Synthetic Metals 304 (2024) 117578

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Efficiency and stability enhancement in FA-based perovskite solar cells

using controlled reduction of graphene oxide interlayer – An
experimental investigation
Rusul Alabada a, Anjan Kumar b, *, Nestor Ulloa c, d, **, Byron Vaca Barahona e, Félix García c,
Atul Makrariya f
a
College of Nursing, Al-Muthanna University, Samawa, Al Muthanna, Iraq
b
Department of Electronics and Communication Engineering, GLA University, Mathura 281406, India
c
Facultad de Mecánica, Escuela Superior Politécnica de Chimborazo (ESPOCH), Panamericana Sur km. 1½, Riobamba 060155, Ecuador
d
Grupo de Investigación y Desarrollo de Nanotecnología, Materiales y Manufactura (GIDENM), Escuela Superior Politécnica de Chimborazo, ESPOCH, Panamericana
Sur Km. 1½, Riobamba, Ecuador
e
Facultad de Informática y Electrónica, Escuela Superior Politécnica de Chimborazo (ESPOCH), Panamericana Sur km. 1½, Riobamba 060155, Ecuador
f
Department of Electrical & Electronics Engineering, IIMT University, Meerut, Uttar Pradesh 250001, India

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

Keywords: Reduced graphene oxide (rGO) as an interlayer and interface engineer, due to its conductivity and hydropho­
Reduced graphene oxide bicity, can be coated on top of perovskite layers to increase the photovoltaic performance and stability of
FAPbI3 perovskite solar cells. Herein, we employed reduced graphene oxide as an interlayer. By controlling the reduction
Stabilized perovskite
level of rGO, its potential for boosting perovskite solar cells’ efficiency was further increased. Results showed
Hole mobility
Efficiency
that increasing the reduction degree of rGO to an optimal level increased its conductivity and hole mobility,
which induced charge transfer at perovskite/hole transport layer and increased the open-circuit voltage of solar
cells. Our rGO reduction controlling strategy enables FAPbI3-based solar cells to record a PCE of 22.29%. In
addition, increasing reduction degree increased hydrophobicity behavior of rGO. It increased perovskite solar
cell resistance against humidity and heating degradation. The developed method in current study can push up
perovskite solar cells to industrialization.

1. Introduction developed a triple cations perovskite Cs5(MA0.17FA0.83)(95)Pb

(I0.83Br0.17)3 to increase PCE of PSCs [6]. They recorded a PCE of 21.1%
In the past decade perovskite materials, due to their stupendous for PSCs. Saliba et al. by incorporation rubidium cations to their struc­
optoelectrical properties and facile and cost-effective synthesis routes, ture reached to efficiency of 21.6% [7].
were applied in different technologies. Perovskite solar cells (PSCs) Despite of efficiency progress of PSCs, still they suffer from unde­
technology is one of the most critical applications of perovskite mate­ sirable stability against light, heating, and humidity. Over time,
rials, which was developed by Myasaka et al. in 2009 [1]. By combining different approaches have been suggested to tackle the instability of
different structures of perovskite materials containing main groups of PSCs. Employing carbon-based materials as electrode is one promising
MAPbX3, FAPbX3, and CsPbX3 (X=I, Br, Cl), the power conversion ef­ method to increase the stability of PSCs [8–10]. Ku et al. substituted
ficiency of PSCs in recent years has passed the 25% [2–5]. Jeon et al. metallic counter electrodes with carbon material and recorded a low
incorporated MAPbBr3 perovskite into FAPbI3 perovskite and developed PCE of 6.64% for PSCs. Interestingly, they observed that their developed
double cation (FAPbI3)0.85(MAPbBr3)0.15 perovskite to increase PCE of devices have considerable resistance against degradation and high­
PSCs. They emphasized composition reengineering to attain a stabilized lighted the advantage of carbon-based PSCs over metallic PSCs ones
phase FAPbI3 with improved optoelectrical properties [4]. Saliba et al. [11]. Another suggested approach to increase PSCs stability is

* Corresponding author.
** Corresponding author at: Facultad de Mecánica, Escuela Superior Politécnica de Chimborazo (ESPOCH), Panamericana Sur km. 1½, Riobamba 060155, Ecuador.
E-mail addresses: [email protected] (A. Kumar), [email protected], [email protected] (N. Ulloa).

https://doi.org/10.1016/j.synthmet.2024.117578
Received 4 October 2023; Received in revised form 2 March 2024; Accepted 4 March 2024
Available online 8 March 2024
0379-6779/© 2024 Elsevier B.V. All rights reserved.
R. Alabada et al. Synthetic Metals 304 (2024) 117578

developing of dimensional engineering to assemble 2D/3D hetero­ 2.2. Synthesis of reduce graphene oxide
structured PSCs [12–14]. In 2016, Ma et al. showed that through
fabricating 2D/3D hybrid perovskite can combine the advantages of 2D GO sheets are reduced to reduced graphene oxide (rGO) using
and 3D perovskites. [4] They observed that in the inverted PSCs, the 2D hydroiodic acid (HI, Merck, 57%) reducing agent at reduction periods
layer did not prevent the carrier transport from perovskite to the elec­ 24, 48, 72, and 96 h. 150 mg of GO sheets are dispersed into 150 mL
tron transport layer (ETL), and the charge separation occurred at the deionized water with ultra-sonication at room temperature for 45 min.
2D/3D perovskite interface [15]. Recently, Ma et al. used π-conjugated After that, 15 mL of HI agent is added to it, followed by ultra-sonicating
organic cations to fabricate 2D/3D bi-layers with aligned energy levels for another 15 min. The obtained suspension is stirred for a period of
for charge transfer at 2D/3D heterojunction. They recorded a champion specified time (24–96 h), followed by centrifuging at 8000 rpm for
PCE of 24.63% with favorite stability against irradiance and heating 5 min. The obtained rGO precipitates are washed with deionized water
[16]. Encapsulation of PSCs is another promising approach to keep safe and h sodium bicarbonate solution to neutralize of pH to 7 and remove
them from degradation [17–19]. Recently, Wang et al. design a impurities. rGO sheets are dried in an oven at a temperature of 40 ℃ for
self-crosslinked polymer material to protect PSCs without any destruc­ 48 h.
tion. Their proposed encapsulation method promotes heat transfer and
avoids heat accumulation. The encapsulated PSCs maintain 98% of their 2.3. Solar cell construction
initial PCE after 1000 h in the damp-heat 85℃/85% RH stability test
[20]. Here, PSCs with a regular architecture of FTO/CTiO2/MTiO2/
In addition to the mentioned methods, the use of an intermediate FAPbI3/spiro-OMeTAD/Au with an active area of 2 mm×4 mm were
layer between perovskite and the hole transport layer (HTL) in regular fabricated. As the first layer, a compact titanium dioxide (CTiO2) thin
PSCs or between perovskite and the ETL in inverted PSCs can also lead to film is spin-coated on the patterned and cleaned FTO substrate at speed
increased stability and improved efficiency in solar cells [21–23]. of 3000 rpm for 30 s. The coated layer is put in a furnace and heated up
Capasso et al. used MoS2 flakes as an active buffer layer over the to 450 ℃. It is kept for 30 min at this temperature. The CTiO2 stock
perovskite layer. They showed that the MoS2 film by preventing the solution was prepared by dissolving 700 µL titanium(IV) isopropoxide
shunt contacts between the perovskite and electrodes acted as a pro­ (Sigma Aldrich, 99.99%) into an acidic ethanol solution via stirring in an
tective layer, and increase transfer carriers from the perovskite to the ice bath for 45 min, followed by filtering to remove non-dissolved ma­
HTL [24]. Li et al. introduced NiOx nanoparticles between the perov­ terials. As the second layer, a mesoporous titanium dioxide (MTiO2)
skite and HTL layers to generate PCSs with considerable stability. They layer is fabricated on the CTiO2 layer. The MTiO2 solution was prepared
found that the NiOx layer avoids penetration of Li+ ions from HTL to by mixing 200 mg commercial TiO2 paste (Dyesol, 25 nm) with
perovskite, leading to higher stability behavior [25]. Graphene oxide 1700 mg of ethanol, followed by stirring at room temperature for 48 h.
has used as a buffer layer for PSCs to increase their stability [26]. Li et al. The deposited MTiO2 layer is put in a furnace and heated up to 500 ℃. It
used functionalized reduced graphene oxide (rGO) as a spacer layer at is kept for 60 min at this temperature. As active layer (with a thickness
perovskite/HTL interface to increase stability of PSCs [27]. of ̴ 470 nm), 1.4 M FAPbI3 solution is spin-coated on the FTO/CTiO2/
Indeed, rGO material with good conductivity and tunable optical and MTiO2 substrate, while 500 µL of toluene (Sigma Aldrich, 99.8%) anti-
electronic properties [28–30] is an appropriate candidate to use an in­ solvent was poured on it during deposition process. To complete for­
termediate layer in regular PSCs. Here, we attempted by employing rGO mation of FAPbI3 layer, it is annealed at 150 ℃ for 15 min. 2.5 mg of
on FAPbI3 to keep safe it from degradation, in addition to increasing its GO, and different rGO materials (24 h, 48 h, 72 h, and 96 h) are
photovoltaic performance. Reduction level of rGO was tailored to in­ dispersed to 1 mL toluene with sonication at RT for 2 h. Then, 50 µL of
crease its conductivity and hydrophobicity. We observed that increasing GO or rGO dispersions were spin coated on the perovskite layers at speed
the reduction level of rGO to an optimal level obtains the favorite rGO of 3500 rpm for 30 s, followed by post-annealing at 70 ℃ for 20 min.
sheets to protect the perovskite layer, while as a connecting bridge be­ 80 µL of standard spiro-OMeTAD HTL precursor was spin-coated on the
tween perovskite and HTL increases charge transfer in devices. The rGO FAPbI3 or FAPbI3/GO or FAPbI3/rGO substrates at speed of 4000 rpm
intermediate layer avoids charge accumulation in the system. Charge for 30 min. At the end, 80 nm Au electrodes were evaporated on HTLs at
recombination was reduced by rGO incorporation to perovskite grain high vacuum level with a rate of 2 ◦ A/s. A schematic view of fabrication
boundaries. Finally, we recorded a champion PCE of 22.29% for target process has depicted in Fig. 2.
PSCs, higher than the 18.90% obtained for the control PSCs.
2.4. Characterizations
2. Experiments
FESEM (Mira3, TESCAN) instrument at 15 KV was used to monitor
2.1. Synthesis of graphene oxide morphology of untreated and treated perovskite films. XRD diffrac­
tometer (Philips PW1730 X-ray) was used to collect the perovskite and
We used the "Improved Hammer" method to convert graphite sheets materials diffraction patterns. UV–VIS spectrophotometer (Thermo
to graphene oxide (GO) sheets [31] with the assistance of sulfuric acid Biomate5) was employed to investigate the absorbance of FAPbI3 layers
(H2SO4, Merck, 98%). 10 g graphite flakes (Merck) and 5 g sodium ni­ and materials. PL spectrophotometer (CARY ECLIPSE) was used to
trate (NaNO3, Sigma Aldrich, 99%) are added into 240 mL H2SO4, fol­ measure the perovskite’s PL spectra. To measure photovoltaic of
lowed by vigorous stirring at a temperature of 2 ℃ for 4 h. After that, different PSCs, they were exposed to a calibrated AM 1.5 G irradiance.
30 g potassium permanganate (KMnO4, Sigma Aldrich, 99%) is mixed Then, their J-V trends were recorded using a Keithley 2401 source.
with the solution, followed by stirring at the fixed temperature of 20 ℃ Contact Angle CAG-20 devices was recorded water droplets’ contact
for 24 h. As the reaction progresses, the solution color changes to light angle on different perovskite layers. A Raman device (Takram
brown. To complete the reaction 500 mL of distilled water and then P50C0R10) was employed to record Raman spectra of different rGO
125 mL hydrogen peroxide (H2O2, Merck, 30%) are added to the solu­ materials.
tion during stirring. The obtained solution is filtered and added it
200 mL diluted hydrochloric acid (3%, Merck), followed by stirring for 3. Results
24 at room temperature. The solution is then centrifuged at 8000 rpm to
remove impurities and SO2- 4 ions. The obtained GO precipitates are dried In this work, the reduction level of rGO is determined by the reaction
in an oven for 24 h at a temperature of 60 ℃. time. The effect of this parameter on the reduction level of GO was
studied using UV–Visible spectra. UV-Visible spectroscopy (Fig. 1a)

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R. Alabada et al. Synthetic Metals 304 (2024) 117578

Fig. 1. (a) UV-Vis, (b) Raman, (c) XRD of different rGO powders.

confirmed the successful GO reduction. The UV-Visible spectrum of GO density, which leads to a more amorphous carbon structure and there­
displayed an absorption peak at 234 nm which ascribed to the π–π* fore, attenuates all Raman peaks [40]. The ratio of ID/IG exhibits an
transition of C– –C [32,33]. Following reduction with hydroiodic acid increase as the reduction time progresses, with the exception of the final
over different periods (24, 48, 72, and 96 h), the peak of rGO was time point at 96 hours. The increase in the ID/IG ratio from 24 to 74 h
observed at 266, 269, 279, and 268 nm respectively. The plasmon peaks could be due to the fact that the reduction process causes some disrup­
shift reveals the decreasing of the carboxyl groups [34]. The red shift in tion of the graphene structure, creating more edge defects and thus
the absorption of rGO indicates the restoration of electronic conjugation increasing the intensity of the D peak. The increase in ID/IG in rGO
within the graphene sheets, suggesting boosted electron density after compared to pristine GO is due to the removal of oxygen functional
reduction [35]. groups, indicating disorder and an increase in the number of sp2 clusters
Raman spectroscopy (Fig. 1b) shows that the characteristic bands D after reduction [41]. This increase in ID/IG ratio may seem counterin­
and G for both GO and rGO are located at 1394 cm− 1 and 1583 cm− 1, tuitive considering that conductivity increases (since defects usually
respectively [36]. The D band indicates lattice defects due to disordered decrease conductivity), but this could be due to the overwhelming effect
sp3 carbon atoms and oxygen functions, while the G band arises because of removing insulating oxygen features, which outweighs the effects of
stretching of sp2 carbon atoms [37,38] in both chains and rings. G and D increased defect density [42]. With the restoration of the C– –C bonds
bands confirm the graphitic structure of materials. Two weak peaks in after a long reduction time (96 h), the intensity of the G peaks increased,
the 2800 cm− 1 to 3200 cm− 1 region are related to the flat G’ band, and leading to a decrease in the ratio of ID/IG. However, after 96 h, the ID/IG
the D+G mode, which confirms presence of defects in GO. The intensity ratio decreases, suggesting that the reduction process may be
ratio between the D peak and the G peak (ID /IG ratio) is commonly used over-optimised and begin to damage the graphene structure, creating
as an indicator of defect density in the rGO structure. A higher ID /IG more defects or possibly agglomerating the rGO particles. This could
ratio reveals more defects [39]. The behaviour of ID/IG in graphene lead to a decrease in conductivity.
exhibits two distinct patterns based on the number of defects as disorder The XRD patterns of rGO materials are shown in Fig. 1c along with
levels grow. In the context of defect density, it has been shown that the those of GO. XRD pattern of GO shows a sharp and intense peak at about
ratio of ID/IG exhibits an upward trend, indicating a rise, within a regime 10◦ , indicating the presence of GO. As the reduction time increases, the
characterized by relatively low defect density. This phenomenon may be intensity of th GO characteristic peak decreases, and after 48–96 h of
attributed to the fact that a larger defect density leads to a greater reduction, this peak disappears completely. Instead, a new peak appears
occurrence of elastic scattering. This phenomenon is seen until a with an angle of 25.5◦ . This change in the XRD pattern indicates that the
threshold of "high" defect density is reached, beyond which the ID/IG GO reduction process affects its structure. The sharp peak at 10◦ cor­
ratio starts to decline. This reduction is attributed to the growing defect responds to the (001) plane of GO, which is characteristic of the layered

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R. Alabada et al. Synthetic Metals 304 (2024) 117578

structure of this material. The appearance of a new peak at an angle of more efficient charge extraction and collection. However, when the
25.5◦ indicates the rGO formation. The shift in the position of GO peak reduction process is extended to 96 h, the photovoltaic parameters start
from 10◦ to 25.5◦ indicates the restoration of the sp2 hybridization in the to deteriorate, indicating a degradation in the performance of the solar
carbon lattice structure of rGO. The appearance of a new peak at 25.5◦ cell. Additionally, the performance of the device is negatively affected
indicates that the reduction process also causes the formation of a new when GO is added, as it is non-conductive and hinders the flow of charge
phase. This peak could correspond to the (002) plane of rGO. The carriers. By employing an rGO with an optimized reduction time of 72 h,
occurrence of this peak suggests that the reduction process causes the a champion PCE of 21.86% with an FF of 77.73%, a VOC of 1.150 V, and a
conversion of GO to rGO, which is consistent with literature on the JSC of 24.46 mA.cm− 2 was recorded for PSCs. While the PSCs uneq­
reduction of GO [43]. uipped with rGO interlayer obtained a champion PCE of 18.90%. Raman
The FESEM image provides a revealing visualization of the FAPbI3 analysis and photovoltaic parameters has shown that the reduction of
(formamidinium lead iodide) perovskite layer (Fig. 3a), an integral part GO occurs between 24 h and 72 h, leading to increased conductivity and
of the structure of our perovskite solar cells. The image reveals a wealth voltage. The optimal reduction time appears to be 72 h, as this results in
of detailed information about the morphology, grain size, and unifor­ improved conductivity, voltage, and photovoltaic parameters. However,
mity of this layer. As seen in Fig. 3a, the perovskite layer has a crystalline when the reduction process is extended to 96 h or when GO is added, the
structure. The crystals are well-defined and separated from each other, performance of the device is compromised, leading to decreased con­
indicating a high-quality layer. The perovskite grains are big with few ductivity, voltage, and photovoltaic parameters. These findings suggest
grain boundaries and range in size from 300 to 500 nanometers. There that careful optimization of the reduction process and the use of
are no holes in the perovskite layer, which is evenly placed over the appropriate materials are crucial for achieving highly efficient solar
substrate. The perovskite layer will likely produce an excellent solar cell cells. To ensure the reproducibility of this work, ten solar cells were
performance based on the FESEM picture because of its acceptable grain prepared from each series. The statistical graph depicting their effi­
size and great uniformity. FESEM delivers a limited perspective even ciency can be found in Fig. 4b.
though it includes structural information. To completely comprehend IPCE spectra of control and 72 h PSCs were measured to provide
the solar cell’s performance, further characterization methods including information on the performance PSCs. As observed in Fig. 4c, the cell
optical absorption, XRD, and photovoltaic measurements are required. modified with 72 h rGO has higher IPCE value than the control cell over
The UV-Vis spectra of the FAPbI3 perovskite layer (Fig. 3b) revealed a the entire wavelength range measured. The integrated current densities
peak in the range of 819 nm, indicating that the perovskite layer has from these curves are 23.97 and 24.34 mA.cm− 2 for the devices control
been properly formed and is able to absorb light in the visible portion of with 72 h PSCs, which support the higher JSC obtained in J-V charac­
the spectrum [42]. The XRD pattern of the FAPbI3 perovskite film shows terizations (See Table 1). The improved IPCE response can be attributed
four diffraction peaks at 14.14◦ ,24.54◦ , 28.34◦ , 31.79◦ , 40.54◦ , and to improved light collection and carrier dynamics in the rGO-based
43.09◦ , respectively, with Miller indices of (001), (111), (002), (012), device. In particular, the alignment of energy levels at the interface
(022) and (003) (Fig. 3c). It shows the successful assembly of FAPbI3 between the perovskite and HTL is likely better aligned due to the
perovskite [44]. presence of rGO. This favors enhanced extraction of holes from the
The J-V diagram represents the photovoltaic performance of PSCs photoactive perovskite layer into the HTL. The results confirm the role of
without or with rGO interlayers (Fig. 4a). In this study, the reduction of rGO in optimizing the photovoltaic performance of the solar cell through
GO from 24 h to 72 h leads to an increase in solar cell efficiency, while at improved charge transfer at the key interface. Fig. 4d shows the reverse
a reduction time of 96 h, the efficiency is reduced. Table 1 lists the and forward J-V scans for control and 72 h PSCs, by inserting the hys­
photovoltaic values for these devices. The photovoltaic parameters teresis index (HI) computed as defined by Sanchez et al. [45]. As
measured provide insights into the performance of the solar cell. In this evident, control and 72 h devices showed a marked hysteric behavior
study, the addition of a layer between the perovskite layer and the hole- but, notably, the rGO interlayer reduces the HI value by 2.67 fold. This
transport layer, along with the reduction of GO from 24 h to 72 h, leads suggests that the 72 h rGO enhances the charge extraction in the PSCs.
to an improvement in the photovoltaic parameters. It is due to the In order to conduct a more comprehensive analysis of the trans­
enhanced charge transport properties of the rGO layer, which enable portation and recombination characteristics of photogenerated carriers

Fig. 2. Schematic view of solar cell fabrication. For more details should be check the solar cell construction sub-section.

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Fig. 3. (a) FESEM, (b) UV-Vis, and (c) XRD of perovskite layer deposited FTO/CTiO2/MTiO2 layer.

[46], the photoluminescence (PL) spectra of the devices, which were Mott− Schottky plot in Fig. 5c was used to calculate the built-in potential
subjected to modification with reduced graphene oxide (rGO), graphene (Vbi). The device with rGO had a higher Vbi than the device without it.
oxide (GO), and a control device, were examined and are shown in This means that the rGO can reduce the backward movement of carriers
Fig. 5a. Obviously, the sample prepared with 72 h rGO shows the at the interface between the HTL and the perovskite and increase the
weakest PL peak, referring to the lowest carriers recombination and thus charge separation, which leads to a high VOC [51].
the best photovoltaic efficiency [47,48]. The PL spectra also support the To calculate hole mobility (μ), dark J0.5-V plots of hole-only devices
results of J-V tests as depicted in Fig. 4a. In order to demonstrate the are fitted with Mott-Gurney law in SCLC region, as follow:
beneficial impact of rGO treatment on the carrier transfer dynamics of √̅̅̅̅̅̅̅̅̅̅̅
3V ε0 εr μ
PSCs, electrochemical impedance spectroscopy (EIS) was performed JD 0.5 = √̅̅̅̅̅̅̅ (1)
under dark conditions at open-circuit voltage. The Nyquist plots of the 8L3
various PSCs are presented in Fig. 5b, and these curves were fitted using
Wherein L is the FAPbI3 layer thickness, JD is the dark current density,
an equivalent model (as shown in the inset of Fig. 5b). The PSC device
and V is the used voltage, ε0 is the vacuum permittivity, εr is the
modified with 72 h rGO exhibits a significantly higher recombination
dielectric constant of FAPbI3 (εr = 47). A μ of 2.51 × 10− 3 cm2 V − 1 s− 1 and
resistance (Rrec) value of 871 Ω. This Rrec value noticeably decreases to
12.31 × 10− 3 cm2 V − 1 s− 1 was measued the control and 72 h device,
257 and 217 Ω for the control devices and the device with the GO layer
respectively. The improved hole mobility indicates positive role of 72 h
atop the perovskite layer, respectively. The largest Rrec was measured for
rGO interlayer for facilitating charge transfer at perovskite/HTL
a cell with 72 h rGO interlayer, implying the mitigation of charge
interface.
recombination rate at the perovskite/HTL interface [49,50]. Besides the
We optimized the reduction level of GO and found that 72 h is the
charge transfer resistance (RCO) of PSCs by employing 72 h rGO inter­
optimal time to reduce GO, which improved the cell efficiency. We
layer was reduced to 84.7 Ω from 147 Ω obtained for control PSCs. It
applied one, two, and three layers of 72 h rGO on the perovskite layer
indicates that 72 h rGO material induces charge transfer at per­
and fabricated PSCs. We tested their photovoltaic performance under
ovskite/HTL interface and reduces photocurrent losses in PSCs. Then, to
simulated sunlight (AM 1.5 G). Fig. 6a shows the J-V curves of these
quantify the carrier concentration, we obtain the capacitance–voltage
PSCs. Table 2 summarizes the photovoltaic parameters for these devices.
(C–V) curve of the PSC where its slope can be used to determine the
The best efficiency was achieved with two layers of 72 h rGO because
carrier density by Mott-Schottky equation (M-S). The linear part of the
they formed a smooth and uniform surface that covered the perovskite

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R. Alabada et al. Synthetic Metals 304 (2024) 117578

Fig. 4. (a) J-V of different PSCs and (b) related PCE distributions. (c) IPCE spectra of control and 72 h PSCs. (d) J-V curve of control and 72 h PSCs in reverse and
forward directions.

discussed (Fig. 7).

Table 1
In the case of one and two layers of rGO (Figs. 7a and 7b), FESEM
Photovoltaic values calculated from J-V response of different PSCs.
images illustrate a uniform distribution of rGO on the perovskite surface.
Device VOC (V) JSC (mA. FF (%) PCE (%) The rGO layers are observed to be smooth and continuous, indicating
name cm− 2)
good coverage and uniformity. These characteristics are believed to
Control Average 1.048 24.12±0.21 71.06 17.96 promote efficient charge extraction, which could explain the observed
Best 24.08
±0.024 ±1.48 ±0.67
increase in the conductivity of the perovskite solar cells. FESEM image of
1.090 72.02 18.90
GO Average 1.040 23.54±0.28 69.84 17.10 the sample with three layers of rGO reveal a markedly different
Best ±0.022 23.52 ±1.07 ±0.45 morphology (Fig. 7c). There is a noticeable accumulation of rGO,
1.010 69.91 17.59 leading to the formation of agglomerates. The rGO layers appear rough
24 h Average 1.080 24.16±0.18 73.68 19.23 and discontinuous, with large areas of the perovskite surface being
Best 24.27
obscured by the rGO. This non-uniform distribution might impede effi­
±0.022 ±0.94 ±0.51
1.110 74.12 19.97
48 h Average 1.104 24.19±0.18 75.37 20.13 cient charge extraction, possibly resulting in a decrease in the overall
Best ±0.023 24.35 ±1.05 ±0.55 efficiency of the solar cells. These FESEM observations align with the
1.130 76.52 21.06 performance data of the PSCs and provide valuable insights into the role
72 h Average 1.120 24.23±0.24 77.27 20.97
of rGO as an interfacial layer. Our findings suggest that while a moderate
Best ±0.021 24.46 ±1.02 ±0.57
1.150 77.73 21.86
amount of rGO can enhance the conductivity of perovskite solar cells, an
96 h Average 1.110 24.18±0.25 76.28 20.47 excessive amount may lead to degradation in performance, presumably
Best ±0.030 24.49 ±1.02 ±0.56 due to the formation of rGO agglomerates that disrupt charge transport.
1.150 76.44 21.53 In addition, Fig. 7d shows cross-sectional FESEM of perovskite layer
with 2 round of rGO deposition treatment. As can be seen, rGO depo­
layer completely and increased the charge extraction. For 2-dep PSCs, a sition acted as an interface treatment and cannot be detected its thick­
champion efficiency of 22.29% is obtained, which is effectively higher ness through FESEM. Therefore, it can be concluded that the rGO
than the control PSCs. Fig. 6b depicts PL spectra of the treated perovskite treatment didn’t affected on light-harvesting layer and perovskite
layers with 1, 2, and 3 repeat of 72 h rGO deposition. As shown, PL thickness is remained around 470 nm.
quenching for 2-dep samples is higher than the 1-dep and 3-dep samples, The hydrophobic nature of rGO can protect perovskite from mois­
which indicates that lower charge recombination in PSCs is accessible ture, which can improve the stability of perovskite solar cell. Fig. 8
with two round deposition of 72 h rGO material. shows the normalized efficiency of PSCs with different number of times
The incorporation of rGO into PSCs as an interlayer between the the rGO deposition in PSCs as an interfacial layer. Fig. 8a shows the
perovskite and the HTL has been investigated using FESEM monitoring. ambient air stability of the PSCs at room temperature in dark conditions
Top-view FESEM images of the perovskite/HTL interface with varying in an environment with RH of 25–30%. The graph indicates that the
the number of times the rGO layer deposition are presented and PSCs with rGO have higher stability than the reference PSC, as their

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Fig. 5. (a) PL of different FTO/CTiO2/MTiO2/FAPbI3 and FTO/CTiO2/MTiO2/FAPbI3/GO or rGO structures. (b) EIS of different PSCs. (C) C-V curves of control and
72 h PSCs. (d) J1/2-V curves of hole-only devices based on control and 72 h perovskites.

Fig. 6. (a) J-V of different PSCs with 1, 2, and 3 round of rGO deposition. (b) PL spectra of perovskite layers treat with 1, 2, 3 round of 72 h rGO deposition. For PL
measurements, substrates was FTO/CTiO2/MTiO2.

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R. Alabada et al. Synthetic Metals 304 (2024) 117578

Table 2 4. Conclusion
Photovoltaic values extracted from J-V responses of PSCs fabrication.
Device name VOC (V) JSC (mA.cm− 2) FF (%) PCE (%) We fabricated regular FAPbI3-based PSCs with the assistance of a
toluene anti-solvent. Then, to increase their photovoltaic efficiency, we
1-dep (72 h) 1.150 24.46 77.73 21.86
2-dep 1.150 24.29 79.77 22.29 developed an rGO interlayer over the FAPbI3 layer. The results showed
3-dep 1.150 24.02 75.72 20.92 that controlling the reduction level of rGO material is a key parameter to
increase the potential of rGO interlayer for improving PSCs’ perfor­
mance. The Raman spectra of rGO during reduction time showed an
efficiency decreases more slowly over time. The PSC with 3 layer of rGO increment in the ID/IG ratio of rGO compared to pristine GO, indicating
(3-dep) has the highest stability, followed by the PSC with 2 layer of rGO disorder and an increase in the number of sp2 clusters after reduction,
(2-dep). This suggests that rGO can improve the moisture resistance of which increases rGO conductivity. It led to charge transfer and hole
PSCs by acting as a hydrophobic barrier between the perovskite layer mobility improvements at the FAPbI3/HTL interface and recorded a
and the ambient air. Fig. 8b shows the thermal stability of the PSCs at a champion efficiency of 21.78% for PSCs. Then, by monitoring the
temperature of 50 ◦ C in dark conditions. The graph indicates that the number of times of rGO deposition, PSCs’ efficiency more boosted to
PSCs with rGO have higher stability than the net PSC. The PSC with 3 22.29% due to further reduction of charge recombination in the solar
layers of rGO (3-dep) has the highest stability, followed by the PSC with cell system. In addition, the hydrophobic nature of rGO improved the
2 layers of rGO (2-dep). This suggests that rGO can improve the thermal ambient air stability of PSCs.
stability of PSCs. The static contact-angle measurements depicted in
Fig. 8c- f provide proof in support for the results of the stability in Consent to participate
ambient air.
Table 3 shows some related research recently reported to use rGO The research in this paper does not involve research on humans and/
materials for increasing efficiency and stability of PSCs. or animals.

Fig. 7. Top-view FESEM of perovskite layer with (a) 1 round, (b) 2 round, and (c) 3 round of rGO deposition. (d) Cross-sectional FESEM of perovskite layer with 2
round rGO deposition.

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R. Alabada et al. Synthetic Metals 304 (2024) 117578

Fig. 8. (a) Ambient air stability of devices at RT in dark conditions in environment with an RH of 25–30%. (b) Thermal stability of devices at temperature of 50 ℃ in
dark conditions. Contact angle of water droplets on (c) control perovskite and perovskite layers with (d) 1 round, (e) 2 round, and (f) 3 round of 72 h rGO deposition.

Table 3
Summary of similar studies with using various rGO-based treatments and comparison to this research. M indicates mesoporous and P indicates planner.
Ref Devise Strategy PCE Stability

n-i-p M rGO in perovskite precursor ̴14.9% Remained ̴40% PCE after 720 h storing in dark condition and RH of 55% and temperature of 25 ℃.
[52]
n-i-p M rGO in HTM precursor ̴20.0% Remained ̴80% PCE after 60 h storing in dark condition at RH of 45% and temperature of 85 ℃.
[53]
n-i-p M rGO as spacer layer between ̴20.0% Remained̴ 95% PCE after 1000 h storing under full-sun illumination at temperature of 60 ℃ in inert ambient.
[54]
HTM and gold
n-i-p M rGO/Bi2O3 in ETL precursor ̴17.0% Remained ̴80% PCE after 60 h storing in dark condition at RH 30–40% at temperature of 25 ℃.
[55]
n-i-p P GO QDs interlayer between ̴18.5% Remained 90% of initial PCE after continuous operation under 1 sun illumination and the damp heat test at 85
[56]
perovskite and HTM ◦
C.
This n-i-p M rGO as spacer between 22.29% Remained 95% PCE after 1840 h ambient air stability with RH of 25–30% at temperature of 25 ◦ C in dark
work perovskite and HTM conditions. Remained 90% PCE after 240 h thermal stability at temperature of 50 ◦ C in dark conditions.

Consent to publish the work reported in this paper.

All the authors are giving consent to publish. Data availability

Funding Data will be available based on reasonable request.

This research received no external funding. References

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