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Design and optimization of non-toxic and highly efficient tin-based organic

perovskite solar cells by device simulation

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DOI: 10.1016/j.heliyon.2023.e19389

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Heliyon
journal homepage: www.cell.com/heliyon

Design and optimization of non-toxic and highly efficient

tin-based organic perovskite solar cells by device simulation
Manisha Ahamad, A.K.M. Akther Hossain *
Department of Physics, Bangladesh University of Engineering and Technology, Dhaka, 1000, Bangladesh

A B S T R A C T

An organic, lead-free, n-i-p planar perovskite solar cell (PSC) based on CH3NH3SnI3 was demonstrated in this work using a solar cell capacitance
simulator (SCAPS). A material cell design of FTO/ZnO/CH3NH3SnI3/Cu2O/Au has been investigated for this study. A detailed analysis has been
performed on the role of thickness, electron affinity, doping concentration of the perovskite layer, ETL, HTL, defect density of perovskite layer and
temperature on PSC performance. For optimum conditions, the energy conversion efficiency is around 26.55%, accompanied by fill factor =
85.58%, open circuit voltage = 1.03 V, short circuit current density = 30.14 mA/cm2, and quantum efficiency of 80%–90%. This model shows the
prospect of CH3NH3SnI3 as a perovskite material to produce toxic-free environment-friendly solar cells with high efficiency.

1. Introduction

The demand for electricity for power commodities is increasing rapidly day by day. Hence there may be an energy crisis in the near
future unless renewable energy sources are vastly used [1]. To tackle the impact of global warming on the environment different types
of renewable energy sources are widely discussed [2]. The most eco-friendly, considerably cost-efficient, and abundantly available
clean energy source is photovoltaic technology which transforms solar energy directly to electrical power [3]. However, solar energy
requires a suitable location to produce energy. The best locations on Earth which have vast exposure to solar radiation over the whole
year are close to the equator [4]. Therefore, most parts of Asia, including Bangladesh, can be benefited from perovskite solar panels.
The perovskite materials have the general formula of ABX3, where A is organic and B is inorganic cation with different electro­
negativity, and X is halogen anion [5]. The general layered structure for perovskite solar cell (PSC) consists of a transparent conductive
oxides such as fluorine-doped tin oxide (FTO), acts as a conductive layer on top of the glass that allows light to pass through to the
active perovskite layer. It is then covered by the electron transport layer (ETL), which is then followed by the perovskite layer. From
the perovskite layer, the ETL aids in the transfer of electrons to the metallic electrode, while the hole transport layer (HTL) helps to
transport holes in the reverse direction. The perovskite layer is the fundamental element of the cell which is in charge of producing
electron-hole pairs and absorbing light. Electrons that are produced in that layer are collected by the metallic electrode (e.g. Au) and
complete the circuit, allowing the flow of current and the generation of electricity. Kojima et al. published the first study on PSC, with a
power conversion efficiency (PCE) of 3.8% [6]. As of 2021, up to 26.3% efficiency is possible using lead-based (Pb) PSC. The efficiency
of Pd based PSC has rapidly increased since then [7,8]. Despite high efficiency, one of the major drawbacks of their industrial
application is their high toxicity [9]. Researchers around the globe are looking for other suitable materials such as MASnI3: 1.3 eV,
RbGeI3: 1.3eV, CsSnI3: 1.22 eV, FASnI3: 1.41 eV, Cs2TiBr6: 1.8eV, RbGeI3: 1.3eV which also possess wide band gap like Pb− based
perovskite [10–14]. Recently, tin-based halide perovskites have gained much attention though they degrade easily when exposed in air
[15]. Singh et al. performed a simulation of a Sn-Ge-based PSC device which yields outstanding electrical performance parameters

* Corresponding author.
E-mail address: akmhossain@phy.buet.ac.bd (A.K.M.A. Hossain).

https://doi.org/10.1016/j.heliyon.2023.e19389
Received 11 March 2023; Received in revised form 6 August 2023; Accepted 21 August 2023
Available online 25 August 2023
2405-8440/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
M. Ahamad and A.K.M.A. Hossain Heliyon 9 (2023) e19389

such as short circuit current (JSC) = 27.18 mA/cm2, open circuit voltage (VOC) = 1.116 V, and fill factor (FF) = 86.40% and PCE =
26.22% [16]. Neol et al. have demonstrated Pb-free MASnI3 based devices which yields efficiency of more than 6%. To avoid air
exposure they fabricate the device in closed nitrogen filled box through a spin coating process [17]. Using CH3NH3SnI3 as a perovskite
absorber layer, Valeti et al. investigated the electrical properties of PSC, and obtained PCE of 29.74% where TiO2 is used as an ETL and
CuSbS2 is used as an HTL [18]. When TiO2 is used as ETL,Cu2O as HTL with CH3NH3SnI3 as an absorber layer, a PCE of 18.27% is
reported by Jha. et al. [19]. Qasim et al. suggested a solar cell where they obtained 21% PCE in the temperature range of 270–280 K
[10]. In FASnI3-based solar cells, Abdelaziz et al. has demonstrated PCE of 14%. They showed that more stable and better device
performance can be achieved by reducing doping concentration level [12]. Although Sn-based perovskites face several drawbacks,
such as lesser stability and lower PCE compared to some Pb-based perovskites, researchers are working to improve their performance
and overcome these limitations, making them potential candidates for future solar cell technologies. Simulation is always a good idea
before fabricating any solar cell to determine the optimum device performance. Optimized simulation outcomes will cut down the
production costs and speed up the process of finding the possible outcomes.
In this study, CH3NH3SnI3 is taken into consideration as an absorber layer because it has a direct bandgap that is ideal for efficient
charge carrier generation, excellent optoelectronic properties and high absorption coefficient. It also has lower toxicity and abundance
in nature than other perovskite materials. Although TiO2 is a very effective ETL layer in PSCs and is frequently utilized, processing of
TiO2 needs extremely high temperatures, which will increase the expense of solar cell. However, the high cost and low electron
mobility of TiO2 make it unsuitable for widespread use in commercial solar cells. TiO2 can also be affected by defects and charge
recombination, which can reduce device efficiency. For increasing the efficiency of PSCs, finding new ETL materials with the smallest
possible defect at interfaces are necessary. In recent years, attention has grown in ZnO, another intriguing ETL material because of its
high electron mobility, excellent transparency, and suitability for low-temperature fabrication. Here, ZnO is used as an ETL in our
structure. ZnO may also be manufactured in various nanostructured forms to boost its performance in perovskite solar cells.
Researchers have discovered that the frequently used Spiro-OMeTAD as HTL, triggers and accelerates the breakdown of PSCs,
therefore shortening their lifespan. Along with increasing the cost, Spiro-OMeTAD compromises the reliability of solar cell. In this
study, Cu2O is used as the HTL in PSCs due to its distinct benefits of low cost and high hole mobility, strong stability, low-temperature
manufacturing, customizable energy levels, excellent band alignment with absorber layer, prolonged lifetime for photo-generated
charge carriers, abundance, and capacity for scalable processing.
Here, the impact of several factors including thickness, doping concentration, defect density and electron affinity of ETL and HTL
and perovskite layer have been investigated. The impact of temperature on PSC has also been explored. Here, a novel (FTO/ZnO/
CH3NH3SnI3/Cu2O/Au) solar cell structure has been considered for study. For the simulation purpose, input electrical parameters have
been computed from research using the density functional theory and confirmed using a variety of literature sources [20]. The
electrical parameters of single junction tin-based solar cell have been carried out by Solar Cell Capacitance Simulator− one dimensional
(SCAPS− 1D) is used under AM 1.5G illumination. To thoroughly optimize every possible parameter of the device for increasing PCE
and reducing manufacturing costs is the primary goal of this study. The electrical performance characteristics of simulated tin-based
PSC devices are compared in Table 1. This comparison reveals that using Cu2O as the HTL material and ZnO as the ETL material
improves the performance of the PSC device. The PCE of the proposed work also demonstrates better result than those of earlier
designs.

2. Device structure and simulation parameters

There are several types of numerical simulation tools such as AMPS, ATLAS, SETFOS, SCAPS, SILVACO and COMSOL to study the
performance of solar cell [21]. In this research work, the solar structure has been optimized using the SCAPS-1D, version 3.3.10 under
AM1.5G illumination which is invented by Burgelman et al. [22]. Simulation can be done under both illuminated and dark envi­
ronment at various temperature. The absorber layer creates electron and hole pairs when exposed to light, which results a voltage
across the PSC. The SCAPS-1D software is used to assess parameters including PCE, FF, VOC, JSC, quantum efficiency (QE), and J-V
characteristics. This software operates by utilizing two equations: continuity and Poisson equations at specified boundary conditions
[23]. The construction of the simulated solar cell is FTO/ZnO/MASnI3/Cu2O/Au, as illustrates in Fig. 1(a). Front contact layer is made
of FTO which is exposed to the sunlight, ZnO has been taken as ETL, Cu2O as HTL and CH3NH3SnI3 as the key light absorbing layer and
Au as the back metal electrode. The lowest energy level of conduction band (EC), electron fermi energy level (Fn), hole fermi energy
level (Fp) and highest energy level of valence band (EV) is shown in Fig. 1(b). Table 2, lists an overview of the input parameters of all
layers which are obtained from the various research paper and their references [10,24–26]. The following are the initial calculated
parameters: VOC = 0.88 V, JSC = 31.06 mA/cm2, FF = 81.23%, PCE = 22.16%. Fig. 2, depicts the J-V characteristic of ideal

Table 1
Comparison of Electrical performance properties of tin-based PSC devices.
PSC configuration VOC(V) JSC(mA/cm2) FF(%) PCE(%) Reference

ITO/ZnO/CdTe/CH3NH3SnI3/CuSCN/Au 0.8149 34.0535 76.57 21.24 [10]

FTO/PCBM/CH3NH3SnI3/CuI/Au 1.0557 34.26863 69.23 25.05 [25]
TCO/ETM/CH3NH3SnI3/HTM/Metal back contact 1.00 28.11 87.69 24.81 [33]
TCO/TiO2/CH3NH3SnI3/Cu2O 0.7397 32.47 76.06 18.27 [19]
FTO/ZnO/CH3NH3SnI3/Cu2O/Au 1.03 30.14 85.58 26.55 Present work

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M. Ahamad and A.K.M.A. Hossain Heliyon 9 (2023) e19389

Fig. 1. Proposed MASnI3 based solar cell: (a) device architecture; (b) Energy band diagram.

CH3NH3SnI3 devices. The quantum efficiency curves of proposed CH3NH3SnI3 devices is shown in Fig. 3.
In order to get optimized result, different device parameters have been varied using the simulator. Both electrons and holes have
thermal velocities that are adjusted to 107 cm/s [27]. Firstly, the thickness of MASnI3 perovskite, ZnO and Cu2O layer are selected as
0.4, 0.05 and 0.2 μm, respectively. The thickness of a particular layer is optimized keeping the fixed thickness of other two layers. The
other layers thicknesses were also varied in a similar way. Thereafter, to acquire the highest possible PCE, the performance for the
different values of parameter on cell is inspected and optimization is carried out for each parameter.

3. Results and discussion

3.1. Effect of thickness

The thickness of the absorber layer has a considerable role on the performance of solar cell devices; hence, the variation of thickness

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Table 2
Parameter settings for the simulation of the MASnI3 solar cell.
Parameters FTO ZnO MASnI3 Cu2O

Thickness (nm) 500 50 400 200

The band gap (eV) 3.5 3.3 1.30 2.17
e− affinity (eV) 4.0 4.0 4.17 3.2
Permittivity 9.0 9.0 6.5 7.5
Effective density of states at CB (cm− 3) 2.2 × 1018 2 × 1018 1 × 1018 2 × 1018
Effective density of states at VB (cm− 3) 1.8 × 1019 1.8 × 1019 1 × 1019 1.8 × 1018
Mobility of e− (cm2. V− 1s− 1) 20 100 1.6 20
Mobility of h+ (cm2. V− 1s− 1) 10 25 1.6 80
The density of n-type doping (cm− 3) 2 × 1019 1 × 1018 0 0
The density of p-type doping (cm− 3) 0 0 2 × 1015 2 × 1019
The density of defects (cm− 3) 1 × 1015 1 × 1015 2 × 1015 1 × 1014

Fig. 2. Simulated J-V characteristic of ideal MASnI3 perovskite devices.

Fig. 3. Simulated quantum efficiency curves of MASnI3 devices.

has been studied thoroughly. The performance of the device is demonstrated in Fig. 4(a), as a function of the layer thickness of MASnI3
perovskite, which has been adjusted from 100 to 1500 nm. It is observed that, PCE and JSC rise quickly as absorber layer thickness
increases up to 700 nm, attaining maximum value of 23.15% and 34.31 mA/cm2, respectively. Beyond this thickness, these parameters
drop gradually. The possible reason for the increase might be as the thickness increases, more photons of higher wavelength getting
absorbed, which helps in generating an excess number of carriers, leading to an improvement in efficiency. However, when the
thickness continues to increase above 700 nm, the PCE declines due to the rise in recombination and reduction of the lifetime of the

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Fig. 4. Effect of absorber thickness variations on (a) solar cell characteristic parameters; (b) recombination rate.

charge carrier in perovskite layer [28]. The VOC and FF also decrease due to increase in recombination processes for higher thickness of
absorber layer [29]. Fig. 4(b), illustrates that increasing thickness leads to higher rate of recombination inside the perovskite material.
More than 700 nm of absorber thickness, VOC does not change significantly. Therefore, the optimum device PCE for 700 nm absorber
layer is 23.15%.
The device performance is also impacted by changing the HTL (Cu2O) thickness, which has been altered from 20 to 300 nm. The
impact of variations of HTL thickness on solar cell is illustrated in Fig. 5 which reveals that the VOC, JSC and PCE are sharply increased
and FF is negligibly reduced in the specified range of thickness. Here, PCE at their maximum level is recorded 22.17% at 300 nm.
Fig. 6, demonstrates the variations electrical parameter that result from changing the thickness of the ETL (ZnO). The ETL thickness
has been altered from 10 to 250 nm to explore the performance of PSCs. Within the given range of thickness VOC, JSC, FF and PCE are
slightly reduced which seems almost constant. That indicates that the effect of ETL thickness on the electrical characteristics of the PSC
is quite little [12]. The highest value for PCE was recorded 22.16%. Hereafter, 20 nm is selected for the optimized ETL thickness.

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Fig. 5. Effect of HTL Thickness variation on solar cell characteristic parameter.

3.2. Effect of electron affinity

The impact of performance on device is demonstrated in Fig. 7(a and b) by changing electron affinity of ETL and HTL. The
simulated ETL affinity is altered between 3.7 and 4.2 eV. In this range, when electron affinity of ETL is beyond 3.9 eV, the PCE went

Fig. 6. Effect of ETL thickness variation on solar cell characteristic parameter.

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downward direction. An electron-hole pair is produced when a photon is absorbed by a semiconductor material. If the electron affinity
is low, the photo-generated electron can be easily stimulated to a higher energy level and transformed into a free electron in the
conduction band. This stimulates charge carrier transmission and enhances the overall device performance, Meng et al. also came at a
similar conclusion [30]. For HTL, the electron affinity is changed in the range from 3.00 to 4.2 eV. It is seen that PCE initially remain
almost constant up to 3.6 eV, beyond this value it drops significantly. Under these circumstances, it can be concluded that the opti­
mized value of electron affinity for HTL and ETL are 3.6 and 3.9 eV, and the PCEs are 22.13% and 22.16%, respectively.

3.3. Effect of doping concentration

Depending on the type of doping, doping materials might either be acceptor or donor type [31–33]. Doping concentration (Na) of
absorber layer values between 1014 and 1018 cm− 3 are used in the simulation to study the impact of acceptor doping concentration. In
Fig. 8, the device parameters along with the changes of the absorber doping concentration are analyzed. It is found that all the pa­
rameters except JSC rise sharply with the increasing Na. This enhancement in device performance is brought about by an increase in the
doping concentration, resulting from a rise of internal electric field and conductivity of the absorber layer [34]. Here, the optimum
doping concentration have been chosen 1018 cm− 3 where the device exhibited 24.05% efficiency. The photovoltaic performance of
PSC for ZnO and Cu2O doping variation have been illustrated in Fig. 9 (a, b). To observe how doping affects ETL and HTL, the doping
concentrations have been modified to be between 1016 and 1020 cm− 3. It is observed that for both HTL and ETL, efficiency increases
with the increasing doping concentration whereas low doping concentrations result in poor performance. The inbuilt electric field
increases with doping density which accelerates carrier transport and enhances conductivity. Therefore the device performance

Fig. 7. Effect of electron affinity of (a) ETL and (b) HTL on PCE.

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Fig. 8. Effect of changing acceptor doping concentration (Na) of absorber layer on solar cell characteristic parameter.

improves [35]. But it is utterly difficult to fabricate HTL and ETL with higher doping concentration. Hence, for both ZnO and Cu2O, the
optimum doping concentration is considered to be 1020 cm− 3 in subsequent modeling operations.

3.4. Effect of defect density of absorber

The stability of PSC is highly affected by the defect density which are inevitable for any material [36]. Various kind of defects have
been found such as vacancies, interstitials, dislocations, and grain boundaries [37]. As in Fig. 10, the device performance is illustrated
with changing absorber defect density from 1015 to 1017 cm− 3. The performance of device dropped rapidly with the increasing defect
density higher than 1015 cm− 3. When defect density increases, there are more traps and recombination routes available that reduces
the effective carrier mobility which leads to shorter carrier lifetimes [33]. The series resistance of the device may be raised by higher
defect densities. The flow of current is impacted by this resistance, which lowers the both PCE and FF. Therefore, the device per­
formance of PSC is deteriorated by the high defect density [38]. Notwithstanding the fact that a high efficiency may be attained at a
low defect concentration, it is apparent that defect density will occur in every material [39]. Therefore, an optimal defect concen­
tration as 1015 cm− 3 is chosen for the subsequent simulations.

3.5. Effect of temperature

The solar cells are typically exposed to the temperature range of 288–323 K, sometimes a higher temperature at the desert [40]. In
this study, the temperature is adjusted between 283 and 353 K with the radiation frequency set to 1 MHz, under the illumination AM
1.5G and 1000 W/m2 intensity. Fig. 11, demonstrates the performance of device with temperature where it is seen that low device
performance is caused by rising temperature. The reason behind this may be due to the fact that the speed of holes and electrons may
increase, and photo-generated charge carrier get into collision with lattice sites. These elements affect the charge carrier lifespan and
recombination rates, which have an adverse effect on PCE [41]. While the temperature reaches 353 K, the device performance turns
into 24.58% of PCE. Hereafter, the ideal device temperature is set as 300 K (room temperature).

3.6. Analysis for final optimized results

On the basis of the obtained results in the previous sections (sec 3.1− 3.5), the SCAPS simulation is run again using the optimal basic
parameters to find the best possible values of performance. Table 3, summarizes the improved parameters of PSC. The optimized
findings for J-V, and QE curve are illustrated in Fig. 12(a) and (b) respectively. The optimized parameter values are as VOC = 1.03 V,
JSC = 30.14 mA/cm2 and FF = 85.58%, PCE = 26.55% and QE of 80–90% in the visible range. According to the analysis of all the
optimized outcomes, the optimum ETL and HTL affinities, thickness, doping concentration, and defect density of the absorber play a

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Fig. 9. Effect of changing doping concentration of (a) ETL and (b) HTL on PCE.

crucial part in the cell performance.

4. Conclusions

Here, lead free FTO/ZnO/CH3NH3SnI3/Cu2O/Au configuration is demonstrated and optimized by SCAPS-1D simulation. The
variation of thickness of ETL, HTL, and absorber layer; electron affinity, doping concentration of ETL, and HTL; defect density of
absorber layer, and the influence of temperature have been analyzed systemically. Notably, the absorber thickness has a greater impact
on the effectiveness of the PSC. The thicknesses of CH3NH3SnI3, ZnO, Cu2O layers were optimized to 0.7 μm, 0.02 μm, and 0.3 μm,
respectively. To improve the PCE enhancing parameter, the effect of varying doping concentration and absorber defect density, as well
as the electron affinities of HTL and ETL, were also investigated and optimized. At 300 K, the device that was optimized showed a PCE
of 26.55% with FF = 85.58%, VOC = 1.03 V, JSC = 30.14 mA/cm2 and QE of 80–90%. In order to construct lead-free Sn-based PSCs with
higher PCE in the near future, the innovative configuration that is described in this research may be useful.

Author contribution statement

Manisha Ahamad; A. K. M. Akther Hossain: Conceived and designed the experiments; Performed the experiments; Analyzed and

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M. Ahamad and A.K.M.A. Hossain Heliyon 9 (2023) e19389

Fig. 10. Effect of absorber defect density on PCE.

Fig. 11. Variation of device parameter with temperature.

Table 3
Optimized value of MASnI3 solar cell.
Parameter ZnO MASnI3 Cu2O

Thickness (nm) 0.02 0.7 0.3

e− affinity (eV) 3.9 3.8
Na 1 × 1020 1 × 1018
1 × 1020
Nt 1 × 1015

interpreted the data; Contributed reagents, materials, analysis tools or data; Wrote the paper.

Data availability statement

Data will be made available on request.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to

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M. Ahamad and A.K.M.A. Hossain Heliyon 9 (2023) e19389

Fig. 12. Optimized Au/Cu2O/CH3NH3SnI3/ZnO/FTO structure: (a) J-V curve; (b) QE curve.

influence the work reported in this paper

Acknowledgements

The authors are grateful to Dr. Marc Burgelman for providing the most recent version of the SCAPS -1D software and BUET for basic
research grant for this work (Grant No. Re-5336(37), Dated 30/06/2021).

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