Journal Pre-proofs

Hybrid Interfacial ETL Engineering using PCBM-SnS2 for High-Performance

p-i-n Structured Planar Perovskite Solar Cells

Pramila Patil, Dilpreet Singh Mann, Umesh T. Nakate, Yoon-Bong Hahn,

Sung-Nam Kwon, Seok-In Na

PII: S1385-8947(20)31632-6
DOI: https://doi.org/10.1016/j.cej.2020.125504
Reference: CEJ 125504

To appear in: Chemical Engineering Journal

Received Date: 10 March 2020

Revised Date: 3 May 2020
Accepted Date: 14 May 2020

Please cite this article as: P. Patil, D. Singh Mann, U.T. Nakate, Y-B. Hahn, S-N. Kwon, S-I. Na, Hybrid
Interfacial ETL Engineering using PCBM-SnS2 for High-Performance p-i-n Structured Planar Perovskite Solar
Cells, Chemical Engineering Journal (2020), doi: https://doi.org/10.1016/j.cej.2020.125504

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 Hybrid Interfacial ETL Engineering using PCBM-SnS2 for High-

Performance p-i-n Structured Planar Perovskite Solar Cells

Pramila Patila, Dilpreet Singh Manna, Umesh T. Nakateb, Yoon-Bong Hahnb,

Sung-Nam Kwona, and Seok-In Naa,

aProfessional Graduate School of Flexible and Printable Electronics, LANL - JBNU

Engineering Institute - Korea, Jeonbuk National University, 664-14, Baekje-daero, Deokjin-
gu, Jeonju-si, Jeollabuk-do, 561-756, Republic of Korea

bSchool of Semiconductor and Chemical Engineering, Solar Energy Research Center, Jeonbuk

National University, 567 Baekje-daero, Deokjin-gu, Jeonju-si, 54896, Jeollabuk-do, Republic

of Korea

 Corresponding author. Tel.: +82 63 270 4465; fax: +82 63 270 2341

E-mail address: nsi@jbnu.ac.kr (S.-I. Na)

1
Abstract

Fullerene derivatives, such as PCBM i.e. [6, 6]-phenyl C61 butyric acid methyl ester, are

actively used as electron-transport layers (ETL) in inverted perovskite solar cells (PSC).

However, limitations, such as low electron transportation, large electron trap region, poor film

formation, and profuse non-radiative recombination, at the perovskite/PCBM interface result

in relatively low performance in inverted PSC. Herein, a significant strategy to overcome these

challenges was envisaged via using tin disulphide (SnS2) combined with PCBM, forming a

uniform mixture of PCBM-SnS2 with high electron transportation and favorable energy levels.

In addition, the greater relative permittivity of SnS2 permits shrinkage in critical electron

captured radius from 0.62 nm to 0.22 nm, thus reducing leakage current and non-radiative

recombination at the perovskite/PCBM-SnS2 interface. The efficiency of PCBM-SnS2 ETL

based inverted PSC reached up to approximately 20% having a high 82% fill factor along with

improved internal and external quantum efficiencies. The PCBM-SnS2 ETL reduced the charge

transportation resistance and increased recombination resistance. The device stability was

improved due to increased hydrophobicity and electrical compactness of the PCBM-SnS2.

Hence, the synergetic effect of PCBM-SnS2 as an efficient ETL has great potential in

improving the performance of planar inverted PSC.

Keywords: Perovskite solar cell; p-i-n structure; Tin disulphide; Electron capture radius;

Stability.

2
Introduction

On the verge of vanishing natural energy resources, organic-inorganic metal halide

perovskite solar cells have raised interest profusely in the last few years due to reduced

processing cost and high power conversion efficiency [1-3]. The numerous benefits of the

perovskite solar cell such as strong absorption coefficient, favorable bandgap, relatively low

trap density, enhanced carrier lifetime, high charge carrier mobility, etc. make them to be

promising photovoltaics for the coming generations [4, 5]. The certified power conversion

efficiency (PCE) PSC rose from 3.8 % to 25.2 % within a very short period of time [6]. The

PSC devices consist of two types of structures namely regular (n-i-p) and inverted (p-i-n),

which are determined by the location of the charge transport layers on the electrode [7]. The

inverted PSC is designed to overcome the limitations associated with normal structures, such

as hysteresis, moisture absorbance, and high-temperature processing [8, 9]. In addition to the

perovskite, the electron transport layer (ETL) and the hole transport layer (HTL) also play a

crucial role in deciding the device performance [10-12]. The most widely used ETL in inverted

PSC is PCBM. Nonetheless, it also endures several shortcomings, which results in lower

efficiencies of inverted PSC. Firstly, the morphology of PCBM ETL is predominantly

dependent on the surface of perovskite lying beneath it [13]. The non-radiative recombination

could be increased due to the uneven coating of PCBM over the rough perovskite large-grained

surface [14]. During the deposition of the electrode, hot metal atoms may permeate through

these openings to form direct contact with the active layer of perovskite, causing excitons

generated in the perovskite layer to quench [15, 16]. This problem is resolved by thermal

evaporation of lithium fluoride and C60/bathocuproine, which covers the PCBM surface [17,

18]. However, these processes add fabrication costs and complexity. Therefore, creating a

consistent one-step process is essential. Secondly, the PCBM’s low electron mobility and high

3
difference in energy levels at the perovskite/PCBM interface restrict efficient charge transport

in ETL. In order to improve the electron mobility and Fermi levels matching, several

researchers have modified PCBM by doping or introducing non-fullerene materials and

polymers into PCBM [19, 20].

In recent years, it has been described that two materials can have a synergetic effect

on charge transportation abilities when used as a composite interfacial layer for improved

interfacial engineering [21-23]. For example, Yang et al. modified PCBM by introducing

graphene quantum dots leading to improved conductivity, enhanced charge extraction and

reduced trap state density of perovskite layer [22]. Yang et al. showed that the introduction of

the polymer at PCBM could improve interfacial electron transport and electron mobility and

suppress interfacial charge recombination in PSCs [21]. However, even though the

conventional interlayers were modified with composite layers, these strategies are not yet

explored for improving PCBM with inorganic metal sulfides in inverted PSC. Metal sulfides

have received considerable attention as potential candidates for n-type semiconductor

alternatives to traditional metallic oxides [24, 25]. Tin disulphide (SnS2) is of particular interest

among the metal sulphides due to its unique chemical and structural properties. It is a cost-

effective and eco-friendly material with a tunable bandgap (2.1 - 3.38 eV) to provide excellent

photoelectric properties, which exhibit various applications in various fields, such as solar cells

and photocatalyst, transistors, etc. [26, 27]. Furthermore, a 2D structured SnS2 can lead to good

interfacial contact with other layers, effective charge transfer, and significantly reduced charge

recombination rate [28]. However, although several techniques, like self-assembly stacking

and atomic layer deposition etc., have been employed and showed improved device

performance, such techniques could add high cost and complexity as well [29, 30]. Hence, a

sustainable, reliable, scalable and practical method to develop a cost-effective device is of main

4
concern in the present scenario. The hydrothermal route is of special concern due to its

simplicity, phase control, high crystallinity, low growth temperature and cost-effectiveness

[31]. Taking into account all the above points, the hydrothermally synthesized 2D SnS2

nanoparticles (NPs) are a potential candidate to modify PCBM ETL for enhanced performance

of the planar inverted PSC.

In this work, we present for the first time SnS2 modified PCBM as efficient ETL in the planar

inverted PSC achieving a high efficiency of approximately 20 %. The high-quality SnS2 NPs

were successfully synthesized via a versatile hydrothermal chemical route followed by

exfoliation and characterizations. We found that the ETL performance of PCBM could be

enhanced with the aid of exfoliated SnS2 NPs, which possess high conductivity and electron

extraction leading to efficient charge transport between ETL and perovskite. In addition, a good

dispersion of exfoliated SnS2 and PCBM in 1,2-Dichlorobenzene permits a trivial solution

processing without any post-treatment of solutions. Subsequently, with facile fabrication

processing, the PSC based on PCBM-SnS2 showed improved PCE of 19.95%, compared to

PCE of 18.22% for the control device based on PCBM. In order to reveal detailed origins for

high performance of modified ETL based inverted PSC, we investigated in details the quantum

efficiencies, photovoltaics parameters, energy level alignment, low critical electron capture

radius, charge recombination, electrical conductivity, impedance, electrical compactness,

smoothness and device stability. The energy level of PCBM-SnS2 was well-matched with

perovskite and charge transportation was improved as a result of the decreased recombination

radius as compared to pristine PCBM, resulting in higher cell performance. Furthermore, the

SnS2 introduction allows efficient protection to perovskite from interacting with the

environment as well as long-device-efficiency enhancement.

5
Experimental

Materials

All the chemicals required for the SnS2 NPs synthesis viz. stannic chloride (SnCl4.5H2O) and

thioacetamide (C2H5NS) were obtained from Sigma-Aldrich. Hydrochloric acid (HCl 35 %,

pure A.R. grade) was used as purchased without any further purification. Lead (II) iodide (PbI2,

99.99%) and lead bromide (PbBr2, 99.9%) were acquired from Tokyo Chemical Industry (TCI)

Chemicals. Formamidinuim iodide (FAI) and methylammonium bromide (MABr) were

procured from the great cell solar. Solvent (DMF, DMSO, and 1, 2-Dichlorobenzene) and

cesium iodide (CsI, purity 99.9%) were procured from the Sigma-Aldrich. Nickel oxide (NiO)

and zinc oxide (ZnO) nanoparticles suspensions were obtained from the Nano Clean Tech,

while PC61BM was purchased from Nano C.

Synthesis

The SnS2 nanopowder was synthesized by a simple hydrothermal chemical route. In typical

chemical synthesis, 0.4 mL of HCl was added to 10 mL of distilled water in order to achieve a

consistent solution. Further, 1 mM SnCl2.5H2O was added to the prepared HCl aqueous

solution and the mixture was stirred briskly for 30 minutes. The volume of the solution was

then adjusted to 40 mL by adding distilled water. An 8 mM thioacetamide was added to the

obtained solution with constant stirring. Lastly, the solution was poured in a Teflon lined

stainless-steel autoclave having 100 mL capacity and heated at 145 °C for 48 hours and cooled

to room temperature. Then, the resulting precipitate was collected by centrifugation, washed

using distilled water and ethanol multiple times. It was dried at 60 °C in a vacuum oven for 5

hours. The resulting powder was crushed to obtain fine particles. The final powder product was

used for exfoliation to achieve highly dispersed nanoparticles solution for ETL modification.

6
The schematics of the synthesis and exfoliation process are demonstrated in the supporting

information S1.

Device fabrication

The glass-coated ITO substrates (15 × 15 mm) were initially cleaned with Mucasol solution,

followed by deionized water, ethanol, acetone and iso-propanol under prolonged ultra-

sonication. They were then dried at room temperature and subjected to UV-Ozone cleaning for

another 30 minutes. The exfoliated SnS2 nanoparticles were dispersed in 1, 2-dichlorobenzene

(~1mg/ml concentration). The different percentages of SnS2 (1, 3, 5, 7 and 10 vol %) were

added into the PCBM with 15 mg/ml concentration and were stirred overnight at 60 °C. The

NiO layer was deposited on the cleaned ITO using precursor inks at 4000 rpm for 30 seconds

by using the spin coating technique followed by annealing for 30 minutes at 300°C. For the

preparation of perovskite solution with the composition of Cs0.175FA0.750MA0.075Pb(I0.880Br

0.120)3, the amount of PbI2 (0.58 g), PbBr2 (0.08 g), FAI (0.019 g), MABr (0.012 g) and CsI

(0.066 g) were dissolved in the solution of dimethylformamide and dimethyl sulfoxide (2:1

volume ratio) in a nitrogen filled glove box. The perovskite layer was coated onto the NiO HTL

by spin-coating using the obtained solution (two-step spinning condition, i.e. 500 rpm for 5

seconds, ii. 4500 rpm for 45 seconds). During the coating process, an anti-solvent treatment

was carried out by dropping 300 μL of chlorobenzene onto the perovskite for 30 seconds s. The

films were annealed for 30 minutes at 100 °C temperature. The PCBM in 1, 2-dichlorobenzene

(15 mg mL-1) and different weight ratios of PCBM-SnS2 mixture of the electron transport layer

were spin-coated onto the perovskite films at 1000 rpm for 15 seconds followed by 8000 rpm

for 40 seconds with annealing at 100°C for 10 minutes. The zinc oxide nanoparticles solution

(ZnO NPs, 2.5 wt% ZnO in 2-propanol) was deposited on the PCBM layer at successive spin-

coating in two steps of 1000 and 8000 rpm for 15 and 40 s, respectively and then the film was
7
annealed at 100°C for 10 minutes. Finally, silver electrodes of 100 nm thickness were deposited

using a thermal evaporator.

Characterizations

Work function and elemental analysis of PCBM and PCBM-SnS2 films were carried out by use

of the Ultraviolet photoelectron spectroscopy (UPS, Fischer Scientific) and X-ray

photoelectron spectroscopy (XPS, Thermo Fischer Scientific). The X-ray diffraction (XRD)

spectrum was studied by X-ray diffractometer (Rigaku Ultima) having Cu Ka radiation

(wavelength = 0.154 nm). The absorption spectra of the PCBM and PCBM-SnS2 films were

recorded by using a UV-visible spectrophotometer (Perkin Elmer Lambda 750). A current

density-voltage (J-V) measurement of the devices was carried out by use of a Keithley 2400

electrometer and solar simulator Oriel Sol3A having one sun condition (i.e. AM 1.5G, 100

mW/cm2). The light intensity was standardized by using a reference crystalline silicon cell. The

PCE and stabilized photocurrent were measured at the bias voltage obtained from the maximum

power point from the typical J-V curve. An internal quantum efficiency (IQE) and external

quantum efficiency (EQE) of the PSC were studied by using a certified system of the incident

photon to current conversion efficiency (IPCE) (IQE-200, Oriel Instruments, USA). The

topography and surface roughness of the PCBM and PCBM-SnS2 were analyzed by using the

atomic force microscope system (AFM, XE7 Park). The perovskite top view images were

recorded by a FESEM (Carl Zeiss-Supra™ - 40 VP). The room temperature photoluminescence

(PL) was recorded by using a spectro-fluorometer (Shimadzu Lab solutions RF) excited at 391

nm wavelength. The CELIV, the transient photovoltage (TPV) and transient photocurrent

(TPC) were analyzed with a multifunctional organic semiconductor parameter test system

(T4000, Mc Science). The electrochemical characterization of the prepared devices was

investigated by using a Compact Stat electrochemical workstation (Ivium Technologies,

8
Netherlands).

Results and discussion

Characterization of SnS2 NPs

The prepared SnS2 powder is a multi-layered material to be exfoliated into a nano-

plate like structure via the exfoliation technique. Low-cost, scalable and high-yield production

of 2-D SnS2 materials is essential for practical applications [32, 33]. Several methods have

been adopted to fabricate 2-D materials, such as mechanical exfoliation, chemical exfoliation,

chemical vapor deposition, and many more [34, 35]. Among them, ultrasound exfoliation is an

easy, effective and economical technique. In this technique, the bulk crystals are dispersed in

particular solvents (appropriate surface tension) and ultra-sonicated for a few hours to provide

2-D nanostructure. This technique is unaffected by air or water, which can be easily scaled up

to get high yield and permits the film formation with enriched properties [36]. Figure 1(a)

represents the exfoliation process via schematics. The exfoliated nanoparticles and highly

dispersed solution are shown in Figure 1(b). The structural properties of the prepared material

were estimated by using the XRD analysis as shown in Figure 1(c) that confirms the hexagonal

structure of SnS2 (JCPDS card no. 23-0677). The estimated values for structural parameters

are tabulated in supporting information table S2. The average crystallite size associated with

each diffraction peaks was estimated from the XRD data using the Scherrer’s formula as shown

in table S2. The average value of crystallite size (~ 5.7 nm) was calculated for SnS2. The

estimated ‘d’ values corresponding to all XRD peaks were larger than the JCPDS standard data.

All diffraction angle values (2θ) corresponding to XRD peaks were smaller than the standard

data as shown in table S2. Dislocation densities associated with each diffraction peak were

estimated from the crystallite size as shown in table S2. The texture coefficient (TC) value,

greater than one (TC > 1), indicates the material growth along the preferred orientation and TC
9
value with ~ 1 reveals random orientation. The highest TC value of 1.73 corresponds to the

(010) plane that confirms SnS2 crystal’s preferred orientation [28]. The thickness and fine

structure of the exfoliated SnS2 particles were analyzed by using AFM in tapping mode. Figure

1(d) shows the AFM image of the exfoliated particles coated on glass. The thickness of the

SnS2 particles was observed at ~6-7 nm (as shown in the inset of Figure 1(d)) that is in good

agreement with the average crystallite size calculated in the XRD analysis. These results clearly

indicate that the bulk SnS2 has been exfoliated into 2-D nano-plate like structures [37]. The

XPS study was carried out to analyze the composition and bonding configuration in prepared

SnS2 NPs, and the results are presented in Figures 1(e) and (f). The fully scanned XPS survey

of the SnS2 is shown in S3, which reveals the presence of Sn and S elements. Figures 1(e) and

(f) show the core level spectra for S and Sn, respectively. As seen in Figures 1(e) and (f), the

two prominent peaks centered at 486.2 and 494.6 eV could be related to the binding energy of

Sn3d3/2 and Sn3d5/2 doublet respectively. In the core level analysis of S 2p, two peaks were

detected at 162.26 and 161.1 eV corresponding to S 2p1/2 and S 2p 3/2, and the detected binding

energies are in good agreement with states of SnS2 [38, 39]. As per earlier reports, the peak

appearing at 161.1 eV corresponded to the S bond with Sn2+, which specifies that there are

some sulfur vacancies of the exfoliated surface of SnS2. In addition, the peak appearing at 486.2

eV was due to Sn2+ bond with S. These results indicate that the process of exfoliation increases

the sulfur vacancies of SnS2 [39, 40]. More importantly, from the crystal structure, morphology

and elemental compositional analyses for SnS2 NPs, it can be confirmed that nano-plates, like

SnS2 NPs, were successfully prepared via exfoliation and hydrothermal route.

Modified ETL in inverted PSC

The inverted PSC device was fabricated by using modified PCBM-SnS2 ETL with the

configuration of ITO/NiOx/perovskite/PCBM-SnS2/ZnO/Ag to evaluate the performance as

10
shown in Figure 2(a). The PSC performance was studied for pristine PCBM ETL as well as

modified different PCBM:SnS2 combination volume% ratios (100:0, 99:1, 97:3, 95:5, and

93:7). The optimized average PCE for various PCBM-SnS2 combination devices along with

pristine PCBM devices is shown in Figure 2(b). The J - V characteristics for devices obtained

under a solar irradiation 100 mWcm-2 and AM 1.5 G are shown in Figure 2(c). The PCBM:SnS2

combination having a volume% ratio of 95:5 was revealed to be a higher performance PSC

device. The modified ETL combination having a volume% ratio of 95:5 was studied in detail

for improved performance of the inverted PSC with respect to pristine PCBM. The PCBM ETL

based best device exhibited a PCE of 18.22% having Voc, Jsc and FF of 1.03 V, 21.87 mA

cm–2 and 80.56 %, respectively. The PSC with PCBM-SnS2 as ETL exhibited a PCE of 19.95

% with a Voc of 1.06 V, Jsc of 22.70 mA cm–2 and FF of 82.87 %. We further studied the time-

dependent power output of the PSC devices by recording the current density at the maximum

power point as shown in Figure 2(d). The PCBM-SnS2 showed a higher current output than the

PCBM devices with a stable current output for over 900 seconds to rule out the problem of

variation in current due to light soaking that has been found in other recent PSC. In order to

unveil the higher performance of the PCBM-SnS2 ETL based device compared to the pristine

PCBM ETL device, the EQE and IQE for both the devices were measured as provided in

Figures 2(e) and (f), respectively. Both EQE and IQE for PCBM-SnS2 based devices have

increased significantly for the entire spectrum, which reveals the better IPCE properties of

PCBM-SnS2 [21]. The PCBM-SnS2 based devices exhibited enhanced EQE peak (~89 %) as

compared to the PCBM devices (~79 %). The enhancement in IQE values for PCBM-SnS2

(~91 %) from PCBM (~81 %) was observed. The higher EQE of PCBM-SnS2 was mainly due

to increased IQE, indicating that the Jsc and EQE shown in PCBM-SnS2 based PSC could be

attributed to the better charge transfer abilities with the use of SnS2 [41, 42].

11
 The plausible mechanism of the PSC performance difference in modified and pristine

PCBM ETL based devices was elaborated by using an energy band diagram, UPS, capacitance

and schematics, as shown in Figure 3. The energy level diagram is presented in Figure 3(a).

The PCBM-SnS2 shows a shift of 0.14 eV as compared to the PCBM. As observed, the Fermi

level of the PCBM-SnS2 (-4.36 eV) is in better alignment with perovskite (-4.23 eV) as

compared to pristine PCBM (-4.50 eV) (The detailed calculation of parameters and perovskite

UPS spectra are provided in the Supporting information). This alignment plays a vital role in

electron transfer and maximizing the built-in voltage and obtaining the optimum value for

open-circuit voltage (Voc) [43]. The valence band (EVB) values were estimated from the UPS

spectrum analysis as in Figure 3(b). The value of EVB for PCBM-SnS2 was observed to be -

5.93 eV, which was tuned from -5.87 eV of pristine PCBM. The greater EVB value of PCBM-

SnS2 compared to perovskite could offer a high potential barrier to hole transfer across their

interface and also benefit the improved Jsc and FF of device [44]. Hence, the hole blocking

property can be significantly enhanced in the modified ETL, which further reduces the

possibility of charge recombination. The nonradiative recombination at perovskite/ETL

interfaces is one of the major problems, which strongly affect the PSC performance, which can

be determined by the electron capture region (ECR). This ECR is responsible for conduction

of charges loss across the interface of perovskite/ETL due to columbic interactions, and is

termed as the critical radius (Rc) [21].

The Rc value can be calculated by using the following formula in equation 1;

𝑞2
𝑅𝑐 = 4𝜋𝑘𝑇𝜀0𝜀𝑟 (1)

Where q represents the elementary charge, k is Boltzmann constant, T represents the

temperature, and ε0 and εr are known as the vacuum permittivity and relative permittivity (of

12
the ETL layers), respectively [21]. The relative permittivity can be experimentally estimated

from a parallel plate capacitor configuration using the formula as in equation 2;

Cd
εr = Aε0 (2)

Where C is the capacitance, A is the area of the plate, and d represents a thickness of ETL

films. After putting equation 2 in equation 1, we get the following modified formula as in

equation 3 to calculate the critical electron capture radius

q2A
Rc = 4πkTCd (3)

The Rc is inversely proportional to capacitance 'C' as per equation 2. The capacitance

was measured for PCBM-SnS2 and PCBM films in parallel plate configuration as a function of

frequency as in Figure 3(c). The Rc was evaluated after putting capacitor values in equation

(3) for PCBM-SnS2 (R2) and PCBM (R1) films, with 0.22 nm and 0.62 nm respectively, as

shown in the inset of Figure 3(c) [45, 46]. The reduced R2 value for PCBM-SnS2 compared to

R1 of pristine PCBM could be due to tuned relative permittivity of modified ETL. The relative

permittivity of SnS2 is 17.7 whereas for PCBM it is 3.82 [21, 37, 47]. Hence, the resultant

relative permittivity of PCBM-SnS2 would be greater than pristine PCBM, which provides a

lower ECR and decreased charge recombination, which eventually leads to increased fill factor

in modified PCBM-SnS2 ETL devices [21]. The pristine PCBM film had a higher

recombination radius and larger charge trap region that hindered the charge transfer and

decreased the overall performance of the device. Another major role of ETL could be to

improve the coverage of the perovskite surface, which is quite important for achieving high

performance in the inverted PSC. Usually, pristine PCBM ETL often shows non-uniform film

formation that results in breaches between the ETL and perovskite layer [13]. During the

deposition of Ag on top of ETL, there may be permeation of metal atoms via openings (pinholes
13
or porous film) resulting in direct contact of the electrode with the perovskite layer [48]. Hence,

the high-quality ETL formation to improve the interface with the perovskite layer is essential.

The addition of inorganic nanomaterials to conducting polymers are reported to improve the

electrical compactness of film by forming a conducting path between the matrix and dispersed

particles [49, 50]. In the same way, PCBM-SnS2 together can form an electrically compact

layer than pristine PCBM [51]. The modified ETL could facilitate easy charge transportation

[52, 53], as shown in the schematic in Figure 3(d). Hence, key factors as mentioned in Figure

3 are a result of synergetic effect of PCBM-SnS2 ETL.

The FESEM cross-section image of the modified PCBM-SnS2 ETL device is shown

in Figure 4(a). The various layers of the inverted PSC device configuration are clearly visible

in the cross-section image. The AFM images for perovskite, PCBM and PCBM-SnS2 are shown

in Figures 4(b) to (d), respectively. As observed from the AFM images, the surface roughness

(RMS) of PCBM-SnS2 was observed to be reduced to 9.173 nm as compared to 10.318 nm of

pristine PCBM. The elemental mapping and energy dispersive spectroscopy (EDS) analyses

were also carried out for modified ETL to investigate the distribution of elements as in Figures

4(e) - (h) and Figure S4, respectively. The mapping images clearly confirm the SnS2 presence

in composite films and uniform distribution of 'C' (from PCBM), Sn and S elements in modified

ETL. This uniform dispersion of SnS2 nanoparticles in modified ETL could also improve the

electrical compactness [54]. The SEM, AFM, elemental mapping and EDS revealed that the

incorporation of SnS2 into PCBM could provide better coverage, and smoother ETL film

formation on the perovskite layer, thus supporting better charge transport in modified PCBM-

SnS2 [23, 54].

The conductivity of PCBM and PCBM-SnS2 with the configuration of ITO/ETL/Ag

was measured by using Linear-sweep Voltammetry (LSV) as shown in Figure 5(a). The
14
conductivity of PCBM and PCBM-SnS2 samples was found to be 27.37 μSm-1 and 35.24 μSm-1,

respectively, which indicates the improved charge transportation with PCBM-SnS2 leading to

the higher Jsc and performance of PSC [23]. As demonstrated in the inset of Figure 5(a), steady-

state PL measurement of the PCBM-SnS2 films displayed more effective quenching as

compared to pristine PCBM that also demonstrates better charge extraction capability from the

perovskite layer [55]. The change of the Voc with varying illumination light intensity was

studied to analyze carrier recombination in the devices. Figure 5(b) shows the plot for Voc

versus light intensity for both (PCBM-SnS2 and PCBM) ETLs. The ideal slope value is 1 kT/q,

and aberration from this value specifies the trap assisted recombination in the devices. As seen

from the graph, the PCBM-SnS2 based devices exhibit an ideality factor value of 1.14 kT/q as

compared to PCBM, showing 1.25 kT/q, suggesting that the trap assisted recombination can

be effectively suppressed in PCBM-SnS2 based devices, subsequently leading to improved cell

performance [56]. In order to support the reduced charge recombination and improved electron

transportation in modified ETL, the electrochemical impedance spectroscopy measurements

were carried out. The Nyquist plots obtained for both ETL devices by EIS measurement under

dark are illustrated in Figure 5(c). The charge transfer resistance (Rct) and interfacial

recombination resistance (Rrec) were measured by using their respective equivalent circuits as

in the inset of Figure 5(c). The low value of Rct signifies efficient charge transportation,

whereas the high Rrec reveals the suppressed degree of charge recombination [57, 58]. The Rct

values for pristine PCBM and PCBM-SnS2 were 6641 and 1798 Ω, respectively. On the other

hand, 4882 and 2379 Ω values of Rrec were noted for PCBM-SnS2 and PCBM, respectively.

The reduced Rct and improved Rrec values for PCBM-SnS2 compared to pristine PCBM imply

better charge transport, higher current density and lower charge recombination. This confirms

the improved performance of PCBM-SnS2 based inverted PSC.

15
 The mobility of charge carriers in operating conditions was analyzed by using the

photo-induced charge extraction with linearly increasing voltage (Photo-CELIV

measurements). The transient photovoltage (TPV) and transient photocurrent (TPC) were also

studied to investigate the recombination processes, charge recombination lifetime and charge-

extraction time, respectively [59, 60]. Figure 6(a) depicts the photo-CELIV data for pristine

PCBM and PCBM-SnS2 films, where the maximum current density (tmax) increased upon

addition of SnS2 into the PCBM. The charge carrier mobilities for PCBM-SnS2 and PCBM

from the photo-CELIV measurements were determined to be 2.89 and 2.54 x 10-1 cm2/(Vs),

respectively. These results indicate that the PCBM-SnS2 based PSC have better carrier

transport/extraction capabilities than PCBM based PSC [61]. In addition, the photocurrent in

PCBM-SnS2 based PSC reduce faster (0.51 µs) than PCBM based PSC (0.61 µs) as shown in

Figure 6(b), indicating that the charge extraction in PCBM-SnS2 based PSC is more efficient

[62, 63]. The recombination lifetime for charge carriers was also analyzed by the TPV

measurements shown in Figure 6(c). The PCBM-SnS2 showed a longer photo voltage decay

(87.35 µs) compared to the PCBM (66.39 µs) based PSC, indicating a longer carrier lifetime

and smaller charge recombination [64]. These results indicate that the enhanced PSC

performance for PCBM-SnS2 based devices could be due to improved carrier transportation

and reduced trap-assisted recombination to provide higher values for Jsc, FF and efficiency.

The more stable photocurrent hysteresis of PCBM-SnS2 (HI=0.1427) than PCBM (HI=0.2106),

as shown in Figure S5, further supported such improved ETL film properties and device

performance in PCBM-SnS2 [64, 65].

The air stability studies for the unencapsulated devices stored in ambient conditions (i.e., 25−30

°C, 45−55 % humidity) following the ISOS-D-1 protocol were recorded for 50 days as shown

in Figure 6(d) [66]. It was observed that the PCE of the PCBM based devices had reduced by

16
63 % of its initial value, whereas that of the PCBM-SnS2 based devices degraded just by 20%

of its initial value under identical exposure conditions. In order to investigate the higher

stability of the modified ETL device, water contact angle measurements for different films on

perovskite were carried out as shown in the supporting S6. It was observed that the water

contact angle increased from 75.99o (for PCBM) to 85.14o (for PCBM-SnS2). The improved

hydrophobic nature of the film can subdue the moisture infusion into the perovskite film, thus

increasing the long-standing stability of devices in the environmental conditions. Further, as

observed from SEM, AFM and EDS mapping, TEM (Figure S7), the introduction of SnS2 into

PCBM to provide smoother ETL-film and better smoothness can also contribute to the

underlying perovskite protection [23, 67, 68]. According to some previous reports, there could

be certain possible reasons leading to enhancement in the stability. i) The 2D SnS2 nanosheets

can initiate the intermolecular Pb--S interactions, thus leading to passivation of the interfacial

sites and suppressing the charge recombination. This can also form a uniform layer on

perovskite, which is beneficial for moisture infiltration and inhibiting perovskite

decomposition or phase separation [30]. ii) The combination of SnS2 with PCBM leads to

efficient electron transfer and diffusion through the perovskite/ETL interface; this to some

extent could hinder the electron-migration degradation process happening within the devices,

thus improving the device stability [69]. As shown in table S8, the PCBM-SnS2 based devices

showed superior device performance as compared to other devices. Thus, it was evidently

indicated that the PCBM-SnS2 based PSC would provide great potential for developing

effective electron transporting layer.

Conclusion

In summary, we have engineered PCBM ETL using nanostructured SnS2 newly introduced in
17
the inverted planar PSC. The systematic optimization of SnS2 loading in PCBM was carried

out to achieve a higher performance and produced enhanced efficiency to approximately 20%

and an improved fill factor of 82%. The improved performance of the inverted PSC could be

attributed to the tuning energy level alignment, improved hole blocking ability and reduced

electron capture radius Rc (0.22 nm). The enhanced film morphology and coverage and

increased electrical conductivity also contributed to the improvement of PSC performance. In

addition, the improved device resistances (Rct and Rrec), carrier mobility and charge

recombination lifetime revealed that the overall device improvement could be due to enhanced

charge extraction and transport with suppressed interfacial recombination and leakage current

by introducing SnS2 in PCBM. Furthermore, the SnS2 modified ETL improved the device

stability probably due to its more hydrophobic and uniformly covered film properties to protect

the perovskite layer from moisture and other impurities. 80% of the initial PCE in modified

ETL was maintained even after 50 days of storage in the ambient atmosphere, unlike the

pristine PCBM having 37% of its initial value. This SnS2 utilization and ETL composite

approach can be highly promising and competitive for enhancing the cell-efficiency as well as

cell stability. This practical and cost-effective improvement of ETL can pave new ways of

advancing the performance of inverted perovskite solar cells.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal

relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The present work is supported by the selection of research-oriented professor of Jeonbuk

18
National University in 2020, the Korea Electric Power Corporation (CX72170050), and the

National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT)

(NRF-2016R1D1A1B04933887).

19
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Figure Captions

Fig. 1. (a) Schematic for exfoliation process of SnS2 (b) TEM image for exfoliated SnS2,

inset shows photograph of exfoliated solution obtained (c) XRD, (d) AFM, and line profile, (e)

High resolution XPS for S 2p and (f) Sn 3d spectra of exfoliated SnS2.

Fig. 2. (a) Schematic device architecture of inverted planar perovskite solar cell (b) Average

data of optimized PCBM-SnS2 concentration (c) J-V Characteristics of devices with PCBM

and PCBM-SnS2 (d) Steady photocurrent output at fixed applied voltage over 900 s as a

function of time for PCBM and PCBM- SnS2 devices (e) External quantum efficiency and (f)

Internal quantum efficiency for optimal PCBM and PCBM-SnS2 devices.

Fig. 3. (a) Energy level diagram of perovskite with different ETLs (b) UPS spectra for

PCBM and PCBM-SnS2 films (c) Capacitance Vs Frequency at room temperature for pristine

PCBM and PCBM-SnS2, (d) Probable mechanism for electron transport with PCBM and

PCBM-SnS2 devices.

Fig. 4. Figure 4: (a) Cross sectional SEM image of ITO/NiO/Perovskite/ PCBM-SnS2/ZnO,

AFM topographic images of (b) Perovskite (c) PCBM (d) PCBM-SnS2, Elemental mapping of

(e) PCBM-SnS2 and present elements as (f) C (g) Sn (h) S

Fig. 5. (a) LSV curves of ITO/ETL/Ag for PCBM and PCBM-SnS2 as ETLs, the inset shows

Steady state PL spectra of devices with PCBM and PCBM-SnS2 (c) Voc of devices as a

function of light intensity for devices with PCBM and PCBM-SnS2 (d) Impedance spectra of

PCBM and PCBM-SnS2 devices, the inset shows equivalent circuit.

Fig. 6. (a) Photo CELIV measurements, (b) Transient Photocurrent, and (c) Transient

Photovoltage measurement for devices with PCBM and PCBM-SnS2, (d) Normalized PCE as
29
a function of time for the devices with PCBM and PCBM-SnS2.

Highlights

 SnS2 (Inorganic) NPs and PCBM (Organic) as hybrid efficient ETL in inverted PSC

 Reduced electron capture radius & recombination at hybrid ETL/perovskite interface

 Improved photo conversion efficiency up to ~ 20 % with high fill factor 82 %

 Enhanced hybrid ETL conductivity, compactness, hole blocking, smoothness, & low

Rct

 Synergetic effect in hybrid ETL results in high performance and stability of PSC

30