Bi to Pb high-resolution Bi doublet spectrum is clearly resolved at 159.3
atomic concentrations obtained in ICP−AES analysis are eV for Bi 4f7/2, and 164.6 eV for Bi 4f5/2, and the spin−orbit
105.31, 39.85, 19.81, 11.84, and 5.9 for Pb:5, Pb:10, Pb:15, split of the f-level of Bi is nearly equal to 5.37 eV, which
Pb:20, and Pb:25, respectively (as listed in Table 1). The null matches with the previous experimental results.42 The high-
Pb to Bi atomic concentration ratio in Pb:0 is equivalent to resolution XPS spectra of Pb 4f are shown in Figure 2c. The
pristine Cs3Bi2Br9 perovskite. On the other hand, 105.31 Bi to deconvoluted Pb 4f spectrum has two main peaks at 138.4 and
Pb atomic concentration ratio in Pb:5 is equivalent to 0.9 143.2 eV corresponding to Pb 4f7/2 and Pb 4f5/2, respectively,
(±0.057) percentage substitution of Pb. Similarly, Pb:10, with an energy difference of nearly ∼5 eV, which correlates
Pb:15, Pb:20, and Pb:25 samples have 2.5 (±0.05), 5 well with Pb2+ state.33 XPS results confirm that Bi belongs to
(±0.057), 8.4 (±0.24), and 16.0 (±0.12) percentages of lead +3 state and Pb belongs to +2 state, and this charge imbalance
in the structure, respectively. Considering the ICP−AES can lead to chemical instability in the compound. To
estimated percentage of Pb substitution, composition of the understand the effect of the charge imbalance-related
perovskite can be roughly estimated as Cs3Bi1.98Pb0.02Br9, phenomenon on electronic/optical properties, we perform
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first-principles calculations using DFT as implemented in
Vienna Ab initio Simulation Package (VASP). Our band
structure simulation reveals that valence band maxima (VBM)
of Cs3Bi2Br9 has an antibonding characteristic which mainly
arises from Bi s and Br p orbitals, whereas conduction band
minima (CBM) is mainly comprised of Bi p and Br p orbitals
(shown in Figure S2 of Supporting Information). For Pb
substitution in the place of Bi lattice positions, there is an
additional sub-band which appears above the VBM of the
pristine compound, as shown in Figure 3a. This additional
Figure 3. (a) Band structure of 6.25% Pb-substituted Cs3Bi2Br9. Br p
and Pb s orbital contributions are shown by cyan and blue circles,
respectively. (b) Comparison of the total DOS and Pb s orbital-
projected DOS for 6.25, 12.5, and 25% Pb-substituted Cs3Bi2Br9. EF
denotes the Fermi energy.
band is predominantly contributed from Pb s and Br p orbitals
having antibonding character. This can be attributed to higher
atomic orbital energy of Pb s than Bi s. The total DOS and
projected DOS for three different Pb concentrations (6.25,
12.5, and 25) due to Pb s are shown in Figure 3b. The sub-
band gap DOS near the VBM increases with increasing Pb
concentrations in the pristine compound mainly due to Pb s
contribution. Here, the Fermi levels lie near the VBM because
Pb2+ is replaced with Bi3+ which creates a charge imbalance.
The charge imbalance due to Pb substitution in the compound
might get compensated by singly charged donor defects, and it
is discussed later in detail.
The normalized diffuse reflectance (DR) spectra of pristine
and Pb-substituted layered perovskites are shown in Figure 4a.
Figure 4. For various Pb-substituted Cs3Bi2Br9 compounds, (a) room-
temperature steady-state UV−vis DR spectra and (b) K−M function
vs wavelength. The pristine Cs3Bi2Br9 perovskite shows a sharp
absorption edge at 475 nm, while Pb-substituted Cs3Bi2Br9 illustrates
a significant amount of redshift in the absorption edge (at 575 nm).
The absorbance of any material in transmission mode is
governed by A = KTd, where KT is the absorption coefficient in
transmission mode and “d” is the thickness of the sample. It is
a well-known fact that the typical absorption spectrum can be
constructed from the DR spectrum (i.e., F(R∞) = K/S = (1 −
R∞)2/2R∞, where K and S are the absorption and scattering
coefficient of the sample, respectively), which matches with the
true absorption spectrum, if and only if the scattering
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coefficient (S) is independent of the wavelength. When the
wavelength of the interacting photon is less than the average
grain size of the absorbing material, the scattering coefficient is
independent of the wavelength, and this condition is satisfied
for the bulk sample/material. By considering the above
assumption, it is found that K (absorption coefficient of the
diffused reflected spectrum) and KT (absorption coefficient in
transmission mode) were proportional to each other. For this
reason, diffused reflection function or Kubelka−Munk (K−M)
function F(R∞) closely matches with the actual absorption
spectra.43 The plot of F(R∞) as a function of energy could be
offset vertically to make it coincide with the logarithmically
plotted transmission spectrum. Hence, we convert the DR
spectrum into absorbance spectrum to calculate the exper-
imental band gap value of Pb-substituted Cs3Bi2Br9. Figure 4b
shows the K−M function as a function of the wavelength of
pristine and Pb-substituted Cs3Bi2Br9 perovskites. The pristine
Cs3Bi2Br9 perovskite shows a sharp absorption edge at 475 nm.
Pb-substituted Cs3Bi2Br9 shows a significant amount of redshift
in the absorption spectrum. As we gradually increase the Pb
concentration in the compound, the absorption edge is getting
shifted to 575 nm. This observation indicates that there is
possibly a change in the band gap of the compound. Zhang et
al. reported that Cs3Bi2Br9 poses a direct and an indirect band
for an optically allowed transition, and the difference between
the direct band gap and indirect band gap is 70 meV.44 The
conventional way to find the nature of the band is to fit the DR
spectra using K−M function. [F(R∞)hν]n vs hν plot could give
us a complete idea about the nature or type of the band; if n =
2, then it is a direct allowed transition or if n = 1/2, then it is
an indirect allowed transition. In this work, we also find that
Cs3Bi2Br9 perovskite poses the same type of nature in the band
from the K−M plot (Figure 5a). The direct band gap of
Cs3Bi2Br9 is 2.67 eV, whereas the indirect band gap is 2.62 eV.
As we increase the Pb concentration in Cs3Bi2Br9, the direct
and indirect band shifts toward the lower values as compared
to the pristine Cs3Bi2Br9. 0.9% lead in Cs3Bi2Br9 starts shifting
the indirect band to a lower energy side, and after 2.5% lead
substitution, it almost fixed at a value of 2.23 eV. Similarly, the
direct band of the Cs3Bi2Br9 shifts toward a lower energy value,
however, with a higher percentage of lead substitution. With
5% lead substitution, direct band starts showing a redshift, and
with 8.4% lead substitution, this direct band is shifted to 2.33
eV. After 16% of Pb substitution in Cs3Bi2Br9, we did not see
any further changes in absorption spectra and optical band gap.
Hence, from these results, we can indirectly say that 16% Pb
substitution is the limit; after that, no further change in the
optical results can be found. To understand a reasonable
reduction in the band gap, we figured out that researchers have
tried to incorporate Bi in the APbBr3 structure, where A = MA
or Cs. These studies are mainly focused toward unraveling the
electronic structure variations with Bi-doping in MAPbBr3
perovskites. For the very first time, Abdelhady et al. revealed
that with Bi-doped MAPbBr3 shows a redshift in the band gap
by 300 meV, as the CBM shifts downward.33 They also
demonstrated that with an increase in Bi concentration, the
majority charge carriers alter from (hole) p-type to (electron)
n-type, as the Fermi level gets closer to the conduction band.
Similarly, Bi doping in MAPbCl3 reduces the band gap of the
compound. Band gap narrowing of 300 meV (a 55 nm red-
shifting absorption edge) is obtained for the nominal 20% Bi-
doped single crystal.39 In 2017, Nayak et al. contradicted this
work and demonstrated that the band position did not change
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Figure 5. Direct (red line) and indirect (blue line) K−M plot of various Pb-substituted Cs3Bi2Br9 compounds (a) Pb:0, (b) Pb:5, (c) Pb:10, (d)
Pb:15, (e) Pb:20, and (f) Pb: 25. Cyan and pink arrows indicate the direct and indirect band gap positions for the pristine Cs3Bi2Br9 compound,
whereas the violet and the orange arrows show the band gap position after Pb-substituted Cs3Bi2Br9.
with Bi doping in MAPbBr3, rather there was sub-band gap
state formation near the conduction band, which gives an
impression of a shift in the band gap.45,46 Alternatively,
Lozhkina et al. show that the position of the excitonic
luminescence peak remains unaffected by Bi doping in
CsPbBr3 which implies that the band gap of the Bi-doped
CsPbBr3 perovskite does not change, instead a newly formed
defect state gives an impression of change in band gap.47 In
recent studies, modification of optical properties in pure
compounds is seen because of the occurrence of defect states
while incorporating heterovalent dopants into halide perov-
skite systems.48−50 Considering these experimental observa-
tions, we found that as we increase Pb concentration in
Cs3Bi2Br9, there is a sudden shift rather than a continuous shift
in the band position for the direct band and the indirect band.
This could be related to the fact that heterovalent substitution
creates charge imbalance which leads to the formation of sub-
bands above the valance band. This newly formed sub-bands
above the valance band maxima could also be seen in our
theoretical calculations (Figure 3a) and experimental optical
results (Figure 4). Continuous increase in Pb concentration in
the compound makes this sub-band more prominent and
forms a defect band, ultimately merges with the valance band,
and gives an impression of change in the band position.
Simulation of optical absorption spectra also (shown in Figure
S3 in Supporting Information) reveals a new peak arising near
640 nm wavelength for 12.5% Pb substitution and 660 nm for
25% Pb substitution, which is getting more pronounced with
the increase in lead concentration, similar to our experimental
optical observations. The intensity of this peak increases with
higher Pb substitution, which is expected because of the
increasing sub band gap DOS as discussed above. We also
calculated the Urbach energy and found that the exponential
sub-band gap absorption is governed by the equation A ∝ eE/Eu,
where A is the absorbance, E is the photon energy, and Eu is
the Urbach energy. Urbach energy is considered to be the
quantitative measure of the disorder (or defect state) present
in the compound (shown in Figure S4 in Supporting
Information). As Pb concentration increases in Cs3Bi2Br9
Urbach energy also increases. Urbach energy for Pb:0, Pb:5,
Pb:10, Pb:15, Pb:20, and Pb:25 is found to be 96, 133, 152,
166, 303, and 684 meV, respectively, which quantitatively tells
us the increase in dis-orderness due to the formation of sub-
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band gap states or defect states as we increase the lead
concentration.
Here, Pb (1.19 Å) possessing similar ionic radius as Bi (1.03
Å) is likely to occupy the 2d Wyckoff site previously occupied
by Bi. Pb2+ substitution at the Bi3+ site is expected to behave
like an acceptor type defect (effectively creating an electron
deficiency in the system); thus, with increasing Pb concen-
tration, compensating donor type defects may form. From the
literature, VBr and Csi28,51 are found to be most likely single
valent donor type defects. In this regard, we have estimated the
probability of formation for three different defects (complex)
scenarios via simulating their formation energies with respect
to Fermi level position. They are (a) PbBi, (b) PbBi + VBr, and
(c) PbBi + Csi. Additionally, we have simulated the possibility
of VBr and Csi forming individually in order to calculate the
binding energies of defect complexes. In Figure 6a−c, stable
Figure 6. Phase diagrams of pristine Cs3Bi2Br9 at three different
chemical potentials (in eV) of Pb: (a) ΔμPb = −1.0, (b) ΔμPb = −1.5,
and (c) ΔμPb = −2.0 against competing elemental, binary, and other
secondary phases shown by colored lines. The shaded (cyan) regions
show the stable region.
thermodynamic regions against various secondary phases for
pure Cs3Bi2Br9 are shown for three different Pb chemical
potentials. As expected, one can see that the stable region
becomes smaller with increasing Pb in the environment, where
different secondary phases containing Pb are likely to form.
Next, we proceed to calculate the defect formation energies at
three different chemical environments, (a) Pb rich, (b) Pb
moderate, and (c) Pb poor, as marked by A, B, and C points,
respectively, in the corresponding phase diagrams (Figure 6a−
c). Figure 7a−c represents the defect formation energies of the
above-mentioned defects and defect complexes. As expected,
PbBi is behaving like an acceptor defect showing a charge
transition level (0/−1) at ∼0.4 eV above the VBM. This deep
transition level indicates that PbBi can act as a trap state which
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Figure 7. (a−c) Defect formation energy vs Fermi level simulated at
three points A, B, and C of the stable region of the phase diagram (see
Figure 6) for three different chemical potentials of Pb.
may explain the first prominent optical absorption peak seen in
the case of the Pb-substituted compound (Figure S3 in
Supporting Information). Looking at Figure 7a−c, one can see
that the probability of Pb occupying at Bi increases in Pb rich
condition, which might explain the experimental observation of
higher Pb retention with increasing concentrations of the Pb
precursor. In contrast to the point defect studies for
Cs3(Sb,Bi)2I9 compounds reported recently, here, VBr turns
out to be energetically more favorable than Csi which further
explains less defect formation energy for the PbBi + VBr defect
complex.28,51 Next, binding energies (Eb) of the defect
complexes have been calculated using the following formula:
Eb(AB) = Eform(AB) − Eform(A) − Eform(B), where Eform(X) is
the defect formation energy of defect X. Here, we have
considered the neutral charge state to simulate Eb. Both the
defect binding energies are negative, which indicates a high
probability of formation of defect complexes as compared to
individual defects, which is also noticeable from Figure 7a−c.
Practically, the probability of formation for defect complexes
over individual PbBi should depend on the position of Fermi
level pinning. From Figure 7a−c, one can see that the Fermi
level will always be pinned in the mid-gap region between PbBi
(expected to be the main acceptor given high experimental
concentration of Pb) and VBr (likely to be the dominant
donor). Looking at the Figure 7a−c, it is observed that the
degree of defect compensation will increase as we increase the
concentration of Pb in the growth environment, which
practically induces higher Pb retention in the sample. In
other words, with higher Pb substitution, the defect
compensation via the singly charged donors will increase,
and PbBi along with VBr (shown in Figure S5 in Supporting
Information) or Csi will eventually introduce new states above
the valence band.
■ SUMMARY
We present a combined theoretical plus experimental study of
phase, electronic, optical, and defect properties of Pb-
substituted Cs3Bi2Br9. We successfully synthesized these
compounds for the first time by chemical reprecipitation
method. The substituted compounds are found to crystallize in
the same structure as that of pristine Cs3Bi2Br9. This is one
kind of heterovalent substitution, as it replaces Bi3+ with Pb2+,
which leads to charge imbalance in the compound. Such
charge imbalance can be compensated by naturally occurring
defects such as Br− vacancies (VBr), cesium (Cs+) interstitial
(Csi) or even more complicated defect complexes. VBr or Csi in
Cs3Bi2Br9 create defect states in between the bands, which
results in redshift in the band, causing an overall reduction in
the band gap. Optical measurements clearly illustrate this fact,
19489
pubs.acs.org/JPCC Article
where the absorption onset position is found to move to higher
wavelength with increasing Pb concentration, reducing the
band gap from 2.62 to 2.23 eV. This sudden appearance of a
band could be related to the formation of a defect band near
the valance band maxima, which gets more prominent with
increasing Pb concentration. First-principles calculations also
confirm the onset of such defect states, responsible for the
redshift. A careful defect physics simulation indicates that the
defect complex PbBi + VBr is more probable to form if Pb is rich
in the environment. This consequently introduces a few deep
level defects. Such a combined theory and experimental insight
into the optical, electronic structure, and defect physics of
heterovalent substitution in perovskite compounds is expected
to be quite useful to strengthen the knowledge required for
application or device perspective of these novel materials.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.0c05880.
Synthesis process for the Pb substitution in Cs3Bi2Br9
and various theoretical calculation method. XRD lattice
indexing (Figure S1), band structure Cs3Bi2Br9 (Figure
S2), absorbance (experimental and theoretical) of
various lead substituted Cs3Bi2Br9 (Figure S3), Urbach
energy of Pb substituted Cs3Bi2Br9 (Figure S4), Band
structure of 6.25% Pb substituted Cs3Bi2Br9 (Figure S5)
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Aftab Alam − Department of Physics, Indian Institute of
Technology Bombay, Mumbai 400076, India; orcid.org/
0000-0001-8458-1006; Email: aftab@iitb.ac.in
M. Aslam − Department of Physics, Indian Institute of
Technology Bombay, Mumbai 400076, India;
Email: m.aslam@iitb.ac.in
Authors
Mrinmoy Roy − Department of Physics, Indian Institute of
Technology Bombay, Mumbai 400076, India; orcid.org/
0000-0002-6503-6405
Supriti Ghorui − Department of Physics, Indian Institute of
Technology Bombay, Mumbai 400076, India
Bhawna − Department of Physics, Indian Institute of Technology
Bombay, Mumbai 400076, India
Jiban Kangsabanik − Department of Physics, Indian Institute of
Technology Bombay, Mumbai 400076, India; orcid.org/
0000-0003-4900-016X
Rekha Yadav − Department of Physics, Indian Institute of
Technology Bombay, Mumbai 400076, India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.0c05880
Author Contributions
M.A. and M.R. have designed the problem and they came up
with the experimental idea. All experiments were performed by
M.R. with the help of Bhawna. M.R. analyzed all experimental
results. XPS data was deconvoluted by Bhawna and R.Y.
Primary manuscript was prepared by M.R. M.A. supervised the
experimental work with result analysis and final editing of the
manuscript. To support our experimental findings, theoretical
https://dx.doi.org/10.1021/acs.jpcc.0c05880
J. Phys. Chem. C 2020, 124, 19484−19491
The Journal of Physical Chemistry C
calculation was also done. A.A., S.G., and J.K. came up with the
theoretical idea for performing the simulation. S.G. and J.K.
designed the calculations. S.G. performed all the first-principles
calculation. S.G. and J.K. analyzed the theoretical results and
contributed to preparing the initial manuscript. A.A. supervised
analysis of the theoretical results and editing of the manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors would like to thank SAIF and IRCC for providing
access to the characterization facilities. M.R., S.G., Bhawna,,
and J.K. also acknowledge financial support from IIT Bombay,
MHRD and R.Y. acknowledges UGC for the same as research
fellowship. M.A. and A.A. would gratefully acknowledge
financial support by NCPRE-Phase II, IIT Bombay through
MNRE, Government of India.
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