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Deep Insights into the Coupled Optoelectronic and Photovoltaic

Analysis of Lead-Free CsSnI3 Perovskite-Based Solar Cell Using DFT
Calculations and SCAPS-1D Simulations
M. Khalid Hossain,* G. F. Ishraque Toki, D. P. Samajdar,* Muhammad Mushtaq, M. H. K. Rubel,*
Rahul Pandey,* Jaya Madan, Mustafa K. A. Mohammed, Md. Rasidul Islam, Md. Ferdous Rahman,
and H. Bencherif

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ABSTRACT: CsSnI3 is considered to be a viable alternative to lead (Pb)-based perovskite solar cells (PSCs) due to its suitable
optoelectronic properties. The photovoltaic (PV) potential of CsSnI3 has not yet been fully explored due to its inherent difficulties in
realizing defect-free device construction owing to the nonoptimized alignment of the electron transport layer (ETL), hole transport
layer (HTL), efficient device architecture, and stability issues. In this work, initially, the structural, optical, and electronic properties
of the CsSnI3 perovskite absorber layer were evaluated using the CASTEP program within the framework of the density functional
theory (DFT) approach. The band structure analysis revealed that CsSnI3 is a direct band gap semiconductor with a band gap of
0.95 eV, whose band edges are dominated by Sn 5s/5p electrons After performing the DFT analysis, we investigated the PV
performance of a variety of CsSnI3-based solar cell configurations utilizing a one-dimensional solar cell capacitance simulator
(SCAPS-1D) with different competent ETLs such as IGZO, WS2, CeO2, TiO2, ZnO, PCBM, and C60. Simulation results revealed
that the device architecture comprising ITO/ETL/CsSnI3/CuI/Au exhibited better photoconversion efficiency among more than 70
different configurations. The effect of the variation in the absorber, ETL, and HTL thickness on PV performance was analyzed for
the above-mentioned configuration thoroughly. Additionally, the impact of series and shunt resistance, operating temperature,
capacitance, Mott−Schottky, generation, and recombination rate on the six superior configurations were evaluated. The J−V
characteristics and the quantum efficiency plots for these devices are systematically investigated for in-depth analysis. Consequently,
this extensive simulation with validation results established the true potential of CsSnI3 absorber with suitable ETLs including ZnO,
IGZO, WS2, PCBM, CeO2, and C60 ETLs and CuI as HTL, paving a constructive research path for the photovoltaic industry to
fabricate cost-effective, high-efficiency, and nontoxic CsSnI3 PSCs.

1. INTRODUCTION
To keep pace with the current growth of solar technologies,
perovskite solar cells (PSCs) have garnered significant research
owing to the significant rise in efficiency from a meager 3.8 to Received: January 15, 2023
25.7% within a decade.1−5 This significant improvement has Accepted: May 10, 2023
been made possible due to the excellent optoelectronic Published: June 14, 2023
characteristics of halide perovskite materials used including
their high absorption coefficient, low exciton binding energies,
long-range charge diffusion lengths, acceptable band gaps, and
© 2023 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.3c00306
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Figure 1. (a) Design configuration of the CsSnI3-based PSC, and (b) the optimized crystal structure of CsSnI3 perovskite.

high charge carrier mobilities.2,3,5−8 As light absorbers in PSCs, absorber layer (PAL), hole transport layer (HTL), the electron
hybrid organic−inorganic halide perovskites, particularly transport layer (ETL), and back-metal contact layers in PSCs,
methylammonium lead triiodide (MAPbI3) and formamidinium affecting solar cell (SC) performance, is crucial for optimizing
lead triiodide (FAPbI3) have received the majority of attention and enhancing PSC performance.26−28 The optical absorption
at this point. The major hindrance toward the path of characteristics of the PAL play a dominant role in influencing the
commercialization and efficient usage of MAPbI3 or FAPbI3- PV characteristics. The transportation and extraction of the
based PSCs is due to the constituent element lead (Pb), which is charge carriers produced due to the absorption of photons in the
highly toxic in nature.9,10 Under these circumstances, the PAL are controlled by the ETL and HTL.29 While the open
European Union and other nations have placed strong circuit voltage (VOC) is determined by the Fermi energy level
restrictions on the usage of Pb-containing materials in electronic difference among the ETL and HTL; the ETL’s accelerated
gadgets, which has accelerated the research on Pb-free PSCs.3,11 charge mobility causes a commensurate rise in the fill factor
Due to the low toxicity and exceptional theoretical PCE, lead- (FF) and short circuit current density (JSC).30−32 Materials
free tin halide perovskites have received a lot of attention in the utilized as ETL and HTL include both organic and inorganic
development of energy-efficient SCs.12 Tin (Sn) is considered components. The most commonly used ETLs like TiO2,33,34
one of the most practical substitutes for Pb in the perovskite ZnO,33,35 C60,36 IGZO,37 PCBM, WS2,34,38 and CeO239 are used
configurations as replacement of the toxic Pb2+ ions with Sn2+ with CuI40 and CBTS41 is as HTL, due to the suitable respective
creates no alteration in the perovskite structure owing to the band gap, charge mobility, band alignment, and transparency.
similarity between the outer shell of Pb and Sn.13 Hence, In order to predict the suitability of a particular material
MASnI3 and FASnI3 have been thoroughly investigated for PV system for PV applications, we need to investigate its optical and
applications and it is predicted that the conversion of the electronic properties systematically and accurately and this
organic−inorganic hybrid perovskite to all-organic perovskite necessitates the usage of DFT approaches,42 which have gained a
through the replacement of MA+ or FA+ with Cesium (Cs) leads lot of popularity in physical, chemical, and biological
to the enhancement in the intrinsic phase and thermal applications since its inception in the 1970s.43 Song et al.
stability.14−17 computed the structural and electronic properties of CsSnI3
It has been demonstrated in the literature that the all- based on the DFT approach using PBEsol exchange-correlation
inorganic CsSnI3 perovskite can be produced via melting− functional implemented in the VASP package to conclude that
solidification and has a melting point of 451 °C, signifying the polar phase (Pmc21) possesses a direct tunable band gap in
superior inherent thermal stability.18,19 In contrast, the MASnI3 the range 0.42−1.41 eV, which is suitable for light-harvesting
and FASnI3 perovskite analogs of halide perovskites begin to applications. 44 The electronic band structure of CsSnI3
deteriorate at about ∼200 °C.20 The aforementioned factors computed using the quasiparticle self-consistent GW method
contribute to the motivation for the exploration of CsSnI3 revealed a band gap of 1.3 ± 0.1 eV for CsSnI3, high hole
material as a potentially useful thermally durable, lead-free mobility, and a low exciton binding energy of 0.1 meV.45 First-
perovskite for next-generation PSCs. For device-operating principle calculations reveal that the band gap of CsSnI3 varies
temperatures in the range 20−100 °C, CsSnI3 exists in the from ∼1.2−1.3 eV over a temperature range from 9 to 300 K due
form of two polymorphs: the desired ″black″ B−γ−CsSnI3 stage to the change in the lattice constant with a linear thermal
and the unfavorable ″yellow″ Y�CsSnI3 stage.18 Comprehen- expansion coefficient of 1.40 × 105 K−1.46 Traoré et al. reported
sive research has been done on the B−γ−CsSnI3 stage, and it has a band gap of 1.21 eV for CsSnI3 using the reoptimized Tran−
been found to have features that are useful for PSC applications. Blaha-modified Becke−Johnson (TB-mBJ) potential, which is
It has a direct ideal band gap of 1.3 eV,18,21 a low exciton binding much higher than the underestimated band gap of nearly zero
energy of 10−20 meV,22 a significant optical absorption computed using local density approximation.47 In order to check
coefficient of ∼104 cm−1,23 and high hole mobility of up to the feasibility of using CsSnI3 as a potential absorber for SCs, we
∼585 cm2 V−1 s−1.18 However, there are just a few findings that have systematically investigated the structural, optical, and
have employed B−γ−CsSnI3 as a light absorber in modules, and electronic properties of the perovskite along with its charge
those findings have had varying degrees of success, underlining density characteristics and Fermi surface topology within the
the difficulties in developing B−γ−CsSnI3-based PSCs.24,25 framework of DFT calculations using the CASTEP software.
A thorough grasp of how the different constituent layers, The best-optimized ground state was utilized for the evaluation
namely, the transparent conductive oxide (TCO), perovskite of the above-mentioned properties of the CsSnI3 absorber.
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The functionality of the device can be improved by combining voltaic processes like light absorption, exciton generation,
the perovskite absorber layer with acceptable replacements for charge transfer and collection, and recombination. Equation 1
conventional ETL, HTL, and back contact metals. By selecting defines Poisson’s equation, which defines the relation between
70 different configurations in the Solar Cell Capacitance electrostatic potential and the charge density distribution.57
Simulator-1D (SCAPS-1D), we thoroughly evaluated the
suitability of a variety of ETLs and HTLs in this work to find d2 q
2
(x) = [p(x) n(x) + ND NA + P n
]
the ideal combination for the CsSnI3 absorber layer for achieving dx 0 r
superior PV performance in comparison to the existing works. (1)
We performed a computational study to create a combination of In this equation, ψ stands for electric potential, εr is the
heterostructures to reduce the time and cost complexity needed relative permittivity, ε0 stands for the permittivity of free space,
to fabricate such a vast number of SC configurations physically. ND/A are the densities of donors/acceptors, n/p refers to the
Based on these considerations, 70 various combinations of ITO/ electron/hole concentration, ρp/n are the hole/electron charge
ETL/CsSnI3/HTL/Au heterostructures have been examined density, and q is the electronic charge.
for the CsSnI3-based PV configurations with a broad variety of The continuity equations for electrons and holes are given by
HTLs including Cu 2 O, CuSCN, NiO, P3HT, CBTS, eqs 2 and 3, respectively:
PEDOT:PSS, Spiro-MeOTAD, CuI, CuO, and CFTS com-
bined with ETLs such as PCBM, TiO2, ZnO, C60, IGZO, WS2, n 1 Jn
and CeO2 (Figure 1a). After selecting the most promising = + (Gn R n)
t q x (2)
combinations, we further investigated the effects of the CsSnI3
absorber and ETL thickness on the performance of the six best-
performing devices in terms of PV parameters, series and shunt
p 1 Jp
= + (Gp R p)
resistance, and operating temperature. Additionally, the impact t q x (3)
of capacitance, Mott−Schottky (MS), generation and recombi-
In these equations, Jn/p stands for the current densities of
nation rate, current−voltage (J−V) properties, and quantum
electrons/holes, Gn/p are the electron/hole generation rates, and
efficiency (QE) were assessed. The acquired SC parameters are
Rn/p stands for the recombination rate for electrons/holes.
finally been compared with previous studies. To design and
Charge carrier drift-diffusion is used to calculate both the
manufacture low-cost, high-efficiency, and lead-free CsSnI3-
electron and hole current densities in the PSC by using eqs 4 and
based solar cells, six competitive and feasible designs for high-
5:
efficiency CsSnI3 solar cells have been investigated thoroughly
using a combination of SCAPS-1D and DFT computations. Jn = q n n +qDn n (4)

2. MATERIALS AND METHODOLOGY Jp = q p p qDp p (5)

2.1. First Principal Calculations of CsSnI3 Absorber
Layer. In this study, first-principle calculations based on DFT In these equations, Dn/p stands for the diffusion coefficient of
were performed with CASTEP code to provide deep insights electrons/holes, and μn/p stands for the mobility of charge
into the ground state configuration, optical, and electronic carriers.
properties of bulk CsSnI3 compound using Pm3̅m symmetry. In At contacts and interfaces, SCAPS-1D solves both Poisson’s
the total energy calculations, the exchange-correlation potential equation as well as continuity equations for the charge carriers.
(EXC) was treated in generalized gradient approximation (GGA) The FF of the device specified by eq 6 is58
proposed by Perdew−Burke−Ernzerhof (PBE).48,49 The Jmp × Vmp
interactions between electrons and nuclei were described with FF =
ultrasoft pseudopotentials of the Vanderbilt, which require a JSC × VOC (6)
relatively smaller basis set and thus are computationally The terms Vmp and Jmp in this context refer to the maximum
favorable.50 The basis sets were expanded with an energy cut- obtainable voltage and current density from the SC. The short-
off of 520 eV. Broyden−Fletcher−Goldfarb−Shannon (BFGS) circuit current density is denoted by JSC, and the open-circuit
algorithm was used to minimize the total energy and obtain the voltage is denoted by VOC. Equation 7 illustrates the device
ground state properties. In reciprocal space, the Brillouin zone efficiency normalized with respect to the power input Pin
integration was performed with the Monkhorst−Pack (MP) equivalent to the AM 1.5G spectrum.59
scheme with a 12 × 12 × 12 k-points mesh for geometry
optimization, whereas, to obtain reliable results, the electronic VOC × JSC × FF
density of states and charge density calculations were carried out =
Pin (7)
with a dense 17 × 17 × 17 k-mesh. The energy minimization
iterations were carried on until the energy difference between 2.3. CsSnI3 Perovskite Solar Cell Structure. The study
two consecutive iterations becomes less than 10−4 eV. During involved simulations of PSCs based on the CsSnI3 absorber
the relaxation of atomic positions, the atoms were allowed to layer. In n−i−p planar structures, the ETL denotes the n-region,
move under the critical force of 0.001 eV/Å and a stress of 0.05 HTL constitutes, and the perovskite layer is located in the i-
GPa. region. When the cell is illuminated, the perovskite i-layer
2.2. SCAPS-1D Numerical Simulation. To model perov- generates an exciton, which is a Coulombic pair of an electron
skite PSCs, the ELIS department at the University of Gent and a hole. When the exciton dissociates at the junction of the i-
developed the SCAPS-1D code. With the help of realistic and and p-layers, the hole moves to the p layer and the residual
accurate back-end physical equations, a wide range of device electron to the n layer. The electric field existing at the interface
architectures can be designed and investigated using the flexible of two different layers speeds up the process of exciton
PV software SCAPS 1D.51−56 This software simulates photo- dissociation.
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Table 1. Input Parameters of TCO, ETL, and Absorber Layer (CsSnI3)60−62

parameters ITO TiO2 PCBM ZnO C60 IGZO WS2 CeO2 CsSnI3
thickness (nm) 500 30 50 50 50 30 100 100 800a
band gap, Eg (eV) 3.5 3.2 2 3.3 1.7 3.05 1.8 3.5 1.3
electron affinity, X (eV) 4 4 3.9 4 3.9 4.16 3.95 4.6 3.6
dielectric permittivity (relative), εr 9 9 3.9 9 4.2 10 13.6 9 9.93
CB effective density of states, NC 2.2 × 1018 2 × 1018 2.5 × 1021 3.7 × 1018 8.0 × 1019 5 × 1018 1 × 1018 1 × 1020 1 × 1019
(1/cm3)
VB effective density of states, NV (1/cm3) 1.8 × 1019 1.8 × 1019 2.5 × 1021 1.8 × 1019 8.0 × 1019 5 × 1018 2.4 × 1019 2 × 1021 1 × 1018
electron mobility, μn (cm2/Vs) 20 20 0.2 100 8.0 × 10−2 15 100 100 1.5 × 103
hole mobility, μh (cm2/Vs) 10 10 0.2 25 3.5 × 10−3 0.1 100 25 5.85 × 102
shallow uniform acceptor density, NA (1/ 0 0 0 0 0 0 0 0 1020
cm3)
shallow uniform donor density, ND (1/ 1 × 1021 9 × 1016 2.93 × 1017 1 × 1018 1 × 1017 1 × 1017 1 × 1018 1021 0
cm3)
defect density, Nt (1/cm3) 1 × 1015a 1 × 1015a 1 × 1015a 1 × 1015a 1 × 1015a 1 × 1015a 1 × 1015a 1 × 1015a 1 × 1015a
a
In this study, these values remain constant during initial optimization to get the best combination of HTL, ETL, and back metal contact.

Table 2. Input Parameters of Different HTLs60

Spiro-
HTL Cu2O CuSCN P3HT PEDOT:PSS MeOTAD NiO CuI CuO CFTS CBTS
thickness (nm) 50 50 50 50 200 100 100 50 100 100
band gap, Eg (eV) 2.2 3.6 1.7 1.6 3 3.8 3.1 1.51 1.3 1.9
electron affinity, Χ (eV) 3.4 1.7 3.5 3.4 2.2 1.46 2.1 4.07 3.3 3.6
dielectric permittivity 7.5 10 3 3 3 10.7 6.5 18.1 9 5.4
(relative), εr
CB effective density of states, 2 × 1019 2.2 × 1019 2 × 1021 2.2 × 1018 2.2 × 1018 2.8 × 1019 2.8 × 1019 2.2 × 1019 2.2 × 1018 2.2 × 1018
NC (1/cm3)
VB effective density of states, 1 × 1019 1.8 × 1018 2 × 1021 1.8 × 1019 1.8 × 1019 1 × 1019 1 × 1019 5.5 × 1020 1.8 × 1019 1.8 × 1019
NV (1/cm3)
electron mobility, μn (cm2/ 200 100 1.8 × 10−3 4.5 × 10−2 2.1 × 10−3 12 100 100 21.98 30
Vs)
hole mobility, μh (cm2/Vs) 8600 25 1.86 × 10−2 4.5 × 10−2 2.16 × 10−3 2.8 43.9 0.1 21.98 10
shallow uniform acceptor 1 × 1018 1 × 1018 1 × 1018 1 × 1018 1.0 × 1018 1 × 1018 1.0 × 1018 1 × 1018 1 × 1018 1 × 1018
density, NA (1/cm3)
shallow uniform donor 0 0 0 0 0 0 0 0 0 0
density, ND (1/cm3)
defect density, Nt (1/cm3) 1.0 × 1 × 1015a 1 × 1015a 1 × 1015a 1.0 × 1015a 1 × 1015a 1.0 × 1 × 1015a 1 × 1015a 1 × 1015a
1015a 1015a
a
In this study.

Table 3. Input Parameters of Interface Defect layers60

defect capture cross section: electrons/holes energetic reference for defect energy total density (cm−2) (integrated over all
interface type (cm2) distribution level energies)
ETL/CsSnI3 neutral 1.0 × 10−17 single above the VB maximum 1.0 × 1010
1.0 × 10−18
CsSnI3/ neutral 1.0 × 10−18 single above the VB maximum 1.0 × 1010
HTL
1.0 × 10−19

In the analysis, the TCO, back contact, and absorber were ance of the SC. Our goal is to find the best charge transport
represented by the indium-doped tin oxide (ITO), Au (gold), materials that establish a compromise between electrical and
and CsSnI3, respectively (Table 1). Figure 1a illustrates the PSC optical outputs in order to improve solar cell performance. The
architecture examined using 7 ETLs and 10 HTLs to determine addition of interface defect density at each of the junctions
the optimal pairing during simulation with SCAPS-1D. Potential specified in Table 3 adds to the practicality of the simulations.
ETL and HTL candidates (Tables 1 and 2) are carefully chosen To determine the impact of operating temperature on the PSC
based on outstanding characteristics like high mobility and performance, simulations were run at an ambient temperature of
suitable electronic affinity, which resolve the VOC deficit issue about 300 K with an incoming power density and a frequency of
caused by nonradiative recombination, which causes the 100 mW/cm2 and 1 MHz, respectively, under the AM 1.5G solar
unwanted quasi-Fermi level splitting phenomenon. In addition, spectrum.
an adequate ETL band gap boosts the photogenerated carrier
rate, in addition to a long diffusion length, preventing JSC 3. RESULTS AND DISCUSSIONS
saturation as perovskite material thickness increases. The 3.1. Analysis of DFT Results. 3.1.1. Structural Properties
interwoven effect of these parameters may hinder the perform- of CsSnI3 Compound. The CsSnI3 perovskite phase has a cubic
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Figure 2. (a) Relaxed geometry, (b) band structure, (c−f) total and orbital density of states, (g) electronic charge density map, and (h) Fermi surface
contour of CsSnI3 perovskite.

structure (space group Pm3̅m, no. 221) formed by the Cs, Sn, Cs−Sn angle θ(Sn−Cs−Sn) is 70.52°, being shorter (larger)
and I atoms with high symmetric atomic positions of (0.0, 0.0, than the I−Cs−I angle θ(I−Cs−I) of 90°. The compound has a
0.0), (0.50, 0.50. 0.50), and (0.00, 0.50, 0.50), respectively63 ground state total energy (E0) of −1589.4673 eV, which yields
(Figure 1b). The fully relaxed geometry of CsSnI3 is shown in the lattice constant (a) of 6.253 Å, close to the experimental
Figure 2a. It can be seen that the Cs atom is located in the middle value of 6.219 Å.64 Additionally, the significant negative forming
of the unit cell; Sn atoms are positioned at the corners of the energy value (Ef = −1589.4673 eV/atom) of the optimized
cube; and iodine atoms are present between the edges of Sn structure shows that it has a stable structural design that is
atoms. The Cs atom is placed at the octahedral position, appropriate for the construction of the solar system.
surrounded by eight neighboring I atoms. The computed 3.1.2. Electronic Properties of CsSnI3 Compound. Based on
distance between Cs and I atoms is found to be 3.14 Å, and the the relaxed structure, the electronic properties of the CsSnI3
I−Cs−I bond angle θ(I−Cs−I) is exactly 90°. The interatomic perovskite are explored by computing the electronic band
distance between Cs and Sn atoms d(Cs, Sn) is 5.44 Å, while the structure, density of states, charge density, and Fermi surface, as
distance between Cs and I atoms d(Cs, I) is 4.44 Å. The Sn− shown in Figure 2. From the band structure calculated along
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Figure 3. Calculated six optical functions ((a) dielectric function, (b) refractive index, (c) conductivity, (d) absorption, (e) reflectivity, and (f) loss
function) of the CsSnI3 perovskite solar absorber.

high symmetry k-points in the Brillouin zone (Figure 2b), it is constituent Cs, Sn, and I atoms, the band gap is formed by the
obvious that CsSnI3 is a direct band gap semiconductor, with hybridization between the electronic states of Sn and I atoms.
valence band maximum (VBM) and conduction band minimum 3.1.3. Electron Charge Density of CsSnI3 Compound. The
(CBM) located at the same value (R-point) of the k-vector in electronic charge density plot (Figure 2g) along the (100) plane
the Brillouin zone. The calculated band gap (Eg) is found to be is used to predict the charge transformation behavior and nature
0.95 eV, slightly lower than the theoretically calculated Eg value of bonding among the constituent atoms, ions, or elements.
of 1.307 eV reported elsewhere.65 The formation of band Hence, to examine the electronic property of a material system
structure can be examined with the density of states (DOS) plots more substantially, charge density distribution essentially
shown in Figure 2c−f. In the total DOS (TDOS) shown in depends on the electronic structure and density of states. This
Figure 2c, there is no overlap of electronic states at the Fermi intricate characteristic displays a valence electron charge density
level, and it has a distinct separation between occupied and figure and heavily depends on the calculation approach,
premises, dimensions, and directions of the process concerned.
unoccupied energy states. Thus, TDOS also confirms that the
The charge density output curves differ from structure to
given material has a band gap at the Fermi level, which is
structure as well. The total electronic charge density map is
consistent with the band structure result. The atomic origin of
examined in order to study the behavior of chemical bonding
the energy bands appearing within valence (conduction) bands inside a compound. In essence, the charge density map/curve is
can be probed by the analysis of partial and orbital DOS (that is made up of structural atoms/ions that show how orbital
lm-decomposed DOS) of the constituent atoms. In Figure 2d, it electrons contribute to the electrical characteristics of atoms/
is found that the Cs atoms have no significant contribution to the ions by collecting charges. Red and blue patterns stand for the
formation of the band edges, and the Cs 5p sites are located far high and low charge densities of the CsSnI3 solar absorber,
away from the Fermi level. However, the observed high-intensity respectively. The fact that the majority of charges explicitly
peak in Figure 2d around −9 eV far below the Fermi level mainly concentrate around I and that the distribution of charges is
originates from the Cs 5p valence electron states, while Cs 6s uniformly spherical about I suggests that the Sn−I bonds are
states have almost no obvious role in the construction of band quite stronger. Furthermore, the electron distributions of Cs, I,
edges. Conversely, the Sn 5s/5p states have a clear contribution and Sn ions do not overlap or transmit any charge. The presence
to the electronic states forming the band gap. Thus, among the of ionic bonding in the particular perovskite is clearly
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demonstrated by the charge density, which is mostly found at the from 0 to 10 eV, which indicates that the compound CsSnI3 can
individual lattice positions of Cs, Sn, and I atoms but not be a prospective option for optoelectronic applications in the
between them. The ionic nature of the molecule is related to the visible and UV region.
spherical charge distribution around all the atoms, which also The refractive index (n) of a material is a crucial physical
displays metallic properties.66,67 Interestingly, the reported property that characterizes its optical characteristics. While the
electronic charge density of CsSnI3 is the same in every real part of the refractive index is linked with the phase velocity
crystalline plane, demonstrating the material’s isotropic of the electromagnetic (em) waves in a particular medium, the
character. imaginary part also known as the extinction coefficient quantifies
3.1.4. Fermi Surface of CsSnI3 Compound. The thermal, the attenuation of the em waves traversing through the
electrical, optical, and transport properties of a compound can material.70 Figure 3b portraying the refractive index displays a
be illustrated and predicted by its Fermi surface topology, and it close resemblance with the real part of the dielectric function, as
can be derived from its electronic band structure.68 The it is derived from ε1 (ω). The calculated static refractive index,
investigated Fermi surface topology at different paths of the n(0) for the compound CsSnI3 is about 3.02 having a sharp peak
Brillouin zone of the CsSnI3 solar absorber is depicted in Figure around 1 eV in the near IR region of the em spectrum, which
2h. From the figure, we found a rectangular benzene shape with a further progress with higher energies to the visible and UV
small hole at the center located at the hub Γ(0.0,0.0,0.0) point, regions but with slightly lower values.
which acts as a hole-like surface. The center Γ(0.0,0.0,0.0) point The ability of a medium to initiate a conduction phenomenon
directly connects the R(0.5,0.5,0.5) point of the corner that as em radiations try to propagate through at optical frequencies
passes through a curved-shaped electron-like Fermi surface. The is determined by its optical conductivity σ (ω). It can be
R(0.5,0.5,0.5) point touches a separate small hole-like circular computed from the complex dielectric function.69 It is obvious
disc at the X(0.0,0.5,0.5) point of the body center. Again, the R from the plot given in Figure 3c that conductivity rises with the
point slightly touches an adjacent curved shape electron-like increase in energy up to around 9 eV, and beyond this energy
Fermi surfaces at the M(0.5, 0.0, 0.5) point of the topology. range, the conductivity decreases having a short oscillatory
Therefore, both electron-like and hole-like Fermi surfaces are phase and eventually becomes static. The increased value of the
visualized, which is an implication of the multiband character of σ (ω) in the visible and the UV regions can be attributed to the
CsSnI3. Also, it may be argued that electronic conductivity may increase in absorption coefficient in this energy range as given in
be primarily caused by the highly dispersive band formed by the Figure 3d.
hybridization of the Sn 5p and I 5s orbitals. An essential optical function for using Kramers−Kroning
3.1.5. Optical Properties of CsSnI3 Compound. Analyzing relationships to determine all optical coefficients is the energy-
the complex dielectric function is crucial to learn more about the dependent reflectance spectrum (R). In CsSnI3 solar absorber
optical behavior of compounds.69 As a result, these character- material, which has an initial greater reflectivity than
istics are extremely important for investigating potential isostructural CsSnCl3 (Figure 3e), the reflectivity spectrum
applications of substances in solar and optoelectronic devices. starts at around 0.25 at zero frequency. Thereafter, R rapidly
In this study, the nature of the calculated six optical parameters is increases until it reaches its maximum value of 0.3 for a photon
ascribed in terms of energy up to 30 eV (Figure 3). To energy of around 2.60 eV. The maximum degree of reflectivity in
investigate how materials react to electromagnetic waves and the UV region in Figure 3e may have been caused by interband
how those waves spread via various media, complex dielectric transitions. In addition, three distinct steep peaks may be seen at
functions are used. A dielectric function with the notation ε(ω) energies of 6.1, 9.7, and 15.1 eV. The maximal reflectance of
= ε1(ω) + iε2(ω) can be used to calculate the optical response of CsSnI3 (0.3) is lesser than that of CsSnCl3 (0.41), which may be
any medium. Using the theoretical methodology, the real part ε1 due to the difference in the electronic states of these two
(ω) and imaginary partε2 (ω) of the dielectric function have materials.
been investigated for the compound CsSnI3 as shown in Figure Figure 3f depicts the loss spectrum (L) of CsSnI3, which
3a. shows how much energy a fast electron loses while traveling
The calculation of the zero-frequency limit, which is the through a compound. The energy loss function only explains
electronic component of static dielectric constant ε1(0), is the how electrons lose energy as a result of electron−matter
most notable measurement of the real part of the dielectric interaction.69 It can be observed that energy loss gradually
function, ε1(ω) as it firmly relies on the band gap of the increased showing maxima at a photon energy of 14.8 eV, with a
compound. The value of ε1(0) computed from Figure 3a is few minor peaks. Then, it quickly accelerated, reaching its peak
about 9 eV. ε1 (ω) denotes the electronic polarizability of a energy loss (2.3), also known as plasma frequency (p), at around
particular material.69 It is evident from the figure that the real 16.2 eV. It is obvious that the majority of energy loss occurs in
part of the dielectric function comprises both negative and the UV spectrum due to the greater photon energy than that of
positive values. The propagation of electromagnetic waves is the band gap energy.
associated with the positive half, whereas their absorption is 3.2. Analysis of SCAPS-1D Results. In this section, the PV
correlated to the negative half as the electromagnetic waves do response of the heterostructure ITO/ETL/CsSnI3/HTL/Au is
not propagate in the compounds in this negative range. The assessed by varying the ETL, absorber, and HTL layers while
highest peak of the ε1(ω) is observed in the visible part of the maintaining the respective thickness for HTL given in the
electromagnetic spectrum, and the value abruptly starts reducing parentheses (Cu2O (50 nm), CuSCN (50 nm), P3HT (50 nm),
toward zero and eventually becomes negative from around ∼6.5 PEDOT:PSS (50 nm), Spiro-MeOTAD (50 nm), NiO (50 nm),
eV, suggesting the maximum absorption in this negative range. A CuI (50 nm), CuO (50 nm), CFTS (50 nm), and CBTS (50
photon’s absorption is related to the ε2(ω), which represents the nm)) and ETL (PCBM (50 nm), ZnO (50 nm), C60 (50 nm),
electronic characteristics of crystalline materials. The sharp IGZO (30 nm), WS2 (100 nm), and CeO2 (100 nm)) for the
peaks in the ε2(ω) depict how charge carriers switch from filled 800 nm CsSnI3 absorber layer constant, and the acceptor
to empty bands. ε2(ω) exhibits significant values in the range concentration and defect densities are set at 1018 cm−3 and 1015
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Figure 4. EBD of CsSnI3-based PSC with CuI HTL, Au back contact, and different ETLs: (a) PCBM, (b) ZnO, (c) C60, (d) IGZO, (e) WS2, and (f)
CeO2.

cm−3, respectively. After the initial simulation, based on the each of the ETL/CsSnI3 and CsSnI3/CuI HTL interfaces have a
performance of 70 different combinations, the best-performing considerable impact on device PV performance parameters such
devices were investigated through different studies discussed in as JSC, VOC, FF, and PCE. The Fermi level is uniform throughout
the following sections. the entire structure under thermal equilibrium conditions, and
3.2.1. Energy Band Diagram (EBD) of CsSnI3. Each studied the incidence of photons on the PSC structure disturbs this
ETL with a CsSnI3 PAL and CuI as HTL influence the valence/ alignment with the formation of quasi-Fermi energy levels.
conduction band offset in the EBD (difference of VBM between When the CBM of the ETL lies above the CBM of the absorber
the HTL and the absorber layer and CBM between the absorber (positive CBO), a spike is formed at the ETL/absorber interface,
layer and ETL). Energy level alignment has a substantial impact which blocks the electron flow. However, a smooth flow of
on the efficiency and performance of PSCs. Photogenerated electrons is ensured in the opposite case of negative CBO.71 On
electrons are injected into the ETL conduction band, whereas the other hand, for effective hole transport, the VBM of the HTL
holes are transferred to the CuI HTL in PSCs. Following that, should be greater than that of the perovskite. The activation
electrons and holes are collected at their respective front (ITO) energy for recombination is defined as Ea = Eg − |CBO/VBO|,
and back (Au) contact metals. However, the electron affinity of and the recombination increases with decreasing Ea due to
each ETL (PCBM, ZnO, C60, IGZO, WS2, and CeO2) should be higher CBO/VBO.72 From the EBDs, shown in Figure 4a−f, it
greater than that of CsSnI3 to extract the electron at the ETL/ can be observed that the VBO at the HTL/perovskite interface is
CsSnI3 interface, and the ionization energy of CuI HTL should small enough for efficient hole transport. Devices with PCBM as
be lower than that of CsSnI3 to extract the holes at the CsSnI3/ the ETL and CuI as HTL exhibit the best PCE of 10.10% due to
CuI HTL interface. Furthermore, energy band mismatches at its smaller CBO, which helps in efficient electron transport as
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compared to the other ETLs (Figure 4a). Almost similar values to the corresponding CuI HTL. Inorganic CuI is one of the most
of CBO are also obtained with ETLs C60 and WS2 (Figure 4c,e). promising inorganic semiconductors for employment as HTL in
However, somewhat inferior PV performance is achieved with PSCs to improve PV capabilities.73,74 Due to its optimum band
ZnO, IGZO, and CeO2 as ETL and CuI as HTL due to higher gap, high absorption coefficient, remarkable conductivity, and
CBO, thereby leading to increased recombination and low reduced valence band offset, which is good for hole transport,
efficiency (Figure 4b,d, f) The worst-case scenario is observed hydrophobicity, environmental stability, solution processability,
with CeO2, which shows the highest CBO and the lowest nontoxicity, and naturally occurring abundance, the p-type
efficiency of 6.23%. semiconductor CuI can be used as a promising component for
3.2.2. Effect of ETL. In this study, a CsSnI3-based PSC was being used as an efficient HTL.75 SCs utilize CuI as HTL,
studied, with 7 ETLs, 10 HTLs, and Au as the back metal contact leading to greater stability and less hysteresis. Moreover, CuI is
initially. Utilizing the SCAPS-1D platform, 70 different less expensive than Spiro-MeOTAD, making it an appealing
configurations of SCs are tested numerically to see how well option for reducing the cost of lead-free PSC manufacturing.
they work, and six sets of optimized SCs are reported. To find 3.2.4. Effect of Absorber and ETL Thickness on PV
the best ETL/HTL combination, 70 different SC configurations Performance. In this subsection, the contour plot representa-
are tested with each of the ETL enlisted in Table 1 and distinct tion is used to examine the impact of the CsSnI3 absorber layer
HTL from Table 2. Based on Table 4, it was apparent that the six with the six best-chosen ETL layer thicknesses on the PV
performance of the PSC configurations. The fundamental and
Table 4. PV Parameters for the Best Configuration for each of most important factor in producing high-performance SCs is to
the ETLs select a proper combination of an absorber and ETL.
Additionally, the right absorber thickness with ETL contributes
VOC JSC PCE
optimized device (V) (mA/cm2) FF (%) (%) to the proper light harvesting and carrier transport from the
ITO/PCBM/CsSnI3/CuI/ 0.909 14.24 78.11 10.1
perovskite absorber layer.
Au Figure 6 depicts how the ETL and absorber layer thickness of
ITO/ZnO/CsSnI3/CuI/Au 0.913 12.01 72.76 7.97 the six best-performed PSC structures mentioned in Table 4
ITO/C60/CsSnI3/CuI/Au 0.909 14.81 69.99 9.43 affect the VOC characteristics. In the case of PCBM, it can be seen
ITO/IGZO/CsSnI3/CuI/Au 0.865 11.63 73.09 7.35 from Figure 6a that the absorber thickness and ETL thickness of
ITO/WS2/CsSnI3/CuI/Au 0.933 13.59 73.08 9.26 ≤0.1 and ≤ 0.2 μm, respectively, deliver a maximum VOC of
ITO/CeO2/CsSnI3/CuI/Au 0.603 15.86 65.06 6.23 0.918 V. With the increase in the ETL and absorber layer
thicknesses, VOC degrades. According to Figure 6b,c, ETLs ZnO
best-performed structures were taken from 70 possible and C60 showed a similar trend as that of PCBM achieving
combinations. Figure 5 illustrates PV characteristics for all the maximum VOC 0.922 V for lower absorber layer thicknesses of
CsSnI3-based configurations while Figure 5a shows VOC for all 0.1 and 0.2 μm and ETL thicknesses of 0.01 and 0.03 μm,
studied ETLs and HTLs. Among the studied ETLs, WS2 ETL respectively. Maximum VOC was achieved for the IGZO ETL-
showed the highest VOC of 0.933 V and CeO2 ETL showed the based structure with absorber and ETL thicknesses of less than
lowest VOC of 0.553 V. ETLs like PCBM, TiO2, ZnO, and C60 0.1 and 0.2 μm, respectively (Figure 6d). However, from Figure
showed similar kinds of VOC ranges from 0.909−0.913 V for the 6e, a somewhat different pattern is observed with WS2 ETL,
most number of cases. From Figure 5b, it can be seen that among where higher VOC values can be achieved with an absorber
all devices, JSC values of 15.9 and 0.298 mA/cm2 of CeO2 ETL thickness less than 0.1 μm and ETL thickness in the range of
were the highest and lowest for all the ETL and HTL 0.2−0.4 μm. In the case of CeO2 (Figure 6f), the pattern of the
configurations investigated. For all the CsSnI3 combinations, variation in VOC is similar to that of ZnO but the range of values
the maximum range of FF was between ∼45 and 78 and ∼44 and of VOC is much smaller as compared to the other ETLs. So, it can
76% for PCBM and IGZO ETLs, respectively, while CeO2 ETL be concluded that higher VOC can be achieved with lower
showed the minimum FF range between ∼39 and 65%. PCBM thicknesses of the absorber and ETL, and the increase in
ETL showed maximum throughput with all the HTLs. In the thickness of these layers can lead to reduced PV performance.
ITO/ETL/CsSnI3/HTL/Au heterostructure, ETLs like PCBM, The effect of changing the ETL and absorber layer thickness
C60, and WS2 resulted in comparatively better efficiency in the on the JSC characteristics of six studied PSCs is shown in Figure
range of ∼9−10%. On the other hand, ZnO, IGZO, TiO2, and 7. When the ETL thickness is between 0.03 to 0.15 μm and the
CeO2 performance was not satisfactory with an efficiency of absorber thickness is 0.2 to 0.3 μm for the PCBM-based ETL
≤8%. structure, the highest JSC value of 14.80 mA/cm2 is observed
3.2.3. Effect of HTL. Ten different HTLs were used in this (Figure 7a). ZnO and IGZO ETL-based SCs exhibit a nearly
analysis to evaluate seven sets of ETLs. Except for TiO2, all of the identical pattern, with almost a similar highest JSC of 15 and
ETL alternatives performed better with the CuI HTL by about 14.94 mA/cm2 when the absorber thickness and ETL thickness
6−10%. The HTLs like CuSCN, NiO, P3HT, PEDOT:PSS, are 0.2 and 0.01 μm, respectively (Figure 7b,d). For the C60
Spiro-MeOTAD, CBTS, and CFTS also appear to be most ETL-based structure, a maximum JSC value of 15.40 mA/cm2
matched with the CsSnI3 absorber when evaluated from the was demonstrated for ETL and absorber thicknesseses less than
performance point of view (Figure 5). With regards to the other 0.15 and 0. 0.2 μm, respectively (Figure 7c). When the absorber
HTLs, the Cu2O, and CuO HTLs underperformed when thickness lies in the range 0.2−0.3 μm and WS2 and CeO2
combined with each ETL. The HTL must be thicker and equal thicknesses were 0.05 and 0.25 μm, respectively, the structures
to the n-type ETL since studied HTLs are p-type layers in order exhibited a maximum JSC of ∼16.4 mA/cm2, (Figure 7e,f). It is
to reduce the likelihood of recombination mainly because it evident from the plots that lower thicknesses of the absorber and
enables the prompt transfer of an equivalent amount of charge ETL are desirable for better performance.
carriers to the structure. Under these circumstances, the Figure 8 depicts the degree of variation of FF with the change
thickness of each ETL was chosen to be either lower or equal in the thickness of the absorber and ETL layers for the six
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Figure 5. Variation of PV parameters (a) VOC (V), (b) JSC (mA/cm2), (c) FF (%), and (d) PCE (%) of the CsSnI3-based solar cell for the studied HTLs
with Au as back contact and different ETLs.

devices under consideration. Figure 8a illustrates that for the and ETL thicknesses were 0.2 and 0.01 μm, respectively (Figure
PCBM ETL-based structure, FF values can drop from 83.10 to 9b,d). Among all the structures, WS2 showed the highest PCE of
75.50% ETL thickness in the range of 0.15−0.2 μm irrespective 11.90% when absorber and ETL thicknesses were 0.2 and 0.3
of the absorber thickness. For ZnO and CeO2-based ETLs, it can μm (Figure 9e), while CeO2 showed the lowest PCE of 6.51%
be observed from Figure 8b,f that higher values of FF can be with absorber and ETL thicknesses of 0.2 and 0.03 μm,
observed for absorber layer thicknesses below 0.2 μm. For CeO2, respectively (Figure 9f). So, with the increment of the absorber
the FF is almost independent of the thickness of the ETL and for and ETL thickness, PV parameters tend to decline, which is
ZnO, it can be observed that there is the least variation in FF for consistent with the previous studies.
ETL and absorber thicknesses beyond 0.1 and 0.2 μm, 3.2.5. Effect of Series Resistance. Shunt (RSH) and series
respectively. C60 being a polymer almost shows the same (RS) resistances, which are mostly created by connections
pattern of variation in FF as that of PCBM, though the maximum between the different layers of PSCs, metal contacts, semi-
value of FF achieved with this ETL is almost 2.8% lower than conductor−metal interface, and faulty SC processing steps, have
that of PCBM (Figure 8c). From the contour plots in Figure a major negative impact on the performance of perovskites. In
8d,e, it can be concluded that for the ETLs IGZO and WS2, high the instance of ITO/ETL/CsSnI3/CuI/Au devices, Figure 10
FF values can be achieved for ETL thicknesses beyond 0.15 μm demonstrates the variation of different PV parameters due to the
irrespective of the absorber thickness. change in RS from 0 to 6 Ω cm2, with the shunt resistance kept
The PSCs incorporated with PCBM and C60 ETL exhibited constant at 105 Ω cm2. It can be observed from Figure 10a,b that
the same trend of PCE with rising absorber and ETL layer VOC and JSC are almost independent of RS for different ETLs.
thickness, as shown in Figure 9a,c. When the absorber layer and While the highest VOC is exhibited by WS2, the lowest value
the ETL thickness were 0.2 and 0.05 μm, PCBM and C60 ETL- occurs in the case of CeO2. The highest and lowest values of JSC
based structures had the same maximum PCE of 10.80%. ETL are shown by CeO2 and IGZO, respectively. However, the FF of
ZnO and IGZO-based structures showed a similar trend of the different devices are affected strongly by RS and as a result of
performance with PCEs of about 8.89 and 8.26%, while absorber this, a similar variation is observed in the case of PCE also
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Figure 6. Contour plots showing the change in VOC for CsSnI3-based structures with (a) PCBM, (b) ZnO, (c) C60, (d) IGZO, (e) WS2, and (f) CeO2
ETLs along with the simultaneous variation in ETL and absorber layer thicknesses.

(Figure 10c,d). In comparison with other structures, the ITO/ 3.2.7. Effect of Temperature. PSCs have generated a lot of
CeO2/CsSnI3/CuI/Au PSC structure showed comparatively attention in the PV area, but when exposed to light often, they
subpar VOC, FF, and PCE performance, in spite of demonstrat- still exhibit thermal instability.76 For instance, PSC performance
ing the highest JSC. will degrade by 10% after just 1000 h of operation at 85 °C,
3.2.6. Effect of Shunt Resistance. In Figure 11a−d, we have which is a significantly shorter period than the lifetime of silicon
investigated the effect of the variation in RSH from 10−107 Ω cm2 SCs.77 In addition, the temperature can be used as a treatment
and a constant RS of 0.5 Ω cm2 on the PV parameters for ITO/ for different layers, or PSCs as a whole while being used as the
ETL/CsSnI3/CuI/Au heterostructure. It can be observed that environment temperature for the simulation studies. Con-
the PV parameters VOC, FF, and PCE are dependent on RSH, but sequently, for future commercial use, it is necessary to clarify the
JSC is almost independent of the variation in RSH (Figure 11b).
temperature effect on PSCs considering variable values.
As RSH rises from 10 and 103 Ω cm2, VOC increases sharply from
Figure 12 illustrates the effects of temperature fluctuations
0.12 to 0.93 V, FF from 15 to 76%, and PCE from 0 to 10%
from 275 to 475 K on the performance benchmarks (VOC, JSC,
except for the CeO2 ETL-based structure. After this increment,
beyond an RSH of 104 Ω cm2, the PV parameters were stable. It is FF, and PCE) for the six devices under the illumination of 1000
believed that manufacturing flaws are the principal cause of the Wm−2 of solar light. For all devices, VOC declines with the
origin of RSH. After a certain RSH threshold is reached, the p-n increase in temperature due to the increase in reverse saturation
junction offers a low-resistance channel for junction current current except the CeO2 ETL-based device, which showed an
flow.60 In a previous report, we observed that VOC rose on almost constant and the lowest VOC for the entire temperature
increasing shunt resistance up to 103 Ω cm2, while JSC remained range. However, the JSC of the structures showed an increment
almost unchanged.60 As a result, obtaining the greatest PCE in due to the increase in the temperature except for WS2 ETL,
an ITO/ETL/CsSnI3/CuI/Au PSCs heterostructure requires which delivered a constant JSC of 13.5 mA/cm2. This increase in
an RSH value of 104 Ω cm2. JSC is due to the lowering of band gap with temperature, which
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Figure 7. Contour plots showing the change in JSC for CsSnI3-based structures with (a) PCBM, (b) ZnO, (c) C60, (d) IGZO, (e) WS2, and (f) CeO2
ETLs along with the simultaneous variation in ETL and absorber layer thicknesses.

enhances the electron−hole pair generation.78,79 Equations 8 the supply voltage goes up, the capacitance increases
and 9 relate how VOC relies on temperature: exponentially until it reaches saturation. Among all the studied
devices, the CeO2 ETL-based structure had the maximum
nKT ijj JSC yz
VOC = logjjj + 1zzzz capacitance at 9000 C (nF/cm2), while C60 ETL-based structure
q j JO z showed the minimum capacitance. Except for CeO2, the other
k { (8)
devices show very low values of capacitance. When there is no
Eg bias, the device is in a depletion state, but when a forward bias of
d(VOC) V q around 0.5 V is applied, the depletion width reduces to a value
= OC
dT T T (9) that is almost equal to the thickness of the absorber layer. So, as
JO, T, Eg, q, n, and k stand for the reverse saturation current, the forward bias voltage increases, the capacitance goes up, and
temperature, band gap, electronic charge, ideality factor, and the Mott−Schottky (MS) relationship stays the same.
Boltzmann constant, respectively. Figure 13a−f demonstrates that among all the studied devices,
FF for all the devices tends to increase up to 350 K and C60 ETL-based structure had the maximum MS value of 0.00017
gradually declines thereafter with the increase in temperature. 1/C2, while the CeO2 ETL-based structure showed the
On the contrary, the PCE of all devices decreases except CeO2 minimum MS value. The broadly used MS technique can be
ETL-based devices while the temperature rises. employed to figure out the built-in potential (Vbi), which shows
3.2.8. Effect of Capacitance and Mott-Schottky. Figure the difference between electrode operation and doping level.
13a−f illustrates the effect of capacitance and Mott−Schottky The primary focus of the MS concept is on the properties of the
obtained with the help of C−V analysis with a constant p-n junction, where the intercept point on the x-axis of the C−V
frequency of 1 MHz for six various configurations of CsSnI3- curve usually corresponds to the Vbi of the corresponding
based perovskites SCs with different ETLs. In Figure 13a−f, as junction, whereas the intercept point of the 1/C2−V curve
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Figure 8. Contour plots showing the change in FF for CsSnI3-based structures with (a) PCBM, (b) ZnO, (c) C60, (d) IGZO, (e) WS2, and (f) CeO2
ETLs along with the simultaneous variation in ETL and absorber layer thicknesses.

signifies the concentration of occupied trapping centers. When G(x), and eq 10 uses this photon flux to figure out the value of
the Vbi values go up, the MS values go down for that device. G(x) for each spectral region and position.
Here, the simulated results for all of the important criteria for
G( , x) = ( , x) × Nphot ( , x) (10)
each device were the same, and so they were comparable and in
line with the findings reported in earlier reports.80,81 The Vbi On the other hand, the recombination rate is the opposite of
values reported in Figure 13a−f are obtained with the help of the generation rate, which annihilates the generated electron−
linear fitting in the portion obeying Mott−Schottky behavior hole pairs and they cannot contribute to the photocurrent. The
and getting the intersection of the (1/C2) line with the density and longevity of the charge carriers affect the rate of
horizontal axis. This method is in accordance with the recombination in PSCs. The defect states in the absorber layer as
publications reported in past.82−85 The generation and well as the interfaces cause the enhancement in electron−hole
recombination rate profiles are also depicted in Figure 14a,b. recombination. All of the devices studied had their best
3.2.9. Effect of Generation and Recombination Rate. Figure recombination rates between 0.9 and 1.0 μm, but ITO/C60/
14a,b demonstrates the carrier generation and recombination CsSnI3/CuI/Au ETL had the greatest recombination peak. The
rates for CsSnI3-based six PSCs over a depth of 0.0−1.5 μm, energy levels created in the middle of the valence-conduction
band mostly contribute to the recombination losses. The
where the other input parameters were identical to the initial
recombination rate distribution of PSCs can be uneven due to
one. The results show that of all the studied devices, generation grain boundaries and shortcomings that form when junctions
rates reach their highest point between 0.9 and 1.0 μm, and and structures are made.81
ITO/ZnO/CsSnI3/CuI/Au had the maximum generation rate 3.2.10. J−V and QE Characteristics. For device config-
among all devices. SCAPS-1D uses the arriving photon flux Nphot urations ITO/ETL/CsSnI3/CuI/Au, Figure 15 shows the
(λ, x) to figure out how many electron−hole pairs contribute to current density−voltage (J−V) characteristics and quantum
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Figure 9. Contour plots showing the change in PCE for CsSnI3-based structures with (a) PCBM, (b) ZnO, (c) C60, (d) IGZO, (e) WS2, and (f) CeO2
ETLs along with the simultaneous variation in ETL and absorber layer thicknesses.

efficiency (QE) for six different ETLs. While ITO/CeO2/ amount of passing photons that are absorbed in the absorber,
CsSnI3/CuI/Au produces the highest photocurrent, ITO/ and hence the QE is lower.86
IGZO/CsSnI3/CuI/Au delivers the lowest amount of photo- 3.3. Comparison of SCAPS-1D Results with Previous
current, which is the reason behind the higher amount of current Work. Table 5 shows a comparison of our results with the
density generated by the CeO2 ETL. The flow of photo- current theoretical and experimental research on lead-free
generated in CsSnI3-based PSCs is thus influenced by the ETL CsSnI3-based PSCs with different configurations. Here, we have
band structure, which is identical to previous results.80 Though disclosed the maximum PCE of 10.1%, while previous studies
CeO2 delivers the maximum photocurrent, it shows the lowest like experimental and simulation reached up to 3.83 and 6.40%,
VOC, which results in a reduction in PCE significantly. The lower respectively. Additionally, we performed a thorough simulation
value of VOC is due to the higher electron affinity of CeO2. to identify an efficient ETL, HTL, and its various characteristics.
Figure 15b illustrates the correlation between quantum However, the goal of all of these simulations was to find the
efficiency (QE) and wavelength (λ) in a wavelength range of perfect combinations that would produce the best results.
300−1000 nm. This QE began to peak at a wavelength of 300 Except this, in comparison with all the previous simulation
nm and fell to 950 nm at the band edge of each active substance. results, all the six studied devices’ performance was significant,
Following the trend of J−V characteristics, the QE was which may help to identify more effective configurations for the
determined to be maximum for the ITO/WS2/CsSnI3/CuI/ near future.
Au structure and minimum for the ITO/CeO2/CsSnI3/CuI/Au
configuration. Because of the increased photon absorption in the 4. CONCLUSIONS
CsSnI3 absorber made possible by the lower band gap (∼1.8 eV) The ideal direct band gap, low exciton binding energy, high
of WS2, a higher QE is produced. CeO2 (Eg ≈ 3.5 eV), on the absorption coefficient, and superior carrier mobility are some of
other hand, has a higher band gap (∼3.5 eV), which lowers the the attractive features, which have established CsSnI3 as a
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Figure 10. Effect of change of RS on PV parameters (a) VOC, (b) JSC, (c) FF, and (d) PCE with a constant RSH for different ETLs.

Figure 11. Effect of change of RSH on PV parameters (a) VOC, (b) JSC, (c) FF, and (d) PCE with constant RS for different ETLs.

dominant absorber material for lead-free PV applications. In the analysis. The main highlights of this exhaustive research work
present study, we performed first-principle computations using are summarized below:
the CASTEP program to examine the structural geometry and
electronic and optical properties of the CsSnI3 (Pm3̅ m (1) From the DFT calculations, we found that CsSnI3 exhibits
symmetry). Additionally, 70 different configurations of PSC a band gap of 0.95 eV, isotropic charge distribution in
using the CsSnI3 absorber are numerically tested using SCAPS- every crystalline plane, and multiband character with both
1D simulations in terms of PV performance, out of which six electron-like and hole-like Fermi surfaces. It also
optimized best-performing PSCs are chosen for a detailed possesses a high absorption coefficient, lower reflectivity

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Figure 12. Effect of change of temperature on PV parameters (a) VOC, (b) JSC, (c) FF, and (d) PCE for different ETLs.

Figure 13. (a) Capacitance and Mott−Schottky (1/C2) plot for the CsSnI3-based perovskite solar cell having different ETLs (a) CeO2 (b) C60, (c)
IGZO, (d) PCBM, (e) WS2, and (f) ZnO.

than CsSnCl3, and high conductivity that can be used for the ETL, HTL, and the perovskite CsSnI3. CuI also acts as
potential optoelectronic applications in UV and visible the best HTL out of the investigated HTLs due to its high
range. band gap and superior absorption coefficient.
(2) For the ITO/ETL/CsSnI3/HTL/Au heterostructures, it (3) The effect of the simultaneous variation of the absorber
is found that PSCs with ETLs such as PCBM, C60, and layer and ETL thickness on PV parameters revealed that
WS2 resulted in higher efficiencies in the range of 9−10%, with the rise in the thickness of these layers, the PV
while other ETLs like ZnO, IGZO, TiO2, and CeO2 performance starts to degrade significantly.
exhibited lower efficiencies of ≤8%. The PV performance (4) It is evident from the analysis of different SC structures
is controlled significantly by the band alignment between that ITO/PCBM/CsSnI3/CuI/Au displays the highest

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Figure 14. (a) Generation rate and (b) recombination rate for absorber CsSnI3-based structures with six different ETLs.

Figure 15. (a) J−V curve for six studied structures of ITO/ETL/CsSnI3/CuI/Au; (b) QE curve for the structure of ITO/ETL/CsSnI3/CuI/Au.

Table 5. Comparison of PV Parameters of CsSnI3-Based structures are analyzed for a deep-level understanding of
Solar Cellsb mechanisms guiding the PV performance. This methodical
study can open fruitful pathways for the fabrication of low-cost,
Voc Jsc PCE
type device structure (V) (mA/cm2) FF (%) (%) ref high-efficiency, and lead-free CsSnI3 perovskite-based high-
1 FTO/TiO2/CsSnI3/ 0.34 20.63 54.18 3.83 87
performance SCs for a lead-free natural environment.

2
Au
FTO/TiO2/CsSnI3/
m-MTDATA/Au
ITO/TiO2/MASnI3/
0.24

0.88
22.70

16.80
0.37

0.42
2.02

6.40
24

88
■ ASSOCIATED CONTENT
Data Availability Statement
Spiro-OMeTAD/ The raw/processed data required to reproduce these findings
Au cannot be shared at this time as the data also forms part of an
2 ITO/PCBM/CsSnI3/ 0.52 10.21 62.50 3.31 89 ongoing study.
NiO2/Al
2

2
ITO/PCBM/CsSnI3/
CuI/Au
ITO/ZnO/CsSnI3/
0.91

0.91
14.24

12.01
78.11

72.76
10.10

7.97
a

a
■ AUTHOR INFORMATION
Corresponding Authors
CuI/Au
a M. Khalid Hossain − Institute of Electronics, Atomic Energy
2 ITO/C60/CsSnI3/ 0.91 14.81 69.99 9.43
CuI/Au Research Establishment, Bangladesh Atomic Energy
2 ITO/IGZO/CsSnI3/ 0.87 11.63 73.09 7.35 a Commission, Dhaka 1349, Bangladesh; Department of
CuI/Au Advanced Energy Engineering Science, Interdisciplinary
a
2 ITO/WS2/CsSnI3/ 0.93 13.59 73.08 9.26 Graduate School of Engineering Sciences, Kyushu University,
CuI/Au
a
Fukuoka 816-8580, Japan; orcid.org/0000-0003-4595-
2 ITO/CeO2/CsSnI3/ 0.60 15.86 65.06 6.23
CuI/Au 6367; Email: [email protected], [email protected]
a D. P. Samajdar − Department of ECE, Indian Institute of
This work. b1: Experimental; 2: theoretical.
Information Technology, Design & Manufacturing, Jabalpur
482005 Madhya Pradesh, India; orcid.org/0000-0001-
performance with a PCE of 10.10%, an FF of 78.11%, a JSC 9518-2692; Email: [email protected]
of 14.24 mA/cm2, and a VOC of 0.91 V. M. H. K. Rubel − Department of Materials Science and
The results obtained using the best configurations are further Engineering, University of Rajshahi, Rajshahi 6205,
validated through an extensive analysis of the effect of series and Bangladesh; orcid.org/0000-0001-9420-4335;
shunt resistance and the operating temperature on the PV Email: [email protected]
parameters. Capacitance, Mott−Schottky, generation and Rahul Pandey − VLSI Centre of Excellence, Chitkara University
recombination rates, J−V, and QE characteristics of these Institute of Engineering and Technology, Chitkara University,
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Engineering, Donghua University, Shanghai 201620, China Optimized Design. Micro Nanostruct. 2022, 171, No. 207403.
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Poonch Rawalakot, Rawalakot 12350, Pakistan; Investigation of Efficient (FAPbI3)1−x(CsSnI3)x Perovskite Solar Cell
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R. A.; Nguyen, W. H.; Burkhard, G. F.; Hoke, E. T.; McGehee, M. D.
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The authors declare no competing financial interest. Near-Infrared Photoluminescence from a Single Material. High Hole

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