Research Article

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Atomic Insights of Stable, Monodispersed CsPbI3−xBrx (x = 0,

1, 2, 3) Nanocrystals Synthesized by Modified Ligand Cell
Arup Ghorai, Somnath Mahato,* Sanjeev Kumar Srivastava, and Samit K. Ray*

etc. But all inorganic lead halide PSCs,

Synthesis of monodispersed, stable halide, and mixed halide perovskite which are more stable than their hybrid
nanocrystals by hot-injection approach is still challenging due to the fast reac- counterparts, still need substantial
tion kinetics and unrevealed ligand chemistry. The atomic scale imaging of improvements to achieve higher efficiency
perovskite nanocrystals using transmission electron microscopy (TEM) is also solar cells to match the latter. It is well
known that CsPbI3 has extended visible
challenging because of their structural degradation due to high electron dose
light absorption spectrum compared to
and soft nature of perovskites. Here, a novel technique is proposed to synthe- CsPbBr3, making it one of the promising
size pure cubic phase, monodispersed, stable CsPbX3 (X = I/Br) nanocrystals candidates for solar cells.[6] However, in
by simply modifying ligand chemistry using olive oil, which also leads to reali- comparison to CsPbBr3, CsPbI3 has been
zation of tuneable composition mixed halide perovskites by simple physical less explored due to its lower phase and
thermal stability under ambient condi-
mixing. Here, the atomic scale images and the probable distribution of Cs,
tion. Interestingly, CsPbI3 falls in the
Pb, and I/Br atoms in single halide and mixed halide perovskites via high- borderline regime with a Goldschmidt
resolution TEM microscopy are presented. The estimated atomic distance tolerance factor (τ) value 0.893 and octa-
(PbPb and PbI/Br) is strongly corroborated with the VESTA structure. hedral factor (μ) value 0.47, in the meta-
Interestingly, the lattice constant (d-value) of the synthesized nanocrystals is stable state. Since this idea is theoretically
smaller (≈3%) than the theoretical predicted one, leading to a higher phase derived for the bulk phase of CsPbI3, it
can also be extended to the nanocrystals,
stability in laboratory ambient conditions (45–55% humidity, 300 K). The the-
as there is no alteration of crystal struc-
oretical analysis using density functional theory enlightens the understanding ture.[7] Theoretically it is also proven that
of higher stability of CsPbI2Br along with the maximum optical absorption in the cubic α-phase CsPbI3 has an extended
the visible regime, as a preferable material for the photovoltaic applications. absorption (bandgap ≈ 1.61  eV) spectrum,
suitable for solar cell device applications,
compared to the most common γ-phase
1. Introduction (≈2.25 eV) or β-phase (≈1.83 eV), as computed by tight-binding
(TB) model. This is mainly due to the rotation of [PbI6]4− octa-
All inorganic lead halide perovskites CsPbX3 (X = Cl, Br and I) hedra for γ-phase or β-phase, which stabilize the top of the val-
have drawn immense attention due to their tuneability visible ance band maxima (VBM) and destabilize the conduction band
to NIR absorption and emission spectra, large carrier diffusion minima (CBM) due to bonding–antibonding character of the
lengths (>3 mm), and high lifetime (82 ± 5 µs)[1] making them orbital overlaps.[8] Synthesis of pure cubic or α-phase CsPbX3,
suitable candidates for advanced optoelectronic devices like especially CsPbI3 is one of the biggest challenges in the conven-
solar cells,[2] light-emitting diodes (LEDs),[3] photodetectors,[4,5] tional hot-injection method, since there is a formation of mixed
phase (α-cubic + γ-orthorhombic)[9] mainly due to the fast
reaction kinetics. CsPbI3 is vulnerable toward moisture, heat
A. Ghorai,[+] S. Mahato and even to applied electric field. Therefore, to enhance the
School of Nano Science and Technology
stability of the metastable state of CsPbI3, several techniques
Indian Institute of Technology Kharagpur
Kharagpur 721302, India have been explored to prevent unwanted octahedral tilting, like
E-mail: somnath.mahato@iitkgp.ac.in A- or B- site doping and X- site stabilizations, chemical addi-
S. K. Srivastava, S. K. Ray tive incorporation or solvent engineering.[10–12] Protesescu et al.
Department of Physics reported that 10% FA substitution in place of Cs in the CsPbX3
Indian Institute of Technology Kharagpur matrix could stabilize the lattice and deliver stable emission.[11]
Kharagpur 721302, India
E-mail: physkr@phy.iitkgp.ernet.in Similarly, Manna et al. have shown that nearly 10% Mn sub-
stitutional doping in place of Pb was enough to stabilize the
The ORCID identification number(s) for the author(s) of this article CsPbI3 nanocrystals over a month, whereas the pristine CsPbI3
can be found under https://doi.org/10.1002/adfm.202202087. nanocrystals degrade within 5 d.[13] However, alteration of Pb
[+]Present
address: Department of Materials Science and Engineering, site might change the optical and electrical properties, which
Pohang University of Science and Technology, 77 Cheongam-Ro, Nam-Gu,
are sometimes unwanted for the device purpose. On the
Pohang 790-784, South Korea
other hand, CsPbBr3 has the suitable Goldschmidt tolerance
DOI: 10.1002/adfm.202202087 factor (τ ≈ 0.92) and octahedral factor (μ ≈ 0.50) making them

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electronically and structurally stable even at ambient condi-
tions.[14] As an alternative, ligand cell, could stabilize the phase
of the perovskite nanocrystals without altering its optical and
electrical properties.
Till now, there are very few reports on (cubic) phase stabi-
lization of CsPbX3 through ligand cell engineering and most
of them are focused on CsPbBr3. Generally, oleyl ammine
(OLAm) and oleic acid (OA) couple is used as a ligand for spe-
cially X-site and B-site, respectively in a high boiling solvent
1-octadecene (ODE).[15] Palazon et al. reported that excess addi-
tion, even exposure of OLAm, there is a progressive disappear-
ance of the exciton absorption peak of CsPbBr3 at 500  nm, at
the cost of increased absorption peak at 314 nm for 0D phase,
Cs4PbBr6 NCs.[16] On the other hand, Rao et al. reported that the
addition of an excess amount of OA converts back the Cs4PbX6
to CsPbX3 and the cycle can be repeated simply repeated with
the addition of OLAm and OA up to two conversion cycles.[17]
Hence, by engineering the ligands concentrations, i.e., ligand
cell we can tune the shape as well as phase of halide perov-
skites. In the conventional synthesis approach of caesium-oleate
(Cs-OA) precursors (ODE, OA), the amount of used OA is not
sufficient for full conversion of Cs2CO3 to Cs-OA, which retards
its reproducibility as well as homogeneity.[18] Hence, modifica-
tion of Cs-precursors is also urgently required to achieve high-
quality stable and uniformly sized perovskites nanocrystals.
Recently, researchers have used a mixed anion strategy for
stabilizing pure cubic phase α-CsPbI3 nanocrystals. Sutton et
al. demonstrated that the substitution of a certain amount of
iodide with bromide allows exhibiting more prominent phase
stability by tuning the tolerance factor between the PbX6 frame-
work and Cs cation.[19] Mixed halide perovskites (MHPs) also
provide a tuneable absorption and emission, which is very
handy for the band selective optoelectronic device applications.
All inorganic halide perovskites suffer from some limitations
like α-phase CsPbI3 is easily converted to its nonperovskite
δ-phase.[20] On the other hand, incorporation of Br widens
the bandgap by narrowing the effective absorption range, so
the power conversion efficiency is compromised. Addition-
ally, wide bandgap solar cells suffer from a large open-circuit
voltage (Voc) deficit as compared to narrower bandgap mate-
rials, especially due to the formation of shallow defect levels
in the former.[21] Keeping all these facts in mind, recent trend
is to use MHPs (bandgap varying from 1.8 to 2.5 eV) as active
materials for highly efficient solar cell devices, which can even
be very useful for tandem solar cells.[22] Though there are sev-
eral reports on anion exchange reactions for mixed halides,[23,24]
there is still a lack of a proper atomically replacement model.
As electron beam induced sample degradation is one of the
common problems for perovskites materials, structural char-
acterizations through electron beam microscopy suffer from
structural alteration or damage like the formation of voids, bub-
bles or tinny precipitates, which are already reported in high
resolution images.[25,26] Recently, Chen et al.[27] observed that
even under ultralow electron dose condition, MAPbI3 starts
to decompose into MA+ and PbI2. So, far there are no reports
on the controlled synthesis of monodispersed, stable CsPbX3
(X = Br, I), especially CsPbI3 and MHPs. Furthermore, atomic
scale structural characterization of inorganic perovskite mate-
rials, without any extensive damage or structural alterations by
Adv. Funct. Mater. 2022, 2202087 2202087  (2 of 13)
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simple high-resolution TEM (HRTEM) is reported rarely, moti-
vating us for this study.
Here we report the synthesis of highly stable, cubic α-phase
CsPbI3 and CsPbBr3 by a modified hot injection method using
olive oil for the first time. Simultaneously, we could synthesize
mixed halide perovskites with tuneable composition and optical
characteristics by simple physical mixing without altering their
crystal structure. Additionally, the modification of Cs (I)-OA
precursor has been employed to achieve better homogeneity
as well as reproducibility and stability in ambient conditions.
The precise atomic scale imaging of the morphology and crystal
structure of single halide (SHP) and MHP NCs are presented,
without any structural degradation under electron beam or
X-ray irradiation. All the atoms of SHP and MHP are easily dis-
tinguishable along with their unit cell on atomic level, which
are modeled by using VESTA software. It is observed that
the lattice constant (d-value) of our synthesized perovskites
nanocrystals is smaller (≈3%) than the reported one, leading
to better ambient stability in agreement with the density func-
tional theory (DFT) calculations. The calculated band structure,
density of states (DOS) and optical properties along with the
charge distribution of CsPbBrxI3−x (x  = 0, 1, 2, 3), are used to
support our experimental results. Finally, as a proof of con-
cept we demonstrate solar cells using CsPbBr(3−x)Ix, (x  = 0, 1,
2, 3) perovskites as an absorbing layer using ITO/PEDOT:PSS/
CsPbBr3−xIx/BCP/C60/Al (p–i–n) device architecture. Un-encap-
sulated air-stable CsPbI2Br based device exhibits a moderately
high efficiency of 8.15% and a fill factor (FF) of 64.5%, which
are superior to other anionic compositions.
2. Results and Discussions
In the hot injection approach, the addition of Cs(I) precursor in
the final step of the reaction leads to fast crystallization process,
immediately after the addition of precursor.[28,29] The ratio of
reactants, Cs, Pb, X (X = Br and I) and ligands play the deciding
factors for the shape, size as well as phase of the perovskite
nanostructures.[30,31] The phase selectivity of the CsPbX3
strongly depends on the crystal structure of Cs-precursor. In
our modified two-step hot injection synthesis approach of all
inorganic lead halide perovskites, we have used olive oil as a
solvent as well as a chelating agent for the synthesis of Cs-OA
and lead oleate (Pb-OA). It is well known that olive oil contains
above 80% of oleic acid (up to 83%) with lesser content of lin-
oleic acid (up to 21%) and palmitic acid (up to 20%). Here, we
have chosen Cs2CO3 and olive oil at 120 °C for the synthesis of
the desired Cs-OA in the initial step (1st step, Figure  1) of the
reaction, and then compared with the conventional synthesis
product of Cs-OA (using Cs2CO3, ODE and OA). When ODE is
used as a solvent and OA as a chelating agent, Cs-OA easily gets
precipitated in the first step of the reaction on cooling to room
temperature (Figure 1, Step-I, left side). On the other hand, the
Cs-OA solution (Figure 1, Step-I, right side) remains transparent
even after several weeks after the preparation, when olive oil
is used as a chelating agent as well as the solvent (Figure S1a,
Supporting Information). Recently, Lu et al. reported that in
most of the conventional synthesis process of Cs-OA, even if
the amount of OA is stoichiometrically sufficient, the reaction
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Figure 1.  Synthesis schematic of CsPbI3 by modified hot injection method, using olive oil. Step-1: synthesis of Cs-OA using ODE+OA (left side) and only
olive oil (right side); Step-II: synthesis of Pb-OA by OA+OLAm (batch-I and batch-III) in ODE solvent and olive oil+OLAm (batch-II and batch-IV) for the
synthesis of CsPbI3 nanocrystals. Schematic diagram (bottom panel), illustrating phase selectivity of our modified synthesis approach using olive oil.

still produces an incomplete conversion of Cs2CO3 to Cs-OA.[18]
Hence, there is a mixture of different Cs-based species, which
affects the homogeneity as well as reproducibility. So, in our
modified synthesis technique of Cs-OA, the excess amount of
fatty acids including OA in olive oil fully converts the Cs2CO3
to its Cs-OA precursor. This modification of the Cs-OA, avoids
the size variation and improves the reproducibility of the hot
injection approach. Additionally, an excess amount of fatty acids
provides an advantage of the phase selectivity by retaining the
cubic crystal structure of CsPbX3. Furthermore, this Cs-OA
can easily be stored for a longer time without any sedimenta-
tion, the digital image of Cs-OA prepared by using olive oil and
ODE+OA after 30 d are shown in the supporting information
(Figure S1a, Supporting Information). In addition, we have
performed the step-2 reaction without heating Cs-OA (olive
oil) solution, giving rise to the red-colored dispersion which
also confirms the improved solubility of Cs-OA in olive oil, as
shown in Figure S1b (Supporting Information).
In the second step, we synthesized Pb-OA using olive oil+
OLAm and ODE +OA +OLAm at 150 °C under N2 atmos-
phere. We performed four sets of reactions: batch-I Cs-OA
and Pb-OA were synthesized by ODE + OA and additionally
used OLAm to solubilize Pb-OA. In batch-II Cs-OA were syn-
thesized by olive oil and Pb-OA by ODE+ OA+ OLAm, while
batch-III Cs-OA were synthesized by ODE+ OA and Pb-OA
by olive oil, and both Cs-OA and Pb-OA synthesized by olive
oil in batch-IV. We also performed the reaction without using
OLAm, but finally, there is no formation of red color suspen-
sion at the end of the reaction (Figure S1c, Supporting Infor-
mation). So, it is apparent that there is an important role of
the ammine in the reaction process, in addition to the solubi-
lization or stabilization of CsPbX3. Several results report that
OA acts as B-site and OLAm as X-site chelating ligand for the
synthesis of stable suspension of CsPbX3 at the end of the
reaction. The corresponding digital photographs of CsPbI3 sus-
pension in hexane for different reaction batches clearly show
different color contrasts (Figure 1). So, it is presumed that there
might be a variation in size, morphology or phase for different
batch samples. To further substantiate this, we have performed
UV–vis absorption and photoluminescence (PL) measurements
for all samples (Figure S2a,b, Supporting Information). Digital
images of PL emission of different batch samples under the
excitation of 325 nm laser are shown in Figure S2c (Supporting
Information).

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Table 1.  Synthesis of CsPbI3 with different precursors highlighting the advantages and disadvantages.
CsPbI3 Cs-precursor Pb/I-precursor
PbI2 + ODE + OA + OLAm
Cs2CO3+ oleic acid (OA)
+1- octadecene (ODE)[32,33]
batch-I
PbI2 + ODE + OA + OLAm Mixture of γ- and α- phases of CsPbI3,
Cs2CO3 + Olive oil
batch-II
PbI2+ Olive oil + OLAm
Cs2CO3+ oleic acid (OA)
+1- octadecene (ODE)
batch-III
PbI2+ Olive oil + OLAm
Cs2CO3 + Olive oil
batch-IV
Interestingly, it is observed that there is a certain change
in the absorption and emission peak positions for different
samples, as tabulated in Figure S2d (Supporting Information).
The morphology of samples for all batches has been studied by
high-resolution transmission electron microscopy (HRTEM). It
is clearly established that first and second batch samples con-
tain a mixture of nanocrystals (NCs) and small nanorods (NRs)
(Figure S3a,b, Supporting Information). On the other hand,
for the third and fourth batch samples, HRTEM micrographs
suggest the formation of only cubic nanocrystals (Figure S3c,d,
Supporting Information). On the other hand, for the third batch
CsPbI3, there exists nonuniform size distribution, mainly due
to the different Cs-sources used in the final step of the reac-
tion. The fourth batch CsPbI3 sample is found to be the best
with uniform size distribution as well as extended visible light
absorption characteristics, in comparison to the other samples.
To further confirm the phase of CsPbI3, we have performed
X-ray diffraction (XRD) measurements of all the samples,
which are shown in Figure S4 (Supporting Information). From
XRD pattern, it is evident that there is the change of phase for
different batch samples, in agreement with our HRTEM anal-
ysis. Interestingly, from the plots 2θ for (100) plane for different
samples shown in Figure S5e (Supporting Information), the
Bragg diffraction peaks (2θ values) are found to be at ≈14.33°
and 14.25° for batch-II and batch-IV samples, respectively,
in which Cs-OA are synthesized by olive oil in the first step.
On the other hand, it is slightly higher at 14.43° and 14.48°,
respectively, for batch-I and batch-III samples prepared using
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Limitations Advantages
Mixed phase (dominated by γ-phase Well-known conventional synthesis
>90%), not scalable, unstable under process.
ambient condition and tedious purifica-
tion procedure
Simple, cost-effective synthesis
lower stability approach.
Poor size distribution, lower stability Simple and cost-effective synthesis
approach, α- phase dominated CsPbI3
nanocrystals.
Long-term stability under ambient Pure α-phase, uniform size distribution
condition is still an issue and improved stability under ambient
conditions (above 30 d)
conventional approach (Cs-OA synthesized by ODE + OA,).
Therefore, we conclude that the Cs-OA synthesized by using
olive oil has a direct impact on the structural phase selectivity
by mimicking the crystal structure of Cs-precursor, Cs2CO3. For
a comparative study of all the synthesized CsPbI3 samples, the
advantages and disadvantages of each synthesis approach for
different precursors are shown in Table 1.
There are a few reports claiming that the phase of the mate-
rials changes to the cubic α-phase[34] in presence of excess OA.
But these cubic phases of CsPbI3 are not thermodynamically
stable. On the other hand, in our synthesized samples, both
OA and OLAm ligands play a vital role in the stability of the
final CsPbX3 product. These ligands bind with the perovskite
moiety differently; OA prefers to bind with the B-site (Pb) and
OLAm prefers to bind with the X-site (Br, I).[15] So, when we
use an excess amount of OA, it preferentially stabilizes the Pb
counterpart along the (110) plane, as fatty acids act as O-donors
to Pb+2 and Pb+2 acts as a borderline Lewis base.[35] The con-
centration of the ligands, especially OA, plays a vital role in
the cubic growth of CsPbX3. This leads to the facile and pref-
erential growth of cubic CsPbX3 structure in presence of olive
oil. Furthermore, OLAm can bind along the (110) plane,[36]
making other facets like (100) or (200) available for the growth
of perovskite nanocrystals. We have also experimented using an
excess amount of OLAm and observed orthorhombic CsPbI3
phase dominated product as the final product. Another advan-
tage of our synthesis approach is to produce a highly stable
cubic phase under ambient condition, which is stable over 30 d
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Figure 2.  X-ray diffraction pattern of single phase material fitted by Rietveld Full-prof software for a) CsPbI3 and b) CsPbBr3 (sample size ≈2 × 2 cm2);
c,d) corresponding 2D-XRD patterns showing main characteristics plane (100) and (200) for α-phase CsPbI3 and additional (110) for α-CsPbBr3, respec-
tively; 3D polyhedral 3 × 3 structures of e) CsPbI3 and f) CsPbBr3 using Rietveld single phase fitting parameters by VESTA software. Representative
colors are Cyan for Cs, yellow for Pb, red for Br, and green for I atoms.
(Figure S5d, Supporting Information). It is noted that the color
of the samples gets slightly darker, mainly due to the formation
of surface defects in presence of moisture through the ligand
loss. On the other hand, in case of CsPbBr3 the ambient sta-
bility is much higher, almost 3 months without showing any
distinguishable sign of degradation. To further examine the
stability of the sample in hexane-water (2:1 volume ratio) mix-
ture, we have performed the PL measurements under 325 nm
laser excitation. It is observed that CsPbI3 degrades in the harsh
water environment very fast within 8.0 h (30% retention of its
initial luminance). On the other hand, CsPbBr3 remains nearly
stable up to 2 d under the same condition by retaining 70% of
its luminescence intensity, which is comparable to the previous
reports[29,37] (Figure S6, in Supporting Information). Generally,
the stability of perovskite nanocrystals dispersion depends on
the ligands binding ability. There are several reasons for the
degradation of perovskite dispersion, the protonation of the
NH2 group of OLAm by OA is one of them.[38,34] The pro-
tonation of NH2 weakens the binding ability of both OLAm
and OA causing extensive ligand loss. There are several reports
with the replacement of this OA+ OLAm pair with other sec-
ondary ammine ligands, to avoid this unwanted protonation
hampering the stability.[39] But in our case, even after protona-
tion, sufficient amount of OA is available, since we have used
an excessive amount of OA. The remaining OA then plays a
crucial role in the enhanced stability of CsPbX3 nanocrys-
tals dispersion in the ambient condition. Following the same
procedure, we have also synthesized cubic phase CsPbBr3
nanocrystals. Due to the suitable tolerance factor, synthesized
CsPbBr3 (τ ≈ 0.92) nanocrystals are more stable in comparison
to CsPbI3 nanocrystals (metastable phase) under ambient con-
ditions. So, in the synthesis process, we have focused more on
the stability of CsPbI3 than that of CsPbBr3.
The phase of as-synthesized CsPbBr3 and CsPbI3 nanocrys-
tals is established from X-ray diffraction analysis (XRD) sup-
ported by a High-resolution transmission electron microscope
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(HRTEM) on the atomic level. The optical characteristics
(absorption and emission) of as-synthesized CsPbBr3 and
CsPbI3 dispersions in hexane are shown in the supporting
information Figure S7 (Supporting Information).
For the structural phase analysis of synthesized CsPbI3 and
CsPbBr3 nanocrystals, we have performed high-resolution X-ray
diffraction (HRXRD) of the films deposited on a cleaned glass
substrate, which is shown in Figure 2. Highly intense character-
istic peaks of CsPbI3 are observed, one at 14.27° for (100) plane
and the other at 28.66° for (200) plane for cubic crystal phase
(α-phase)[40] (Figure  2a). Similarly, for CsPbBr3 film we have
observed highly intense peaks at 2θ = 15.36°, 21.56°, 30.78° and
shoulder peaks at 37.89° and 43.86° for (100), (110), (200), (211),
and (220) planes, respectively [30] (Figure  2b). All the peaks
observed here signify the formation of cubic phase (α-phase)
of both CsPbI3 and CsPbBr3 nanocrystals, revealing high
phase selectivity of our synthesis approach. We have observed
that in the conventional synthesis process (OA+ OLAm,
batch-I, mainly there is the formation of mixed phase CsPbX3
nanocrystals dominated by orthorhombic phase (γ-phase), as
shown in Figure S4a (Supporting Information). Several reports
indicate that controlling the phase of as-synthesized inorganic
perovskite nanocrystals by hot injection methods is very dif-
ficult, due to fast reaction kinetics.[32] But we did not observe
any major characteristics peaks for the orthorhombic phase
(γ-phase) in our samples of batch-III and batch-IV. Therefore,
we conclude that the olive oil plays the crucial role in deter-
mining the growth direction of the nanocrystals to achieve
CsPbX3 nanocrystals. Earlier we have discussed that the excess
fatty acid of olive oil preferably binds with the Pb-site of the
seed and facilitates the growth only along the (100) direction,
leading to the cubic α-CsPbX3 nanocrystals. To further deter-
mine the crystallographic parameters such as phase, space
group, atomic position etc., we have performed the Rietveld
refinement with single-phase fitting using Full-prof program.
Rietveld refinement shows that CsPbI3 and CsPbBr3 thin films
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Figure 3.  a,b) High-resolution TEM images showing lateral dimension of 13.36 × 13.41 and 13.56 × 12.98 nm and c,d) magnified view of the yellow
squared region from (a) and (b) for CsPbI3 and CsPbBr3 nanocrystals at doses of ≈4.494 × 103 and 7.491 × 103 e− Å−2, respectively. FFT pattern of the
white squared region of (a) and (b) and the diffraction spots marked by yellow circles correspond to the cubic phase of CsPbI3 and CsPbBr3 along the
[002] Zone axis (ZA). Due to the degradation under the electron beam, the red circles correspond to the orthorhombic phase of CsPbI3 and CsPbBr3
along the [202] and [020] ZA and green circles corresponds to the tetragonal phase of CsPbI3 along [040] ZA.

are of pure cubic α-phase (space group Pm-3m, no. 221) and the
α-phase content is close to 100%. The extracted lattice constant
for both CsPbI3 (d = 6.20 Å) and CsPbBr3 (d = 5.84 Å) is almost
3% smaller than their reported α-phase values, leading to higher
structural stability of the nanocrystals in the ambient condi-
tion (45–55% humidity). To investigate the crystallinity, we have
simultaneously performed 2D-XRD analysis of both CsPbBr3
and CsPbI3 samples, as shown in Figure  2c,d. The formation
of well distinguished Debye rings indicates fine grain size and
polycrystalline nature of the samples. Discontinuous and nonu-
niform intensity along the Debye rings clearly suggest there is
a preferred orientation or texture along the (100) plane, sup-
porting our directional growth hypothesis in presence of olive oil
or excess OA. By Rietveld refinement, the schematic 3D repre-
sentation of the cubic polyhedral crystal structure of CsPbI3 and
CsPbBr3 is shown in Figure 2e,f, respectively, using the VESTA
program. In the 3D structure of both CsPbI3 and CsPbBr3, nei-
ther any lattice distortion nor octahedral inclination in the cubic
[PbI6]4− octahedra is observed, strongly corroborating our atomic
scale imaging analyses (to be discussed next).
For a deep insight into the microstructure and crystalline
quality of CsPbI3 and CsPbBr3 nanocrystals, we have performed
high-resolution transmission electron microscopy (HRTEM)
analysis shown in Figure  3. TEM images presented in
Figure 3a,b suggest the uniform size distribution (Figure S8a,b,
Supporting Information) and cubic shape of both CsPbI3
(13.36  nm  × 13.41  nm) and CsPbBr3 (13.56  nm × 12.98  nm)
nano­ crystals, respectively. The average size of CsPbBr3
(≈12 ± 2 nm) nanocrystals is found to be slightly lower than that
of CsPbI3 (≈17 ± 3 nm), as shown in Figure S8c,d (Supporting
Information). The high-resolution lattice images of CsPbI3
and CsPbBr3 presented in Figure  3c,d, from the yellow region
marked in Figure  3a,b, respectively reveal an excellent crystal-
line quality with minimal atomic defects. The corresponding
fast Fourier transform (FFT) patterns of CsPbI3 and CsPbBr3,
chosen from the selected white squared area of Figure  3a,b,
are presented in Figure  3e,f, respectively. All properly indexed
crystal planes in the FFT patterns reveal that both CsPbI3 and
CsPbBr3 NCs, viewed from the zone axis [002], are mostly in
cubic α-phase. A few diffraction spots for orthorhombic (γ-) and
tetragonal (β-) phases of CsPbI3 are also observed, which may
be attributed to the high electron dose induced phase transfor-
mation of halide perovskites.[41,42] However, at a relatively lower
electron dose, all the diffraction spots correspond solely to pure
cubic (α-) phase of nanocrystals, as shown in the Figure S11,
supporting information. To further investigate the phase purity
along with the atomic arrangement of both CsPbI3 and CsPbBr3
nanocrystals, we have depicted magnified atomic resolution
images processed by a digital micrograph software in Figure 4.
From Figure 4a,b it is quite clear that the growth of CsPbI3 and
CsPbBr3 nanocrystals are predominantly along the (100) plane,
which is in agreement with our XRD analyses. We can easily
identify all the individual atoms along the [100] plane by fol-
lowing their intensity/contrast pattern as well as the position
of bright and dark features, with the colored circles cyan for Cs,
yellow for Pb, green for Br and red for I, respectively shown in
Figure  4c,d. Cs, Pb and I atoms show higher contrast on the
other hand Br column showing weaker contrast, as observed
by Yu et al. for CsPbBr3.[43] The corresponding atomic posi-
tion is well-matched with the cubic unit cell structures of both
CsPbI3 and CsPbBr3. From the structure, we could extract the
bond lengths, for CsPbI3 as PbPb = 6.23 Å and PbI = 3.08 Å
(Figure S9a, Supporting Information), while those for CsPbBr3
a PbPb = 5.85 Å, and PbBr = 2.89Å (Figure S9b, Supporting

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Figure 4.  Magnified TEM images of a) CsPbI3 and b) CsPbBr3 nanocrystals showing directional growth along the (100) plane with lattice spacing of
0.62 and 0.58 nm, respectively. Proposed atomic arrangements form the magnified TEM images representing c) CsPbI3 and d) CsPbBr3 unit cell, with
the colored circles Cyan for Cs, yellow for Pb, red for I, and green for Br atoms, respectively. Calculated Pb-Pb, PbI, and PbBr bond distances from
HRTEM images and comparison with Rietveld fitted XRD data for e) CsPbI3 and f) CsPbBr3.

Information). The calculated values are tabulated in Figure 4e,f,
which are in good agreement with calculated crystal parameters
from the XRD data.
The bond angles of IPbI and BrPbBr are found to be
exactly 90°, which suggests the absence of any lattice distortion
in CsPbI3 and CsPbBr3 nanocrystals, making them ambient
stable for over a month in hexane solution. The selected area
electron diffraction (SAED) patterns from the TEM images
of both the nanocrystals are indexed to (200), (220), and (020)
planes along the [004] zone axis, as shown in the Supporting
Information, Figure S10, indicating pure cubic crystalline
nature. The absence of any orthorhombic or tetragonal planes
ascertains their phase purity, which is supported by the single-
phase fitting of XRD using Rietveld full-prof software.
We have carried out simple physical mixing of α-CsPbI3 and
α-CsPbBr3 to obtain mixed halide perovskites with the compo-
sition of CsPbBr2I and CsPbI2Br (Video S1, Supporting Infor-
mation). To investigate the atomic ratios, we have performed
X-ray photoelectron spectroscopy (XPS) of all the four samples
CsPbI3, CsPbI2Br, CsPbIBr2, and CsPbBr3. The survey analyses
of all the compositions are shown in Figure S12 (Supporting
Information). We did not observe any noticeable change in the
peak position of the binding energy of corresponding atoms
indicating their same chemical oxidation states but the peak
position gets slightly changed mainly due to the change of
chemical environment.[44] The elemental XPS spectra of CsPbI3,
CsPbBr2I CsPbBrI2 and CsPbBr3 are shown in Figure S13 and
corresponding peak positions are tabulated in Table ST1 (Sup-
porting Information). The calculated atomic ratio of all the
halide perovskites is tabulated in Table ST2 (Supporting Infor-
mation). So, from the XPS analysis, we can conclude that even
simple physical mixing of CsPbI3 and CsPbBr3 (same concentra-
tion) with different ratios can yield MHPs with desired com-
position. For example, when we mix CsPbI3:CsPbBr3 in 1:2
ratios it produces CsPbIBr2, but not a composite of CsPbI3 and
CsPbBr3. There exit some halide vacancies in our calculated
atomic ratio for all the perovskites, which is known to be very
common for these halide perovskites.[45,46]
HRTEM images along with the FFT and SAED patterns of
the mixed halide CsPbI2Br and CsPbBr2I perovskites are shown
in Figure S14a–f (Supporting Information). Similar to CsPbI3
and CsPbBr3, the morphology of the mixed halide remains
unchanged. To visualize the atomic arrangements in the MHPs
we have zoomed in the lattice images and processed it with dig-
ital micrograph software, which are presented in Figure  5a,b.
The possible positions of the atoms for CsPbBrI2 and CsPbBr2I
are well distinguishable the HRTEM images with the iodine
atoms denoted by red circles along with Cs, Pb and Br atoms
by cyan, yellow and green circles, respectively. As the structures
are cubic (symmetric), all the anionic positions of both CsPbI3
and CsPbBr3 are equally favorable when we mix them with a
certain ratio. From the image contrast/size of high-resolution
TEM images, we have constructed an atomic model showing
possible atomic arrangements in CsPbBrI2 and CsPbBr2I using
3D VESTA software, which are shown in Figure 5c,d. It may be
noted that when we observe along the c-axis, Br and I atoms
of CsPbI2Br and CsPbBr2I are placed on top of each corner Pb
atoms, causing an increase in contrast or size at corresponding
magnified HRTEM images presented in Figure  5a,b. How-
ever, HAADF-STEM images along with the simulated HRTEM
images can identify specifically the atomic columns, bond dis-
tance and angles, which had been reported previously.[47–49]

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Figure 5.  Magnified HRTEM images of a) CsPbI2Br and b) CsPbBr2I nanocrystals, showing their atomic arrangement in a unit cell; cyan circle for Cs,
yellow for Pb, and red and green for I and Br atoms, respectively. Corresponding VESTA model for the atomic positions of Br and I atoms in c) CsPbI2Br
and d) CsPbBrI2, with colors of the circles remaining same as above. The digital images of the dispersion of corresponding nanocrystals in hexane are
shown in the inset. Calculated PbPb, PbI, and PbBr bond distances in e) CsPbI2Br and f) CsPbBr2I using HRTEM images and their comparison
with Rietveld fitted XRD data.

From the VESTA simulated data, we could estimate the atomic
distance between two atoms (Cs to Cs, Pb to Pb, I to I, Br to
Br, and Br to I). On the other hand, from HRTEM images,
we calculated the atomic distance using Digital Micrograph
simulation, which are in close agreement with those extracted
from VESTA model. The corresponding digital images of
nanocrystals dispersion in hexane are also shown in the inset
of Figure  5c,d. The measured PbPb distance 6.10 Å, 5.94 Å
and PbI = 3.08 Å, PbBr = 2.99 Å, respectively, for CsPbI2Br
and CsPbBr2I by HRTEM, clearly supports our assumption
of atomic positions in the respective unit cells. PbPb bond
length distributions histogram for both the MHPs are shown
in Figure S15 (Supporting Information), PbI and PbBr his-
togram is shown in Figure  5e,f. The calculated and measured
bond distance from XRD and HRTEM supports each other, cor-
roborated by the proposed unit cells model of both CsPbBrI2
and CsPbBr2I.
We have also studied the change in XRD peak position of
CsPbIxBr3−x (x  = 0, 1, 2, 3) nanocrystals with the halide sub-
stitution, as shown in Figure 6a. Figure 6b shows that with an
increase in iodine content in CsPbBr3−xIx, the characteristics
(100) diffraction peak is gradually shifted to lower 2θ values.
As the iodine content increases in CsPbBr3−xIx (x = 0, 1, 2, 3),
the effective size of the crystallite increases leading to a gradual
shift of the diffraction peak to a lower 2θ value.[50] The char-
acteristic (100) diffraction peak of CsPbBr2I and CsPbBrI2
observed at 14.98° and 14.6°, respectively falls within the range
between 14.21° (CsPbI3) and 15.33° (CsPbBr3). Additionally, for
the MHPs, there is a broadening of diffraction peak compared
to pure CsPbI3 and CsPbBr3, which may be due to the phase
segregation during the synthesis.[51] The measured 2D XRD pat-
tern of the mixed halides exhibits polycrystalline behavior, with
corresponding Debye rings shown in Figure S16c,d (Supporting
Information) suggest the oriented growth of nanocrystals.
The optical properties of the as-synthesized lead halide
perovskites with varying compositions have been studied
by UV–visible (UV–vis) absorption and photoluminescence
(PL) emission spectroscopy. In Figure  6c, we have observed
a single absorption peak for cubic phase CsPbI3 nanocrystals
at 690  nm corresponding to the bandgap of ≈1.79 eV.[52] Simi-
larly, for cubic phase CsPbBr3, the absorption peak at 505  nm
having an equivalent bandgap of ≈2.45  eV is observed.[53] On
the other hand, Figure 6c shows the absorption peaks at inter-
mediate wavelength of 630 and 569  nm for CsPbI2Br and
CsPbBr2I MHPs, respectively. PL emission spectra also follow
the similar trend of variation of emission energy by substi-
tution I with Br. Under the excitation of 325  nm laser, sharp
emission peaks are observed in Figure  6d at 692 and 508  nm
for CsPbI3 and CsPbBr3, respectively. On the other hand, MHPs
exhibit emission in between the wavelength range of 508 and
692 nm following a linear trend, with CsPbBr2I peak at 570 nm
and CsPbBrI2 at 644 nm. We have tabulated all the parameters
of optical characterizations of perovskites with different ani-
onic compositions in Figure S16a (Supporting Information). As
expected, the variation of absorption and emission peaks with
the halide composition is found to be almost linear, from the
fitted straight line shown in Figure S16b (Supporting Informa-
tion). This indicates that even a simple mixing can be a reliable
technique for the synthesis of MHPs by varying the ratio of the
CsPbI3 and CsPbBr3 concentration in dispersions. We have also
measured photoluminescence decay (PL-decay) characteristics
of all four perovskite samples at their maximum emission peak

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Figure 6.  a) X-ray diffraction pattern of perovskite CsPbBrxI1−x (x  = 0, 1, 2, 3) nanocrystals with different composition. b) A closer view of the blue
circled peak (panel a) for (100) plane showing a continuous shift to lower Bragg angle with increasing iodine proportion. c) UV–vis absorption and
d) PL emission (under 325 nm laser excitation) of perovskite nanocrystals showing color tunability with composition. e) Time resolved PL character-
istics of different CsPbBrxI1−x (x = 0,1,2,3) dispersion in hexane excited with the peak wavelength and f) a digital photograph of the acronym “SNST”
written using different perovskite nanocrystals inks, followed by illumination with 325 nm laser source.

position and fitted with a bi-exponential function shown in
Figure 6e. As we increase the iodine proportion from CsPbBr3
to CsPbI3, the radiative lifetime (τ2) value gradually increases
from 22.88  ns to 62.75  ns. This drastic change is attributed to
the increase in crystallite size from CsPbBr3 to CsPbI3. Fur-
thermore, perovskite NCs which are smaller in size (CsPbBr3)
may limit the diffusion of excitons or charge carriers, leading
to lower carrier lifetime.[54] For visual demonstration of color
tenability, the acronym of our academic school “School of
Nanoscience and Technology” (SNST) is written using four dif-
ferent halide perovskite nanocrystals inks in hexane; the letter
“S” using CsPbI3 “N” using CsPbBr3, “S” using CsPbI2Br and
“T” using CsPbIBr2. Figure 6f shows a digitally captured photo-
graph with the letters excited with a 325 nm laser source.
We have calculated the electronic bandgap and optical
absorption edges of all four perovskite samples with dif-
ferent composition by DFT with mBj approximation, fol-
lowing Γ-X-M-Γ-X-R paths in the first Brillouin zone and com-
pare the trend with our experimental results. In general, the
band structure of all the four cubic structures (CsPbBr3−xIx
x  = 0, 1, 2, 3) are quite similar with a gradual increase in
bandgap with the increase in Br content, in agreement with
our experimental result. The valance band maxima (VBM)
and conduction band minima (CBM) for all four structures
are located at the “R”-point; hence by absorbing photons
these semiconductors can generate electron-hole pair (exci-
tons) without any energy loss by interacting with phonons.[8]
The extracted electronic bandgaps of CsPbI3 (Figure S17a,
Supporting Information), CsPbBrI2 (Figure  7a), CsPbI2Br
(Figure  7b), and CsPbBr3 (Figure S17b, Supporting Informa-
tion) are found to be 1.41, 1.49, 1.63, and 1.96  eV, respectively.
On the other hand, the experimental optical bandgaps of the
corresponding composition are 1.79, 1.93, 2.17, and 2.45  eV,
respectively. The experimental (optical) and theoretical (elec-
tronic) bandgaps are in good agreement, and follow the
same trend with change of composition, which is shown in
Figure S18a (Supporting Information). In both theoretical and
experimental study with increasing Br content, the bandgap
increases as Br (2.96) has a higher electronegativity compared
to I (2.66). The total density of states (t-DOS) along with par-
tial density of states (p-DOS) of CsPbI3 and CsPbBr3 are shown
in Figure S17c,d (Supporting Information) along with those for
CsPbI2Br and CsPbIBr2 in Figure  7c,d, respectively, indicating
electron distribution probability in the energy spectrum. The
VBM is formed for SHP (CsPbI3, CsPbBr3) mainly due to the
contribution of p-orbitals of Br or I atoms and s-orbitals of Pb,
indicating efficient hybridization. Whereas, CBM is formed due
to the contribution of p-orbitals of Pb and a very small contri-
bution of p-orbitals of Br or I.[55] On the other hand, for the
MHPs (CsPbIBr2 and CsPbI2Br), VBM is composed of I-5p and

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Figure 7.  Theoretically calculated (mBj-approximation) band structures of cubic phase MHP a) CsPbI2Br and b) CsPbBr2I with their corresponding DOS
in (c) and (d). 3D mapping of electron localization function field along e) I-plane for CsPbI2Br and f) Br-plane for CsPbBr2I, respectively.
Br-4p states combined with a small amount of Pb-6s and CBM
is composed of mainly Pb-6p states. But, there is no signifi-
cant contribution of Cs+ on the band structure of perovskites,
except to maintain the stability of the structure by providing
charge balance to the [PbX6]4− octahedral framework.[56] For
CsPbI2Br, I-5p orbital contribution to the VBM is higher than
the Br-4p contribution; an increase in Br content increases
its contribution to the VBM for CsPbBr2I, which is quite evi-
dent in Figure  7c,d.[56] On the other hand, Pb-6p contribution
to the CBM remains unchanged for the MHPs. Theoretically
calculated absorption coefficient of the four perovskite struc-
tures as a function of photon energy is plotted in Figure S18b.
From the theoretical calculation, it is observed that the absorption
spectrum gradually shifts toward the higher energy as bromine
content increases. This is in good agreement with our experi-
mental absorption curves shown in Figure  6c. Chen et al.[56]
reported that both α- and β-phases of CsPbI2Br possess better
thermal and phase stability compared to CsPbI3 due to mixture of
halide elements, though optical properties are quite comparable
to CsPbI3 and MAPbI3. Here also we observe that the bandgap
is comparable for CsPbI3 and CsPbI2Br, in fact the absorption
coefficient is higher in case of CsPbI2Br as compared to CsPbI3
(Figure S18b, Supporting Information). So, CsPbI2Br can be
used as a promising candidate for ambient stable optoelectronic
device applications, especially for solar cells and detectors.
For the detailed study on the charge distribution of Pb-X
(X = Br, I) bond, we have analyzed the Bader charge distribu-
tion based on the topological analysis of electron densities
and electron localization function (ELF) based on the location
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of bonds, electron pairs, and bond strength by integrating the
electron density in Figure S19a–d for CsPbI3 and CsPbBr3 and
Figure  7e,f along the I-plane and Br-plane, respectively, for
CsPbI2Br and CsPbBr2I. Charge distribution along the alterna-
tive plane for CsPbI2Br and CsPbBr2I shown in the Figure S20
(Supporting Information). From 2D (Figure S19a,b, Supporting
Information) and 3D (Figure S19a,b, Supporting Information)
charge distributions plots of CsPbI3 and CsPbBr3, it is quite
clear that the PbI bond is comparatively more covalent in
[PbI6]4− octahedra compared to the PbBr bond in [PbBr6]4−
octahedra. This is mainly due to the larger size and polariz-
ability of I compared to Br, following Fajan’s Rule, adequately
supporting the higher stability of CsPbBr3 compared to CsPbI3.
The 2D charge distributions of CsPbI2Br and CsPbIBr2 are
shown in the Figure S19e–h (Supporting Information), along
I- and Br-plane. As compared to CsPbBr2I, charge distribution
of CsPbI2Br is slightly overlapped along the PbXPb bond,
indicating its superior charge conductivity required for the
improved device performance.
Finally, as a proof of concept, an inverted (p–i–n) solar cell
device has been fabricated using α-CsPbBrxI3−x (X = 0, 1, 2, 3)
in the configuration of ITO/ PEDOT: PSS/ CsPbBrxI3−x/ C60/
BCP/ Al and measured under A.M 1.5g  standard illumination
in ambient condition (45–55% humid condition). A schematic
of the fabricated device is shown in Figure S21a (Supporting
Information). The energy band diagram of the fabricated device
is schematically presented in Figure S21b (Supporting Infor-
mation). The thickness of each layer was measured by cross-
sectional FESEM image, as shown in Figure S21c (Supporting
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Information). Interestingly, it is observed that a maximum
short circuit current density (Jsc) is obtained in case of CsP-
bI2Br based device compared to CsPbI3, CsPbBr3 as well as
CsPbBr2I perovskites, as predicted from the Bader charge dis-
tribution theoretically. Corresponding J–V curves of the fab-
ricated devices with the variation of anionic compositions of
MHP CsPbBrxI(3−x) are shown in the Figure S21d (Supporting
Information). Though the open circuit voltage (Voc) of CsPbBr3
based device (≈1094  mV) is found to be maximum, the Jsc is
quite low (≈6.78  mA cm−2) mainly due to its larger bandgap
(2.45  eV). On the other hand, for CsPbI2Br device, the Voc of
the champion device is ≈979  mV, comparable to the CsPbI3
(≈926  mV) and CsPbBr2I (1021  mV) based devices. There are
several reports stating that a slight amount of Br− doping in
CsPbI3 nanocrystals can improve the optical and electrical prop-
erties by reducing its surface defects,[57,58] mainly due to the
increase in tolerance factor toward an ideal value as compared
to CsPbI3. But the Jsc value of CsPbI2Br (≈12.91 mA cm−2) based
device is found to be maximum among all other anionic com-
position variable-based devices. An improved short circuit cur-
rent for CsPbI2Br device also supports the reduced defect state
density resulting in an enhanced charge transport behavior. As
it is well known that iodine loss, ligand loss in CsPbI3 under
ambient condition is a common phenomenon,[59,44] which cre-
ates some nonradiative electrical defects on the surface of the
film, hampering the charge transport in the device. As a result,
we have observed a lower Jsc value for the CsPbI3 device as com-
pared to the CsPbI2Br one. The CsPbI2Br device shows a max-
imum fill factor of 64.5% and an efficiency of 8.15%, which are
superior (an enhancement of 57% over CsPbI3) to other devices
processed under the same ambient condition. Reduced series
(≈19.58 Ω cm2) resistance of the CsPbI2Br based device further
confirms the reduction of defect states due to Br incorporation
leading to superior film quality. In Table ST3 (Supporting Infor-
mation), we have summarized all the device parameters of the
fabricated devices under the same ambient condition (45–55%
humidity) with the variation of perovskite composition. A fur-
ther optimization of the device fabrication process including
contact metallization and surface passivation under a controlled
atmosphere (glove box) can boost the solar cell conversion
efficiency using our synthesized α-CsPbBrxI3−x nanocrystals as
active light absorbing materials.
3. Conclusion
In conclusion, we have modified the well-known hot injection
synthesis approach of CsPbX3 nanocrystals by using olive oil
instead of conventionally used oleic acid. Excess fatty acids
in olive oil, direct the growth along the (100) plane leading to
100% cubic CsPbX3 (X = Br, I) nanocrystals with superior sta-
bility under ambient atmosphere, improved homogeneity and
reproducibility. The method also provides a simpler route to
synthesize mixed halide perovskites of desired composition by
physical mixing of CsPbI3 and CsPbBr3 without altering their
crystal structure. High-resolution TEM images clearly reveal the
crystal structure along with the atomically distinguishable Cs,
Pb, and I/Br atoms, bond distance for SHP and MHP nanocrys-
tals, which are well supported by XRD Rietveld refinement data.
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DFT band structure calculation by mBj approximation follow
the same trend of bandgap change with the anionic replace-
ment; CsPbBr3> CsPbBr2I> CsPbBrI2> CsPbI3 in line with the
experimental results. Calculated absorption coefficient and ELF
charge distribution suggests CsPbBrI2 as one of the promising
candidates for the solar cell device along with its enhanced sta-
bility. Finally, CsPbI2Br based solar cell (p–i–n) device shows
a maximum Jsc (≈12.91  mA cm−2) due to the reduced surface
defect states, hence exhibiting higher efficiency (≈8.15%) com-
pared to other perovskite-based devices fabricated under the
same condition.
4. Experimental Section
Materials: Caesium carbonate (Cs2CO3, 99.99%), lead iodide (PbI2,
99.99%), lead bromide (PbBr2, 99.99%), oleyl ammine (OLAm), oleic
acid (OA), poly (3,4-ethylenedioxythiophene)-poly(styrenesulfonate)
(PEDOT:PSS), fullerene-C60, and bathocuproine (BCP) were brought
from Sigma-Aldrich. Olive oil was procured from Bertolli, while all other
solvents brought from Alpha Aesar. All the chemicals were used without
further purification.
Synthesis of CsPbX3 (X = Br, I): This is a two-step reaction, where in
the first step Cs-OA was prepared and in the second step CsPbX3 was
synthesized.
Synthesis of Cs-OA: Here, Cs-OA synthesized in two different ways:
in first, conventional synthesis process was followed using Cs2CO3
(814 mg) and 2.5 mL of oleic acid (OA) in 40 mL of 1-octadecene (ODE).
Initially, the mixture was heated at 120 °C for 1 h then followed by an
increase in temperature of 150 °C under N2 atmosphere for 15–30 min
for complete solubilizations of Cs-salt to Cs-OA, until a transparent
solution was formed. Then the solution cooled to room temperature and
stored for future use.
In the other process, Cs2CO3 (814 mg) and 40 mL Olive oil were used
in a round bottom two-neck flask and heated at 120 °C for 1 h under
vacuum conditions. Followed by raise in temperature to 150 °C under
N2 atmosphere for 10–15 min to get the desired transparent solution of
Cs-OA and stored for further use to synthesized CsPbX3.
Synthesis of CsPbX3 (X = Br, I): Here, four sets of reactions were
performed. For batch-I and batch-II, 870 or 690  mg of PbI2 or PbBr2,
respectively, were taken in two-neck round bottom flask. Then 5  mL of
ODE was added and stirred continuously at 120 °C for 1 h. Then 1  mL
of OA and 1 mL of Oleyl ammine (OLAm) were injected to the mixture
simultaneously under inert N2 atmosphere. Instantly, the temperature
was raised to 150 °C with vigorous stirring until the solution became
transparent. Then 4  mL of the as-synthesized Cs-OA (using ODE+OA
or Olive oil) preheated to 100 °C, swiftly injected to the mixture. After
that the reaction mixture immediately turned into red (CsPbI3) or green
(CsPbBr3) and cooled instantly in an ice bath, to stop the reaction.
In another case, same amount of PbI2 or PbBr2 and 5  mL olive oil
were used instead of ODE and heated 120 °C under vacuum for 1 h. Then
1 mL of OLAm was injected in the reaction mixture under N2 atmosphere
to get a transparent solution. Similarly preheated Cs-OA was injected
and cooled immediately to get desired CsPbI3 or CsPbBr3 nanocrystals.
Purification of CsPbX3 (X = Br, I): The as-synthesize CsPbX3 (X = Br, I)
purified through centrifugations using excess hexane. The centrifugation
process (20 000 rpm) repeated for several times to remove excess OA/
OLA/Olive oil from the product. Finally, the sedimentation was collected
and re-dispersed in hexane. The collected dispersion was stored in a
sealed vial for further characterizations or device fabrications.
Mixed Halide Perovskite (CsPbI2Br, CsPbBr2I) Synthesis: Mixed halide
perovskite were synthesized by simple physical mixing technique.
Both purified CsPbI3 and CsPbBr3 with similar concentrations were
mixed in 2:1 ratio and kept for 1 h to obtain CsPbI2Br. Similarly, when
we mix them in 1:2 ratios and kept for 1 h we get CsPbBr2I as product.
As-synthesized CsPbI2Br and CsPbBr2I stored in a sealed vial and
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used for characterizations or device fabrications without any further
purification.
Statistical Analysis: The average size of the nanocrystals was
measured using the histograms shown in Figure S8c,d (Supporting
Information). For XRD analysis, Rietveld refinement was used using
Full-prof software. Simulation of the HRTEM images was performed
using Digital Micrograph software. 16 devices were fabricated at a time
followed by their characterizations. The highest efficiency value of the
inverted perovskite solar cells out of 40 devices is reported here. Density
functional theory was performed using Wien2K software. The details are
given in the Supporting information.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors would like to thank Dr. Mantu Modak of Saha Institute
of Nuclear Physics for the Rietveld refinement analysis and Mr.
Baidyanath Roy and Ms. Shaona Bose of IIT Kharagpur for the
stability measurements. The DST FIST facility of IIT Kharagpur for XPS
measurements is acknowledged. The financial support received under
the Meity NNETRA “SWI” project is gratefully acknowledged.
Conflict of Interest
The authors declare no conflict of interest.
Data availability Statement
Research data are not shared.
Keywords
atomic resolution TEM, caesium lead halide perovskites, colloidal
syntheses, density functional theory, inverted perovskite solar cells
Received: February 21, 2022
Revised: May 12, 2022
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