Solar Energy 269 (2024) 112366

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Structural modification and analysis of novel inverted perovskite

photo-voltaic device by incorporating atomic layer deposition and
surface passivation
Sindhu S. Nair a, b, Preeti Thakur a, Fayu Wan c, Atul Thakur a, c, *
a
Centre for Nanotechnology, Amity University Haryana, Gurugram, Haryana, 122413, India
b
University of Technology and Applied Sciences - Al Mussanah, Muladdah, Mussanah, Sultanate of Oman
c
School of Electronics and Information Engineering, Nanjing University of Information Science & Technology, Nanjing, 210044, China

A R T I C L E I N F O A B S T R A C T

Keywords: Perovskite solar cells are now sporting a higher efficiency in an unprecedented manner within a brief time frame,
Halide double perovskite and hence the researchers focus more on its possibilities in large scale production and thereby commercializa­
Inorganic charge transport material tion. The toxicity of lead, problems with impairment, and the instability of the organic ions in the perovskite light
Atomic layer deposition
absorbers have been recognized as the primary barriers to the development and commercialization of photo­
Surface passivation
Buffer layer materials
voltaic systems using perovskite materials. Studies show that the application of potential inorganic charge
Encapsulation transport materials along with promising halide-based double perovskite absorbing materials like Cs2TiBr6 in the
various layers of tandem solar cells helps to increase charge extraction, transport, and collection and hence
provides long-term operational stability along with better charge mobility. Growing high-quality, conformal,
reproducible thin films of inorganic materials via atomic layer deposition is an effective technique to attain the
benefit of fine, and precise control of material characteristics and layer thickness, including doping, morphology,
and stoichiometry. In this work, we developed, through numerical simulations, a novel inverted non-lead double
perovskite photovoltaic device structure with the integration of all inorganic layer elements by Atomic Layer
Deposition, that has resulted in an efficiency of 16.81 %, and is significantly higher compared to the formerly
published efficiency of power conversion of the same inverted lead-free solar cell without passivation and buffer
layers. With the advantages of lower temperature processing, flexibility, and negligible JV-hysteresis issues, the
novel perovskite photovoltaic device has demonstrated an 81.18 % of fill-factor and 1.56 V of open-circuit
voltage.

1. Introduction into the perovskite material and charges flowing from the perovskite
absorber layer [2–5]. These factors damage all layers of the photovoltaic
The inorganic, organic, and hybrid materials used in perovskite solar cell, causing the perovskite absorber layer material to decompose and
cells (PSCs) have drawn a lot of attention in over a decade because of the stimulates non-stoichiometric defects due to oxygen vacancies and ti­
rapidity with which they are becoming commercially viable. Despite the tanium interstitials [6]. By substituting possible organic or inorganic
fact that the perovskite solar cells have previously demonstrated an metal halide compounds for the liquid electrolyte in all layers of the
outstanding 24.85 % power conversion efficiency, cells have yet to reach solar cell, this inherent instability in solar cell devices has been elimi­
the full potential they have [1]. Compared to other photovoltaic tech­ nated [7].
nologies, perovskite solar cells face additional difficulties, particularly The most promising perovskite materials are those with remarkable
regarding the semi-permanent stableness of the functioning photovol­ energy conversion efficacy, including methyl-ammonium lead halide
taic devices, owing to certain external factors such as impairment from (MAPbBr3) and formamidinium lead halide (FAPbI3). Even so, the
exposure to illumination, temperature raise, air-moisture, and oxygen presence of toxic lead (Pb) in these materials raises concerns about their
from air, etc., as well as internal aspects such as dopants diffusing out potential impact on both human health and the environment. [8,9]. The

* Corresponding author.
E-mail address: [email protected] (A. Thakur).

https://doi.org/10.1016/j.solener.2024.112366
Received 25 November 2023; Received in revised form 18 January 2024; Accepted 19 January 2024
Available online 25 January 2024
0038-092X/© 2024 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
S.S. Nair et al. Solar Energy 269 (2024) 112366

absence of inorganic lead in the halide double perovskite based photo­ Table 1
voltaic devices makes them a feasible substitute for third-generation Comparison table of different band gap values and effective charge mass of
photovoltaic applications. This is primarily because of toxicity con­ potential Cs2TiX6 (X - Cl, I, & Br) materials.
cerns, and their ability to enhance the stability of perovskite compounds Parameter Cs2TiCl6 Cs2TiI6 Cs2TiBr6
by eliminating organic cations, which contribute to instability [10,11]. Direct allowed bandgap, ega (eV) 3.79 1.71 2.84
The family of vacancy-ordered double perovskites with the chemical Direct band gap, egd (eV) 3.68 1.69 2.75
formula A2 B(I) B(III) X6 is a potential alternative, in which the Experimentally reported bandgap, ege (eV) 2.8–––3.4 1.0–––1.2 1.8–––2.3
poisonous Pb ions were replaced at random by a quadrivalent atom and Effective electron mass, me (m0) 3.5 1.8 2.7
Effective hole mass, mh (m0) 2.20 0.55 0.90
an empty lattice-site to ensure electric-charge neutrality [12]. One
References [16,17] [17,18] [14–18]
among the major drawbacks of these valency-ordered double perov­
skites is the indirect and large bandgap of these materials and another
alternative is to use the combination of tetravalent cations instead of finding from different numerical studies that the J-V hysteresis effects
trivalent and monovalent cations in valency ordered double perovskites have been suppressed effectively by using an inverted (PIN) device ar­
(A2B(I)B(III)X6) and form a new valency-ordered double perovskite chitecture and thus the photovoltaic cell can improve its efficiency [22].
structure, A2 BX6 [13]. Fig. 1 shows the general arrangement of the Numerical studies were conducted on a PIN structure of perovskite solar
crystals of A2BX6 (A&B-cation and X-anion) (the valency-ordered double cell using inorganic Cs2TiBr6 and developed a unique, very effective
perovskite structure), and it consists of cubic-crystalline structure with structure containing solely inorganic charge transport elements [15].
ƒm − 3 m space group. The optimized perovskite photovoltaic cell, on a device structure of
Among various valency ordered double perovskites, A2TiX6, an FTO/MoO3/Cs2TiBr6/SnO2/Au and a total thickness of around 700 nm,
abundant bio-compatible material, Titanium, based valency-ordered demonstrates an approximately 15.58 % power conversion efficiency
halide double perovskites have been identified as a desirable material [15,22].
for photovoltaic applications, with better stability under various atmo­ Photovoltaic devices based on perovskites need to be optimized for
spheric conditions like air, light, moisture, and thermal-stress [8]. several factors in order to be commercially successful, including high
Typically, the potential A2TiX6 materials are non-toxic in nature and power conversion efficiency, semi-permanent stability, suitable large-
being solution-processable [13–15]. Ti- cation and X- anion regularize scale surfacing technics, consideration of tandem and semitransparent
the band edge property requirements in the crystal structure and allows applications, nontoxicity and inexpensive materials and production cost.
to tune up energy-gap, effective carrier masses, and absorption profile. Structural modification is necessary for attaining prominent functioning
In most of the efficient A2TiX6, a large monovalent cation like Cs+ is of solar cell device and hence necessity is there to modify the obtained
considered in the place of A- site cation, because of the spectator novel perovskite solar cell structure by incorporating atomic layer
behavior that helps to order the spacing between BX6 octahedra without deposition (ALD) in all charge transport layers, buffer layer and
any direct contribution to the band-edges [14]. Table 1 comprises the encapsulation. ALD is a slow thin film deposition technique and reck­
values of direct-allowed bandgaps (eg-a), direct bandgaps (eg-d), experi­ oned as an extremely promising approach to develop pinhole-free
mental band gaps (eg-e), and effective masses (me & mh), for various conformal thin layers that offer exceptional consistency and precise
potential absorber layer material, Cs2TiX6, (X – metal halides – Cl, I, & yet easy control over layer and properties of the material. In comparison
Br). Table 1 clearly demonstrates the decrease in band gap that is seen as with standard techniques such as CVD (chemical vapor deposition) or
the halogen group moving over Chlorine (Cl) to Bromine (Br) to Iodine PVD (physical vapor deposition), low vacuum and low temperature
(I). The experimentally reported bandgaps of Cs2TiBr6 is the most suit­ deposition techniques have been employed in ALD, which allows for
able one with a tuning possibility ranging from 1.8 eV to 2.3 eV, while exceptional conformality, consistent coating on 3D structures, and high
comparing with their counterparts. precision control over film thickness owing to the selective chemisorp­
Through the steady oxidation state of Ti atoms, Cs2TiBr6 exhibits tion of the precursors [2]. Due to its ability to deposit, ALD has been
remarkable adaptability under continuous sunlight or humid situations. shown to be useful in a variety of applications over wide areas at lower
Additionally, it has been demonstrated through experiments that a temperatures including batteries, microelectronics, and photovoltaic
Cs2TiBr6 cell with an adjustable bandgap of 1.4 eV to 1.8 eV and devices, such as c-Si (crystalline silicon) and CIGS (copper indium gal­
diffusion lengths of valence electron/hole greater than 100 nm might lium diselenide) thin film photovoltaic devices [23–27].
correspond to an enhancement in power conversion efficiency of Proper buffer layer and encapsulation material selection is also
approximately 3.22 percent [14]. The proper selection of transport layer critical to develop a highly efficient perovskite solar cell. The current
materials is also essential to achieve an efficient perovskite solar cell research is focused on developing an inverted, inorganic, eco-friendly
structure. According to previous studies, using inorganic charge trans­ perovskite photovoltaic device using Cs2TiBr6, and the optimization of
port materials in the transport layer has advantages such as low prep­ the solar cell structure, including charge transport materials, buffer
aration costs, increased chemical stability, enhanced thermic stability, layers, electrodes, and encapsulation, is identified utilizing SCAPS 1D -
increased electric-charge carrier-mobility, desirable bandgap, better Solar cell capacitance simulation software. The proposed unique
transparence in the ultra-violet, visible, and infrared, and ease of ma­ perovskite photovoltaic device arrangement is developed using a sys­
terial synthesis through the solution process [15,19–21]. Another major tematic approach to achieve optimized device parameters for improved
functionality, such as the open-circuit voltage (Voc), current density
(Jsc), the fill factor (FF), and the power conversion efficiency (PCE).

2. Numerical analysis and device configuration

2.1. SCAPS 1D simulation parameters

Currently, researchers are being focusing on software-based simu­

lation study for the numerical analysis and optimization of various
photovoltaic device structures using the Poisson equation and the
Continuity equation. The comprehensive numerical simulations and
Fig. 1. General Crystal structure with space group ƒm − 3 m of A2BX6 dou­ device modelling are conducted using the SCAPS 1D, a highly com­
ble perovskite. mended and general-purpose tool, with AM1.5G luminescence [29].

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S.S. Nair et al. Solar Energy 269 (2024) 112366

Various equations involved in the process of structural simulation and friendly planar inverted hetero-junction perovskite solar cell structure
the output performance-based optimization of different solar cell pa­ has modelled and developed with the photovoltaic cell structure con­
rameters are Poisson equation (2.1.1), Transport equation (2.1.2), sisting of FTO(Glass)/HTL/Perovskite-Absorber/ETL/Metal Contact
Continuity equation (2.1.3), Diffusion length (2.1.4), Diffusivity (2.1.5), [8,15,22]. Changes to the interface defect-density, width, and defect-
Open circuit voltage (2.1.6), and Carrier lifetime (2.1.7). density of different layer materials have been made in order to eval­
uate the functioning of the unique solar cell device. Necessary optimi­
∂2 ϕ ∂E q[ ]
zation techniques have been adopted throughout the modelling process
= − = − p − n + ND (x) − NA (x) ± Ndef (x) (2.1.1)
∂2 x ∂x εs for developing an environment friendly solar cell device and obtained an
optimized efficiency of 15.6 % with a short-circuit current of 16.589
In the above Poisson equation, ϕ represents electro-static potential of
mA/cm2, an open circuit voltage of 1.1 V, and a fill factor of 85.76 %
solar cell, E – electric field, p and q – elementary charge, ε – permittivity
[15]. The optimized device contains MnO3 in the hole transport layer,
of the material, NA and ND - doping density of acceptor and donor, n –
SnO2 in the electron transport layer, and Cs2TiBr6 as the absorbent
free charge density, and Ndef – defect density.
material, and all these layer materials are inorganic materials. In addi­
∂n ∂p tion to better visibility across the infra-red region, ultra-violet region,
Jn, p = nqμn E + qDn + pqμp E + qDp (2.1.2)
∂x ∂x and visible spectra, and solution processing accessibility, these inorganic
materials, with inexpensive preparation costs, excellent chemical and
The transport equation describes the charge transport model of the semi- heat stability, increased mobility of the charge carriers, and large band
conductor in which total current–density, Jn,p, is represented as the sum gaps, have potential advantages. Table 2 represents various input pa­
of diffusion current density and electron – hole drift. The charge diffu­ rameters used for the numerical simulation of Cs2TiBr6 based solar cell
sion coefficient is represented as Dn for electrons and Dp for holes, and structure.
the charge mobility is represented as µn for electrons and µp for holes. The inorganic materials used in the charge transport layer of a
∂n,p 1 ∂Jn 1 ∂Jp ( ) photovoltaic device offer feasible characters like prominent hole
= + (Gn − Rn ) + + G p − Rp (2.1.3) mobility and low cost, however, the solvent employed during the
∂t q ∂x q ∂x
layering damages the absorber material and brings down the constancy
The Continuity equation represents the continuity model of the device in of the entire photovoltaic device. The issue brought on by the solution
terms of concentration gradient of charge carriers, ∂n,p/∂t, current process can be resolved via atomic layer deposition, an approach for
density of electron and hole, Jn and Jp, generation and recombination of producing incredibly thin and homogeneous films. Structural variations
electron and hole, Gn/Gp and Rn/Rp. in solar cells can result in more robust thermal resistance, increased
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ mass production potential, greater light absorption, faster carrier
Ln,p = Dn,p τn,P (2.1.4) transport, fewer recombination losses, and improved conversion effi­
ciency [31]. Hence this work focuses on the structural modification of
Where Ln,p represents diffusion length, and τn,p represents lifetime of
solar cell to achieve a more stable, efficient solar cell device by intro­
electron and hole. The diffusivity of electron and hole is given in
ducing charge transport materials grown by atomic layer deposition and
equation (2.1.5), where (KB T)/q indicates the thermal voltage.
adding thin layers of passivation material of 5 nm thickness upon the
[( ) ]
KB T perovskite absorber material, and a 5 nm thick buffer layer upon the top
Dn,p = μn,p (2.1.5) of the electron transport layer.
q
Finally, the layers in the solar cell structure must overlaid using
The open circuit voltage is calculated using the following equation proper encapsulation, in order provide insulation from external envi­
(2.1.6), where IL and IO indicate the current generated by light and ronmental factors. Fig. 2(a) represents the modified form of the photo-
saturation current. voltaic cell structure, and the Fig. 2(b) represents the energy level dia­
[ ( )] gram. Numerical simulation conducted on the modified structure to
nkB T IL
VOC = ln +1 (2.1.6) analyze the opto-electronic performance of the novel device.
q IO

1 3. Results and discussions

τ= (2.1.7)
σ Nt Vth
The simulation results need to be verified with existing experimental
( )
B √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ results for substantiation before starting with performance analysis of
α(λ) = A + hv − Eg (2.1.8) solar cell. On a standard planar n-i-p photovoltaic device structure,
hv
FTO/TiO2/Cs2TiBr6/P3HT/Au, a SCAPS-1D-based numerical analysis
The carrier lifetime, τ, is represented in equation (2.1.7), in terms of σ – has been conducted by applying necessary simulation parameters, and
capture cross section, Nt – defect density and Vth – the thermal velocity
of charges. Finally, the optical absorption coefficient α(λ) is calculated Table 2
using equation (2.1.8), which demonstrates the relationship between Introductory input parameters for various layer materials of the PSC structure
α(λ), energy gap, Eg, of the perovskite absorber layer, planks constant, h, [22].
and the photon frequency, ν [28–30]. The effectual mass used for holes I/P parameters SnO2 Cs2TiBr6 MnO3
and electrons are 0.9 me and 1.79 me respectively. Also, carrier-lifetime
Thickness, d (nm) 30 100–500 10
value of both the charges is 24 ns, and a diffusion lengths of 103 nm for Bandgap, Eg (eV) 3.5 1.8 3.0
holes and 121 nm for electrons are utilized in the simulation [22]. The Electron affinity, χ (eV) 4 4 2.5
standardized test parameters of one sun photo illumination, 1000 W/m2 Permittivity, εr 9 10 12.5
irradiance, 1.5G air mass, and an ambient temperature of 300 K are used Effective density states, Nc (1/cm3) 2.2 x 1017 6.0 x 1019 2.2 x 1018
Effective density states, Nv (1/cm3) 2.2 x 1016 2.14 x 1019 1.8 x 1019
for all relevant simulations. Doping density, ND (1/cm3) 1.0 x 1018 3.0 x 1019 0
Doping density, NA (1/cm3) 0 3.0 x 1018 1.0 x 1018
Charge-mobility of electrons, µn(cm2/ 20 0.236 25
2.2. Structural modification of photo-voltaic device Vs)
Charge-mobility of holes, µp(cm2 / Vs) 10 0.171 100
Defect density, Nt(1/cm3) 1.0 × 1015 4.17 × 1015 1.0 × 1015
Employing a SCAPS-1D simulator based numerical study, an eco-

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Fig. 2. (a) Solar cell device with modified structure (b) Energy states of photovoltaic device.

the results are equated with the existing experimental results for vali­
dation. The JV characteristics and the output parameters of the analyzed
structure is represented in Fig. 3, and which depicts the proximity be­
tween reported experimental results [32] and the simulation results.
Performance analysis have conducted for developing an eco-friendly
inverted planar photovoltaic cell structure without surface passivation,
buffer, and encapsulation layers. The optimized device architecture is
shown in Fig. 4 along with various output parameters and JV curve. This
unique structure, FTO/MnO3/Cs2TiBr6/SnO2/Au, has an approximate
width of roughly 700 nm and could be able to generate current densities
of 16.589 mA/cm2, with 15.68 % conversion efficiency for an open-
circuit voltage, Voc, of 1.11 V and 85.76 % fill factor.

3.1. Modified device structure

Structural modifications in solar cells aim to create an environment

that minimizes recombination, maximizes charge carrier mobility, op­
timizes charge separation, and reduces resistive losses, all of which
contribute to faster and more efficient carrier transport within the de­
vice. Hence, structural modification done on the device structure by
Fig. 4. O/P parameters and JV Characteristic curve of inverted all inorganic
environment friendly Cs2TiBr6 based photovoltaic cell without ALD layers.

applying surface passivation layer upon the absorber layer and a thin
layer upon the SnO2 material as a buffer layer. All the charge transport
materials are replaced with charge transport materials grown by atomic
layer deposition instead of conventional methods like spin coating,
chemical-bath deposition, spray pyrolysis, electro-deposition, and vac­
uum evaporation. Charge transport layer, passivation layer and buffer
layer grown by atomic layer deposition and developed a new structure
that has the potential to improve the overall efficiency and the con­
stancy of the photovoltaic device. The designed novel device can pro­
vide good controllability, excellent stoichiometry, better step coverage,
low growth temperature, precise thickness control, and low impurity
concentration.
In the hole transport layer, MnO3, grown by atomic layer deposition,
is required to possess a shorter valence band at its maximum for the
valence band maximum of the absorber, which helps to extract holes by
blocking electrons. Similarly, SnO2 grown by atomic layer deposition is
required in the electron transport layer to maintain a conduction band
minimum aligned with that of the absorber layer, which helps to block
Fig. 3. O/P parameters and JV Characteristic curve comparison between holes and transport electrons effectively. This conduction band modifi­
experimental data and simulation results of Cs2TiBr6 based solar cell. cation using atomic layer deposition can act as a high performance

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planar inverted solar cell device with high voltage and long-term sta­ 3.3. JV characteristic curves of the simulated structures
bility. The modified form of perovskite solar cell device consists of the
novel structure Glass/FTO/MnO3/Cs2TiX6/Passivation/SnO2/Buffer/ Perovskite-absorber layer consists of a non-toxic double perovskite
Au, and further optimizations have done on this novel structure to material, Cs2TiBr6, which was showing suitable fill factor of 81.16 % for
achieve high performance with much more stability. an open-circuit voltage of 1.56 V, current–density, Jsc, of 13.29 mA/
cm2, and a power conversion efficiency of 16.81 % while comparing
3.2. Surface passivation, buffer layer and encapsulation with its counter parts, Cs2TiI6, Cs2TiF6 and Cs2TiCl6. Fig. 5 represents
the analysis plot of JV characteristics of solar cells using four types of
Passivation layer, also known as a barrier layer, is an extremely thin halide based double perovskite, Cs2TiX6 [Halides (X) – Cl, I, F and Br],
layer that deposited upon the surface of the absorber layer, and research materials. Various output performance parameters of the tested devices
has shown that it is amazingly effective in enhancing both the stability are described in Table 3 and it reveals that Cs2TiBr6 is the most suitable
and performance of solar cell devices by enhancing the fill factor and material for the absorber layer. The proposed solar cell device will be a
open circuit voltage [33]. In comparison with promising passivation potentially green technology because Cs2TiBr6 is an environmentally
materials, Al2O3 and ZrO2, ZnO is identified as one of the more attractive friendly, thermally resistant, and biodegradable material.
passivation layer materials because of its natural passivation properties,
wide bandgap, high crystallinity, matching energy levels, excellent
3.4. Impact of absorber layer thickness
surface topography, and better electron mobility [34]. The thickness of
ZnO passivation is preferably 5 nm and which can produce a strong
For a viable structure of solar cell devices, it is crucial to optimize the
chemical match with the perovskite layer. A 5 nm thick Zn:SnO2 layer
overall thickness of the photovoltaic device. The thickness of each layer
above the electron transport layer is considered as one potential buffer
has been analyzed and the simulation studies have done on the opti­
layer material for inverted planar photovoltaic cells. This atomic layer
mized device structure FTO/MnO3/Cs2TiBr6/ZnO/SnO2/Zn:SnO2/Au.
deposition aids to bring down the recombination losses and improves
The optimized structure underwent the appropriate investigation after
the electron transport through the interface, which leads to enhance the
the hole transport layer and electron transport layer thicknesses were
solar cell performance. Most perovskite solar cell devices need encap­
adjusted from 5 nm to 50 nm. The optimized layer thickness of charge
sulation to shield the layers from external environmental elements like
transport layer is 10 nm for hole transport layer and 30 nm for electron
heat, phase transition, oxygen, light and moisture [2,35,36]. The
multilayer atomic layer deposition process is shown to be more effective
Table 3
and suited for stable solar cell devices among several potential encap­
Photovoltaic performance while using different perovskite absorber materials
sulation techniques, such as glass-glass encapsulation, thin film encap­
(PAM).
sulation, and polymer encapsulation [35]. Hence, a bilayer of PET,
polyethylene terephthalate, coated with an inorganic aluminum oxide, Parameters Cs2TiF6 Cs2TiI6 Cs2TiCl6 Cs2TiBr6
PAM
Al2O3, of around 50 nm thick can be used for the external encapsulation
in the novel solar cell device. Voc (V) 1.6 1.55 1.17 1.56
Jsc (mA/cm2) 11.92 14.06 24.85 13.29
FF (%) 82.11 80.84 68.99 81.16
PCE (%) 15.79 17.62 20.15 16.81

Fig. 5. Comparison chart of JV Characteristic curve of novel structure using different absorber layer materials.

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transport layer. The absorber layer plays a vital role in the photovoltaic 3.5. Quantum efficiency of the simulated structure
performance of the entire device, and hence detailed analysis is con­
ducted on the thickness of absorber layer by varying the layer thickness The photosensitivity of a solar cell is represented by quantum effi­
from 100 nm to 500 nm. ciency, and which indicates the amount of incident photons converted to
Fig. 6 represents the JV curves of novel perovskite solar cell structure electrons [30,38]. The absorption of perovskite absorber and the band-
for various absorber layer thickness from 100 nm to 500 nm. Charge gap of the front material have a substantial impact on quantum effi­
carriers are created when photons hit the perovskite absorber. An in­ ciency. Materials with a wider band gap may also have higher quantum
crease in the thickness of the absorber material increases the chance of efficiency [36,37]. This is true because materials with broader bandgaps
absorbing photons with longer wavelengths. This increases the quantity have high optical spectrum transmittivity and low optical spectrum
of charge carriers generated, which improves the efficiency of the solar absorption, and as a result, the absorber, where the charge carriers are
cell. The efficiency of the device is found to be increasing and decreases created, receives the maximum amount of light. From Fig. 8 it can be
the fill factor while increasing the layer thickness. The behavior of observed that the perovskite solar cell structure with passivation layer
current density with respect to open-circuit voltage is represented in and buffer layer is having higher quantum efficiency than the cell
Fig. 6. Structural modification done on the novel device by adding 5 nm structure without passivation and buffer layer.
thick passivation layer above the perovskite layer and a 5 nm buffer
layer above the electron transport layer by maintaining a total thickness 3.6. Effect of working temperature
below 1000 nm. The rightest performance obtained for the device is at
300 nm thickness, and the output parameters corresponds to absorber The output performance of the perovskite solar cells is significantly
layer thickness is mentioned in Fig. 7, and this 300 nm thickness is us­ influenced by the working temperature, and most of the devices function
able to achieve the objective to maintain the total device thickness of better at elevated temperatures and are quite stable at room temperature
1000 nm as well as to provide better power conversion efficiency of of 300 K. To examine how temperature affects device performance and
16.81 % by maintaining a suitable fill factor above 81 %. stability at higher temperatures, the operating temperature is altered
between 280 K and 440 K with 20 K intervals. Fig. 8 represents the

Fig. 6. Effect of thickness of the Cs2TiBr6 material.

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Fig. 7. Performance parameters of novel structure for various perovskite absorber layer thickness.

Fig. 8. Comparison of quantum efficiency.

impact of operating temperature on various output parameters of the maintained while open circuit voltage considerably decreases, and it is
optimized perovskite photovoltaic device. As the temperature rises, the represented in Fig. 9(c) and (d).
fill factor decreases, and furthermore, device efficiency decreases, as The optimized inverted all inorganic eco-friendly halide double
shown in the results of Fig. 9(a) and (b), which is mainly due to the perovskite photovoltaic device with structural modification consists of
dependency of the reverse saturation current on temperature. The band FTO/MnO3/Cs2TiBr6/ZnO/SnO2/Zn:SnO2/Au along with suitable
gap becomes unstable as temperature rises due to the high rate of ion encapsulation. The overall performance of this novel solar cell device is
recombination. Due to the absorber flaws, current density remains compared with output parameters of different device structures and

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Fig. 9. Impact of working temperature on optimized device parameters (a) Efficiency (b) Fill factor (c) Current density and (d) Open circuit voltage.

presented in Table 4. This innovative device outperforms earlier work on circuit voltage of 1.56 V, which is closer to similar lead based solar cell
reference [15] and has an overall thickness of about 900 nm. The devices.
modified device consists of lead free inorganic double perovskite solar
cell device and can produce power conversion efficiency of 16.81 % and 4. Conclusion
current density of 13.29 mA/cm2 for a fill factor of 81.6 % and open
Structural modification of perovskite solar device is the key route
Table 4 towards the commercialization, hence in this numerical analysis,
Performance evaluation of similar perovskite solar cell devices. SCAPS-1D is utilized to study the impact of structural modification and
atomic layer deposition on an efficient inverted perovskite solar cell
Optimized structure of Voc Jsc FF PCE References
photovoltaic device (V) (mA/ (%) (%) device. Structural modification done on the device, FTO/MnO3/
cm2) Cs2TiBr6/SnO2/Au, by adding 5 nm thick passivation layer above the
ITO/PEDOT: PSS/ FASnI3/ 0.47 22.45 67.8 7.09 [39]
perovskite layer and a 5 nm buffer layer above the electron transport
SnF2-TMA/ Ag layer by maintaining a total thickness below 1000 nm. The spectral
ITO/PEDOT:PSS/MAPbI3/ 1.02 20.7 76.4 16.2 [40] properties of each layer have a significant impact on the light-absorption
ZnO/AgNW/ALD Al2O3 capacity, photocurrent production, and overall device efficiency of the
coated PET
photovoltaic device. The modified structure consists of an additional
ITO/Poly-TPD/PFN/ 1.15 19.7 81.8 18.6 [41]
Cs0.25FA0.75Pb encapsulation layer to provide overall protection from pervasion of
(I0.80Br0.20)3 /LiF/C60/ water evaporation, thermal stress, oxygen, and heat. Studies revealed
PEIE/SnO2/Zn:SnO2/Au that the modified solar cell device, FTO/MnO3/Cs2TiBr6/ZnO/SnO2/Zn:
ITO/PTAA/ 1.12 20.8 79.3 18.5 [42] SnO2/Au, produces a better photovoltaic characteristics and it is
Cs0.25FA0.75MA0.15Pb
(I0.85Br0.15)3 /C60/BCP/
pictured in Fig. 10. According to the findings, structural changes to
SnOx/Zn:SnOx/IZO perovskite solar cells enhance their crystallinity, stability, and perfor­
FTO/MnO3/Cs2TiBr6/ 1.10 16.59 85.76 15.68 [15] mance, opening the door for their use in environmentally friendly solar
SnO2/ Au cell devices and boosting their long-term performance.
FTO/MnO3/Cs2TiBr6/ZnO/ 1.56 13.29 81.16 16.81 This Work
SnO2/Zn:SnO2/Au

8
S.S. Nair et al. Solar Energy 269 (2024) 112366

Fig. 10. Comparison of JV characteristics of novel structure with and without ALD.

Declaration of competing interest [9] A. Zakutayev, et al., Emerging inorganic solar cell efficiency tables (version 2),
Jphys Energy 3 (2021), https://doi.org/10.1088/2515-7655/abebca.
[10] M.A. Green, A. Ho-Baillie, H.J. Snaith, The emergence of perovskite solar cells, Nat.
The authors declare that they have no known competing financial Photonics 8 (2014) 506–514, https://doi.org/10.1038/NPHOTON.2014.134.
interests or personal relationships that could have appeared to influence [11] J.L. Mendes, et al., Interfacial states, energetics, and atmospheric stability of large-
the work reported in this paper. grain antifluorite Cs2TiBr 6, J. Phys. Chem. C 124 (2020) 24289–24297, https://
doi.org/10.1021/acs.jpcc.0c08719.
[12] C. Kupfer, J. Elia, M. Kato, A. Osvet, C.J. Brabec, Mechanochemical Synthesis of
Acknowledgments Cesium Titanium Halide Perovskites Cs2TiBr 6-xIx (x = 0, 2, 4, 6), Cryst. Res.
Technol. 58 (2023) 2–7, https://doi.org/10.1002/crat.202200150.
[13] S.R. Kavanagh, et al., Frenkel Excitons in Vacancy-Ordered Titanium Halide
This research work was supported in part by the National Key Perovskites (Cs2TiX6), J. Phys. Chem. Lett. 13 (2022) 10965–10975, https://doi.
Research and Development Program of China under Grant org/10.1021/acs.jpclett.2c02436.
2022YFE0122700. The author(s) would like to acknowledge the support [14] M. Chen, et al., Cesium Titanium (IV) Bromide Thin Films Based Stable Lead-free
Perovskite Solar Cells, Joule 2 (2018) 558–570, https://doi.org/10.1016/j.
provided under the DST-FIST Grant No. SR/FST/PS-I/2018/48 of Govt. joule.2018.01.009.
of India. PT is thankful to DST-SERB TARE fellowship vide Sanction [15] Sindhu S. Nair, Preeti Thakur, Fayu Wan, A.V. Trukhanov, L.V. Panina, Atul
Order No TAR/2022/000414. Thakur, Performance evaluation and the optimization of an inverted photo-voltaic
cell with lead-free double perovskite material and inorganic transport layer
materials, Solar Energy, Volume 262, 2023, 111823, ISSN 0038-092X, doi.org/
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