Solar Energy 213 (2021) 59–66

Contents lists available at ScienceDirect

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

Enhancement of the photovoltaic performance and the stability of

perovskite solar cells via the modification of electron transport layers with
reduced graphene oxide/polyaniline composite
H.R. Mohseni a, b, c, 1, M. Dehghanipour a, b, 1, N. Dehghan a, b, F. Tamaddon d, M. Ahmadi c,
M. Sabet e, A. Behjat a, b, *
a
Department of Physics, Faculty of Science, Yazd University, Yazd, Iran
b
Photonics Research Group, Yazd University, Yazd, Iran
c
Department of Physics, Faculty of Science, Vali-e-Asr University of Rafsanjan, Rafsanjan, Iran
d
Department of Chemistry, Faculty of Science, Yazd University, Yazd, Iran
e
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, Rafsanjan, Iran

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

Keywords: The performance of perovskite solar cells (PSCs) may be improved through the incorporation of suitable ma­
Reduced graphene oxide-polyaniline terials into electron transport layer (ETL). In this study, reduced graphene oxide/polyaniline composite (G-PANI)
Triple cation was introduced into mesoporous TiO2 (mp-TiO2) precursor solution to enhance the performance of triple cation
Electron transport layer
perovskite solar cells (TC-PSCs). As it was observed, the modification of mp-TiO2 could increase the short-circuit
Perovskite solar cell
current density (Jsc) and the fill factor (FF) parameters of the fabricated devices. So, by employing G-PANI
nanocomposite into the mp-TiO2 ETL layer, a champion power conversion efficiency of 16.48% was obtained,
33.7% higher than that of pure mp-TiO2 devices. This occurred through improvements in the crystalline struc­
ture, mitigate charge recombination at the TiO2/perovskite interface, reduce charge trapping at the perovskite
surface through grain boundaries passivation, and tailor edge absorption of the perovskite films. The proposed
approach not only increases the photovoltaic parameters of TC-PSCs but also improves the shelf stability of TC-
PSCs. The obtained results prove that G-PANI composite as compared to pristine reduce graphene oxide is a
better candidate for modification of mp-TiO2 ETL to boost the performance of PSCs and also stabilize them.

1. Introduction
Presently, many countries in the world have turned to renewable
resources to meet their energy needs and reduce the effect of pollution
(Gielen et al., 2019). Due to the growth of the world population, the
energy demand is increased, and the proportion of the renewable types
of energy is expected to rise globally. Among renewable energies, solar
energy has attracted significant attention in the field of research. Upon
the discovery of the principles of operating photovoltaic devices by
Becquerel in 1839, research in this area began and different types of
solar cells, such as silicon solar cells (Tiedje et al., 1984), quantum dots
solar cells (Doosthosseini et al., 2015; Nozik, 2002), dye-sensitized solar
cells (O’Regan and Grätzel, 1991), organic solar cells (Meissner and
Wohrle, 1991; Zhao et al., 2016) and perovskite solar cells (PSCs)
(Aeineh et al., 2018; Kojima et al., 2009; Yang, W.S. et al., 2015) were
proposed. Over the past decade, the new generation of organometal
halide PSCs has been the fastest-growing technology. This is owing to
the excellent optoelectronic properties and the low fabrication cost of
such cells. The power conversion efficiency (PCE) value has reached
23.4% (Yoo et al., 2019), which makes PSCs a viable rival to silicon solar
cells. The fast increase in the PCE value of PSCs is mainly attributed to
the excellent properties of perovskite materials, such as high absorption
in a wide range, low rate of recombination, long carrier diffusion length,
high charge-carrier mobility and suitable and tunable bandgap (Chen
et al., 2018; Dehghan and Behjat, 2019; Mozaffari et al., 2018; Torabi
et al., 2019).
PSCs have two major configurations, i.e. mesoporous (Aeineh et al.,
2018) and planar (Liu et al., 2013), which benefit from a scaffold and a

* Corresponding author at: Department of Physics, Faculty of Science, Yazd University, Yazd, Iran.
E-mail address: abehjat@yazd.ac.ir (A. Behjat).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.solener.2020.11.017
Received 26 August 2020; Received in revised form 28 October 2020; Accepted 4 November 2020
Available online 27 November 2020
0038-092X/© 2020 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
H.R. Mohseni et al.
thin flat layer respectively. Mesoporous PSCs consist of compact TiO2,
mesoporous TiO2 (mp-TiO2), a light-harvesting layer and an Au layer.
However, in a planar configuration, a light-harvesting layer is deposited
with any scaffolding material between a compact TiO2 electron trans­
port layer (ETL) and an Au layer. Based on our knowledge, the highest-
efficiency PSCs have been reported for mesoporous structures so far.
Also, the stability of mesoporous devices has been reported to be higher
than that of planer structures (Yao et al., 2017). A large body of research
refers to the mp-TiO2 layer as an effective ETL which plays a vital role in
facilitating the collection of electrons and the transportation of photo­
generated electrons to FTO substrates (Chen et al., 2019; Yang, Y. et al.,
2015; Ye et al., 2018), modifying the TiO2/perovskite interface (Masood
et al., 2020) and reducing the hysteresis effect in PSCs (Sidhik et al.,
2018). However, mp-TiO2 ETLs suffer from high charge recombination
(Chavan et al., 2019). Recently, to address this issue and improve the
performance of PSCs, researchers have used different materials in mp-
TiO2 layers (Agresti et al., 2017; Giordano et al., 2016; Pourradi et al.,
2019; Yue et al., 2015). Among them, graphene (Han et al., 2015) and its
derivatives (Cho et al., 2016; Ryu et al., 2017; Wang, J.T.-W. et al.,
2014) have proved to be good candidates due to their high conductivity,
transparency, flexibility, and low cost (Nouri et al., 2018; Ryu et al.,
2017). Additionally, efforts have been focused on increasing the stability
of PSCs (Bai et al., 2019; Kim et al., 2019; Saliba et al., 2016; Uddin
et al., 2019). Among different approaches that address the stability issue
of PSCs, the use of perovskite materials with mixed cations and halides,
especially Cs+-containing perovskites, has widely been favored as an
effective way of stabilizing PSCs (Niu et al., 2016; Saliba et al., 2016;
Singh and Miyasaka, 2018; Yi et al., 2016).
The present study is conducted to evaluate the effects of reduced
graphene oxide/polyaniline (G-PANI) nanocomposite on the perfor­
mance and stability of mesoscopic-type PSCs. The study starts with the
fabrication of a mixed cation PSCs absorber by the adding of a small
amount of G-PANI to an mp-TiO2 ETL layer. Using the sequential
deposition method, the PSCs are fabricated in ambient conditions with
controlled humidity. Furthermore, the effect of G-PANI concentration
on the cell performance is explored by the addition of different amounts
of G-PANI to the mp-TiO2 precursor. The G-PANI-applied devices yield a
champion power conversion efficiency (PCE) of 16.48%, which is about
a 33.7% improvement, as compared with reference cells (12.32%).
Additionally, non-encapsulated PSCs with G-PANI-containing materials
exhibit excellent long-term stability. The results of the study show that
G-PANI nanocomposite is preferable to pristine RGO to boost the effi­
ciency of PSCs and stabilize them.
2. Experimental
A detailed account of the material synthesis, solution preparation,
device fabrication, and characterization is presented in the Supporting
Information, Experimental details section.
3. Results and discussion
In this study, reduced graphene oxide (RGO) and a reduced graphene
oxide/polyaniline (G-PANI) nanocomposite were successfully synthe­
sized and then characterized through some measurements. There were
also effective interactions between PANI and RGO layers (For more
details, refer to the Supporting Information, Figures S1-S3).
Based on the experimental details expressed in the Supporting In­
formation section, triple-cation perovskite solar cells (TC-PSCs) were
fabricated by the spin-coating of the (Cs/FA/MA)Pb(IBr) perovskite on
the mesoporous TiO2 (mp-TiO2) ETL layer through a sequential depo­
sition method. This configuration was further modified by the addition
of G-PANI nanocomposite to a diluted mp-TiO2 precursor. A G-PANI
solution was added to the mp-TiO2 precursor at the volume ratio of 0%,
2%, 4%, and 8% to fabricate perovskite films labeled as Ref., GP-2%, GP-
4%, and GP-8% respectively. Additionally, for comparison, mp-TiO2 was
60
Solar Energy 213 (2021) 59–66
modified with pristine RGO. For this purpose, 4% of an RGO solution in
terms of volume ratio was added to the mp-TiO2 precursor, and the
corresponding perovskite films were labeled as G-4%. To study the
difference between the TC-PSCs fabricated with pure mp-TiO2 and those
fabricated with modified mp-TiO2, the morphological, crystallographic,
and optical characterizations of the prepared perovskite layers were
carried out. Furthermore, the overall performance of the fabricated solar
cells was evaluated through PCE measurements.
3.1. Study of the effects of ETL modification on the perovskite film
properties
The optical properties of the devices were studied and compared
through optical transmittance, UV–vis absorption spectra and Tauc plot
analysis (Fig. 1). As shown in Fig. 1a, when mp-TiO2 was modified with
RGO or G-PANI, the absorption of the perovskite layer was increased. It
can also be seen that the light absorption of the perovskite film improved
as the amount of the G-PANI precursor was increased in mp-TiO2.
Through optical transmittance measurements (Fig. 1b), it was found
that, when the volume of G-PANI increased to 8% in the mp-TiO2 pre­
cursor, the transmittance of the modified mp-TiO2 layer would signifi­
cantly reduce. For the samples with 4% of G-PANI, however, the
transmittance of the modified mp-TiO2 would increase. So, it can be
argued that, in contrast with the GP-4% device, the GP-8% device had
improved absorbance due to the blurring of the mp-TiO2 layer not the
improving of the light-harvesting ability of the perovskite film. This is
why the albeit absorbance of the GP-8% device was higher than that of
the 4%-GP device. No further improvement, however, can be expected
in the efficiency of the corresponding device (See Fig. 4b). Moreover, the
Tauc plots in Fig. 1c show a slight redshift in the value of the bandgap
energy (Eg) of the perovskite film from 1.58 eV (for the pure mp-TiO2
devices) to about 1.56 eV as G-PANI was incorporated into the mp-TiO2
(for the GP-4% devices). Accordingly, the absorption edge of the
perovskite layers changed from 782 nm to 791 nm, resulting in the
increased photocurrent density of TC-PSCs (Tang et al., 2018; Yi et al.,
2016). This redshift was also observed in the steady-state photo­
luminescence (PL) measurements of the devices (Fig. 2a), which is in
agreement with the corresponding absorption spectra.
As depicted in Fig. 2a, the incorporation of RGO and G-PANI in mp-
TiO2 suppressed the peak intensity of PL. The PL intensity reduced step
by step from Ref., GP-2% to GP-4%. This PL quenching was due to the
promoted charge transfer at the TiO2/perovskite interface arising from
the G-PANI incorporation. The figure also shows the mitigation of
recombination at the TiO2/perovskite interface. However, when the G-
PANI additive increased to 8%, the PL intensity increased again, which
was caused by the excess G-PANI. This increase in the PL intensity is
suggestive of a reduction in the crystallinity of the perovskite film
(Zheng et al., 2019; Zheng et al., 2018), which is clear in the corre­
sponding XRD pattern in Fig. 2b. Besides, the PL quenching in the
perovskite film with 4% of G-PANI is more than that in the perovskite
film with 4% of RGO, which proves a better electron transfer in the GP-
4% device.
The X-ray diffraction (XRD) technique was employed to investigate
the effect of the mp-TiO2 modification on the crystalline properties of
the perovskite layer. As it can be seen in Fig. 2b, there are some peaks at
about 14.02, 24.4 and 28.2 related to the preferred (0 0 1), (1 1 1), and
(0 0 2) crystal planes respectively (Wang et al., 2019). It is also shown
that, for the devices fabricated with 2% and 4% of the G-PANI additive,
the PbI2 peak (at 12.7◦ ) is partially suppressed. In the case of G-PANI-
8%, however, the peak is enhanced. The samples fabricated with 4% of
G-PANI proved to have a lower PbI2 peak intensity than those fabricated
with 4% of RGO. Additionally, among the investigated samples, the
sample with 4% of G-PANI had more orientation in the (0 0 1) direction,
which implies its better crystalline structure. It is worth noting that there
was not any non-perovskite phase like δ-FAPbI3 in the XRD patterns of
the fabricated samples, suggesting the presence of an appropriate
H.R. Mohseni et al. Solar Energy 213 (2021) 59–66

Fig. 1. (a) Absorbance spectra of perovskite solar cells with different mp-TiO2 substrates. (b) Optical transmittance of different mp-TiO2 layers. (c) Corresponding
Tauc curves of different triple-cation perovskite solar cells.

Fig. 2. (a) The steady-state photoluminescence spectra and (b) the XRD patterns of different perovskite samples.

amount of CsPbI3 in the PbI2 precursor.
To study the morphology of different perovskite films, scanning
electron microscopy (SEM) was performed. The surface morphologies of
the deposited perovskite films atop different pure and modified mp-TiO2
layers are shown in Fig. 3. As it can be seen, by the modification of the
mp-TiO2 precursor with pristine RGO or G-PANI, the surface defects of
the perovskite layer were significantly reduced. Also, the addition of G-
PANI to the mp-TiO2 precursor passivated the grain boundaries (GBs) of
the perovskite layer and created a compact layer (Fig. 3c). Actually, in
devices with pure mp-TiO2, there are obvious gaps within the grains of
perovskite, which serve as centers for charge carrier trapping and in­
crease the charge recombination in the perovskite layer (Lee et al., 2018;
Uratani and Yamashita, 2017). In this study, RGO was added to mp-
TiO2, and those gaps nearly disappeared. Moreover, G-PANI was intro­
duced into mp-TiO2, and the GBs faded almost completely. This is
consistent with the XRD pattern and PL quenching.

61
H.R. Mohseni et al.
Fig. 3. (a) FESEM images of the perovskite films coated on pure mp-TiO2 and the mp-TiO2 modified with (b) 4% of reduced graphene oxide (RGO) and (c) 4% of
reduced graphene oxide/polyaniline nanocomposite (G-PANI).
3.2. Photovoltaic properties of PSCs achieved via ETL modification
First, to probe the impact of the G-PANI concentration on the
photovoltaic (PV) performance and to find the optimal volume of G-
PANI in the mp-TiO2 precursor, hole transport layer (HTL)-free TC-PSCs
with various amounts of G-PANI were fabricated, and their cur­
rent–density/voltage (J-V) values were measured under AM 1.5 with an
intensity of 100 mW/cm2 (simulated illumination). Figure S4 (Sup­
porting Information) presents the J–V curves of the champion devices
modified with different amounts of G-PANI. Also, the PV values of the
whole fabricated HTL-free TC-PSCs as well as their average values are
presented in Table S1 (Supporting Information). The results showed that
the highest performance of the devices was achieved when the volume
ratio of G-PANI was 4% in the mp-TiO2 precursor. The results presented
in Table S1 show that the modification of mp-TiO2 with the G-PANI
nanocomposite led to an increase in the PV values of the TC-PSCs.
Nevertheless, when the amount of G-PANI in the mp-TiO2 ETL layer
exceeded 8%, the PV values decreased. Based on this observation, 4% is
suggested as the optimum amount of G-PANI incorporation. This is
62
Solar Energy 213 (2021) 59–66
consistent with the results of the XRD and optical analyses in this study.
After the optimum volume ratio of G-PANI incorporation was found
in the mp-TiO2 precursor, TC-PSCs with an HTL layer were fabricated
with the same amounts of RGO and G-PANI. This was done to prove the
preference of G-PANI over pure RGO in the modification of mp-TiO2 ETL
layers. By comparing the fabricated devices based on 4% of G-PANI and
RGO, one can see the greater role of G-PANI than RGO to improve the
performance of TC-PSCs. This can be due to the improved conductivity
of RGO in combination with PANI, as earlier reported (Wang, L. et al.,
2014). To prove this issue, current–voltage (I-V) measurements were
performed to calculate the direct conductivity (σ0 ) of the mp-TiO2
modified with different materials (Fig. 5a). For this purpose, the equa­
tion I = σ 0 AD− 1 V was used, where A is the area (≈10 mm2) and D is the
thickness (≈200 nm) of the mp-TiO2 layer. The σ 0 values of 2.08 ×
10− 3mS − 3mS − 3mS
cm , 3.17 × 10 cm , and 7.31 × 10 cm were calculated for the pure
mp-TiO2 and the mp-TiO2 modified with RGO and G-PANI respectively.
As shown in Fig. 4a, the improved conductivity of the mp-TiO2 modified
with G-PANI indicates a strengthened charge transfer in the ETL layer,
which boosts the short-circuit current density (JSC) (Chen et al., 2016).
H.R. Mohseni et al. Solar Energy 213 (2021) 59–66

Fig. 4. (a) The J-V and (b-e) statistical distributions for PCE, VOC, FF, and JSC of the perovskite solar cells (PSCs) fabricated based on pure mp-TiO2 and the mp-TiO2
ETL modified with reduced graphene oxide/polyaniline (G-PANI) nanocomposite or pure reduced graphene oxide (RGO). For each group, 12 devices were measured.
(f) The IPCE spectra of different PSCs and the integrated current densities from the IPCE.

The J–V curves of the best-performing devices modified with RGO and
G-PANI are presented in Fig. 4a, while Fig. 4b-e show the corresponding
statistical distribution of their PV parameters. Also, the PV parameters of
the TC-PSCs fabricated with an HTL layer based on RGO and G-PANI are
summarized in Table 1. According to the table, the average value of Jsc
for the GP-4% device (24.45 mA/cm2) suggests a remarkable enhance­
ment, as compared to the values of G-4% (22.21 mA/cm2) and the
reference (Ref.) cells (19.08 mA/cm2). Besides, the IPCE spectra of Ref.,
G-4% and GP-4% devices were measured to elucidate the JSC improve­
ment (Fig. 4f). The value of the integrated JSC obtained from IPCE was
20.4 mA/cm2, 22.11 mA/cm2 and 24.62 mA/cm2 for Ref., G-4% and GP-
4% devices respectively. These values were in agreement with the
average JSC calculated from J-V measurements (See Table 1). These
results are consistent with the PL quenching, the redshift in the
absorption edge of the films and the FESEM, and XRD measurements of
the perovskite films, as discussed in the previous section. Table 1 pre­
sents a champion PCE of 16.48% obtained for the G-PANI-based devices;
it is about 33.7% higher than that for the Ref. PSCs.
3.3. Study of the shelf stability of the fabricated devices
The shelf stability of the un-encapsulated TC-PSCs inside a dry airbox
(20% RH) for over 1870 h was measured in dark at the temperature of
20–30 ◦ C. Fig. 5 shows the normalized PCE variation curves of different
fabricated devices. The PCE of the Ref. device declined to about 15% of
its original value after 1870-hour aging time. Under the same test con­
ditions, however, the GP-4% devices displayed just a slow degradation
and maintained about 82% of their initial PCE over 1870 h of aging time.

63
H.R. Mohseni et al. Solar Energy 213 (2021) 59–66

Fig. 5. (a) I-V measurements of different modified mp-TiO2 layers, (b) Stability test of different perovskite solar cells inside a dry airbox with the relative humidity of
about 20% in dark at room temperature.

modified ETL layers with graphene or its derivatives is presented in

Table 1
Table 2. It can be concluded that RGO/PANI composite is a better
Photovoltaic (PV) parameters of the perovskite solar cells (PSCs) with a hole
candidate than graphene and RGO to modify ETL layers in the direct
transport layer based on pure mp-TiO2 as well as modified with RGO or G-PANI
nanocomposite. The active area of the devices was 8 mm2. The average values of structure of perovskite solar cells”.
the PV parameters were measured from 12 individual PSCs.
4. Conclusion
Device Voca (V) Jbsc (mA/cm2) FFc (%) PCEd (%)

Ref. Average 0.96 19.08 59.86 10.94 In summary, through a sequential deposition process, TC-PSCs were
Best 0.96 20.45 62.60 12.32
fabricated in ambient air. To improve the performance and the ambient
G-4% Average 0.96 22.21 60.41 12.78
Best 0.99 23.53 63.70 14.81 stability of the cells, a reduced graphene oxide/polyaniline (G-PANI)
GP-4% Average 0.97 24.45 62.13 14.71 composite was successfully added to mesoporous TiO2 (mp-TiO2). It was
Best 0.96 26.96 63.60 16.48 found that introducing a moderate amount of G-PANI into mp-TiO2
a
Voc: open-circuit voltage, b Jsc: short-circuit current density, c FF: fill factor, would be very beneficial for the fabrication process. The mp-TiO2 de­
d
PCE: power conversion efficiency vices modified with G-PANI proved to have compact perovskite films
with better orientation in (0 0 1) plane. It was also observed that G-PANI
This stability test suggests that perovskite devices with a moderate additives could cause a redshift in the absorption edge of the film, which
amount of G-PANI have higher shelf stability than Ref. devices. Inter­ increased the photocurrent density of the TC-PSCs. In addition, the
estingly, the results also show that G-PANI-based devices are relatively charge recombination at the TiO2/perovskite interface was mitigated
more stable than RGO-based ones. As earlier reported by (Castro- due to the incorporation of mp-TiO2 with the G-PANI nanocomposite,
Méndez et al., 2019; Ji et al., 2017), GBs in a perovskite layer play a which led to a higher charge transport by the device. The TC-PSCs
critical role in the unstable behavior of PSCs. Perovskite degradation in modified with G-PANI showed better shelf stability than the other de­
humid conditions starts at the surface of the film and then, through GBs, vices. According to the comparative results, G-PANI-based devices can
diffuses to the whole perovskite film. So, GBs passivation has emerged as be claimed to have better photovoltaic performance than reduced gra­
an effective method to improve the stability of PSCs (Liu et al., 2020; Niu phene oxide (RGO)-based ones. In brief, G-PANI modification serves as a
et al., 2018). In the present study, the addition of G-PANI to the mp-TiO2 new low-cost and simple method to enhance the photovoltaic parame­
precursor significantly passivated the GBs (Fig. 3c). This increased the ters and the stability of TC-PSCs, which can be easily generalized to
stability of the corresponding PSCs. other multi-cation perovskite solar cells.
“A comparison of this research with similar studies that have

Table 2
Summary of similar studies for ETL modification with graphene and its derivatives in comparison to this study.
Author Fabricating ETL modification details Perovskite PCE Champion Stability
method improvement PCE

(Cho et al., 2016) One-step RGO was added to the ETL (FAMA)Pb 4% 19.4% Not reported
mp-TiO2 layer (IBr)3
(Wang, J.T.-W. One-step Graphene was added to the MAPb(ICl)3 11% 15.6% Not reported
et al., 2014) ETL mp-TiO2 layer
(Han et al., 2015) Sequential RGO was added to the ETL MAPbI3 17% 14.5% Not reported
deposition mp-TiO2 layer
(Bi et al., 2017) One-step Graphene was added to the MAPbI3 5% 16.5 ≈10% loss after 1000 h of testing in in a dry cabinet
PCBM ETL (<30% humidity) without encapsulation
(Tavakoli et al., Two-step RGO was added to the ETL MAPbI3 ≈21% 15.2% ≈10% loss after 720 h of testing in ambient
2016) ZnO layer conditions with encapsulation
(Balis et al., One-step RGO was added to the ETL c- MAPbI3 20% 13.6 ≈10% loss after 1200 h of testing in a dry cabinet
2020) TiO2 layer with the humidity of 10% without encapsulation
This work Sequential RGO/PANI was added to the (CsMAFA)Pb 34% 16.48 ≈18% loss after 1870 h of testing in a dry airbox
deposition ETL mp-TiO2 layer (IBr)3 with the humidity of 20% without encapsulation

64
H.R. Mohseni et al.
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.
Acknowledgements
The authors wish to thank Iran National Science Foundation (INSF)
for the financial support of this research (Research proposal No:
96003879), S. Dalirnasab in Department of Chemistry, Yazd University
for carrying out UV-Vis and PL measurements and F. Doosthosseini for
fruitful guides to the synthesis of FAI and MACl.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.solener.2020.11.017.
References
Aeineh, N., Castro-Méndez, A.S.-F., Rodriguez-Cantó, P.J., Abargues, R., Hassanabadi, E.,
Suarez, I., Behjat, A., Ortiz, P., Martínez-Pastor, J.P., Mora-Seró, I., 2018. Optical
Optimization of the TiO2 Mesoporous Layer in Perovskite Solar Cells by the Addition
of SiO2 Nanoparticles. ACS Omega 3 (8), 9798–9804.
Agresti, A., Pescetelli, S., Palma, A.L., Del Rio Castillo, A.E., Konios, D., Kakavelakis, G.,
Razza, S., Cinà, L., Kymakis, E., Bonaccorso, F., 2017. Graphene interface
engineering for perovskite solar modules: 12.6% power conversion efficiency over
50 cm2 active area. ACS Energy Lett. 2 (1), 279–287.
Bai, S., Da, P., Li, C., Wang, Z., Yuan, Z., Fu, F., Kawecki, M., Liu, X., Sakai, N., Wang, J.
T.-W., 2019. Planar perovskite solar cells with long-term stability using ionic liquid
additives. Nature 571 (7764), 245–250.
Balis, N., Zaky, A.A., Athanasekou, C., Silva, A.M.T., Sakellis, E., Vasilopoulou, M.,
Stergiopoulos, T., Kontos, A.G., Falaras, P., 2020. Investigating the role of reduced
graphene oxide as a universal additive in planar perovskite solar cells. J. Photochem.
Photobiol. A 386, 112141.
Bi, E., Chen, H., Xie, F., Wu, Y., Chen, W., Su, Y., Islam, A., Grätzel, M., Yang, X., Han, L.,
2017. Diffusion engineering of ions and charge carriers for stable efficient perovskite
solar cells. Nature communications 8 (1), 1–7.
Castro-Méndez, A.F., Hidalgo, J., Correa-Baena, J.P., 2019. The role of grain boundaries
in perovskite solar cells. Adv. Energy Mater. 9 (38), 1901489.
Chavan, R.D., Yadav, P., Nimbalkar, A., Bhoite, S.P., Bhosale, P.N., Hong, C.K., 2019.
Ruthenium doped mesoporous titanium dioxide for highly efficient, hysteresis-free
and stable perovskite solar cells. Sol. Energy 186, 156–165.
Chen, B.-X., Rao, H.-S., Li, W.-G., Xu, Y.-F., Chen, H.-Y., Kuang, D.-B., Su, C.-Y., 2016.
Achieving high-performance planar perovskite solar cell with Nb-doped TiO2
compact layer by enhanced electron injection and efficient charge extraction.
J. Mater. Chem. A 4 (15), 5647–5653.
Chen, G.-S., Chen, Y.-C., Lee, C.-T., Lee, H.-Y., 2018. Performance improvement of
perovskite solar cells using electron and hole transport layers. Sol. Energy 174,
897–900.
Chen, L., Cao, H., Wang, S., Luo, Y., Tao, T., Sun, J., Zhang, M., 2019. Efficient air-stable
perovskite solar cells with a (FAI)0.46(MAI)0.40(MABr)0.14(PbI2)0.86(PbBr 2)0.14 active
layer fabricated via a vacuum flash-assisted method under RH> 50%. RSC Adv. 9
(18), 10148–10154.
Cho, K.T., Grancini, G., Lee, Y., Konios, D., Paek, S., Kymakis, E., Nazeeruddin, M.K.,
2016. Beneficial role of reduced graphene oxide for electron extraction in highly
efficient perovskite solar cells. ChemSusChem 9 (21), 3040–3044.
Dehghan, M., Behjat, A., 2019. Deposition of zinc oxide as an electron transport layer in
planar perovskite solar cells by spray and SILAR methods comparable with spin
coating. RSC advances 9 (36), 20917–20924.
Doosthosseini, F., Behjat, A., Hashemizadeh, S., Torabi, N., 2015. Application of silver
nanoparticles as an interfacial layer in cadmium sulfide quantum dot sensitized solar
cells. J. Nanophotonics 9 (1), 093092.
Gielen, D., Boshell, F., Saygin, D., Bazilian, M.D., Wagner, N., Gorini, R., 2019. The role
of renewable energy in the global energy transformation. Energy Strategy Rev. 24,
38–50.
Giordano, F., Abate, A., Baena, J.P.C., Saliba, M., Matsui, T., Im, S.H., Zakeeruddin, S.M.,
Nazeeruddin, M.K., Hagfeldt, A., Graetzel, M., 2016. Enhanced electronic properties
in mesoporous TiO2 via lithium doping for high-efficiency perovskite solar cells. Nat.
Commun. 7, 10379.
Han, G.S., Song, Y.H., Jin, Y.U., Lee, J.-W., Park, N.-G., Kang, B.K., Lee, J.-K., Cho, I.S.,
Yoon, D.H., Jung, H.S., 2015. Reduced graphene oxide/mesoporous TiO2
nanocomposite based perovskite solar cells. ACS Appl. Mater. Interfaces 7 (42),
23521–23526.
Ji, F., Pang, S., Zhang, L., Zong, Y., Cui, G., Padture, N.P., Zhou, Y., 2017. Simultaneous
evolution of uniaxially oriented grains and ultralow-density grain-boundary network
in CH3NH3PbI3 perovskite thin films mediated by precursor phase metastability. ACS
Energy Lett. 2 (12), 2727–2733.
65
Solar Energy 213 (2021) 59–66
Kim, H., Lee, J., Kim, B., Byun, H.R., Kim, S.H., Oh, H.M., Baik, S., Jeong, M.S., 2019.
Enhanced Stability of MAPbI3 Perovskite Solar Cells using Poly (p-chloro-xylylene)
Encapsulation. Sci. Rep. 9 (1), 1–6.
Kojima, A., Teshima, K., Shirai, Y., Miyasaka, T., 2009. Organometal halide perovskites
as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131 (17),
6050–6051.
Lee, J.-W., Bae, S.-H., De Marco, N., Hsieh, Y.-T., Dai, Z., Yang, Y., 2018. The role of grain
boundaries in perovskite solar cells. Mater. Today Energy 7, 149–160.
Liu, M., Johnston, M.B., Snaith, H.J., 2013. Efficient planar heterojunction perovskite
solar cells by vapour deposition. Nature 501 (7467), 395–398.
Liu, Z., Cao, F., Wang, M., Wang, M., Li, L., 2020. Observing Defect Passivation of the
Grain Boundary with 2-Aminoterephthalic Acid for Efficient and Stable Perovskite
Solar Cells. Angew. Chem. 132 (10), 4190–4196.
Masood, M.T., Qudsia, S., Hadadian, M., Weinberger, C., Nyman, M., Ahläng, C.,
Dahlström, S., Liu, M., Vivo, P., Österbacka, R., 2020. Investigation of well-defined
pinholes in TiO2 electron selective layers used in planar heterojunction perovskite
solar cells. Nanomaterials 10 (1), 181.
Meissner, D., Wohrle, D., 1991. Organic solar cells. Adv. Mater. 3, 129–138.
Mozaffari, M., Behjat, A., Mirjalili, B.F., 2018. The effect of solution process control on
the formation of the α-FAPbI3 perovskite: FAPbI3 versus MAPbI3 solar cells. Sol.
Energy 174, 780–785.
Niu, G., Yu, H., Li, J., Wang, D., Wang, L., 2016. Controlled orientation of perovskite
films through mixed cations toward high performance perovskite solar cells. Nano
Energy 27, 87–94.
Niu, T., Lu, J., Munir, R., Li, J., Barrit, D., Zhang, X., Hu, H., Yang, Z., Amassian, A.,
Zhao, K., 2018. Stable High-Performance Perovskite Solar Cells via Grain Boundary
Passivation. Adv. Mater. 30 (16), 1706576.
Nouri, E., Mohammadi, M.R., Xu, Z.-X., Dracopoulos, V., Lianos, P., 2018. Improvement
of the photovoltaic parameters of perovskite solar cells using a reduced-graphene-
oxide-modified titania layer and soluble copper phthalocyanine as a hole
transporter. Phys. Chem. Chem. Phys. 20 (4), 2388–2395.
Nozik, A.J., 2002. Quantum dot solar cells. Physica E Low Dimens. Syst. Nanostruct. 14
(1–2), 115–120.
O’Regan, B., Grätzel, M., 1991. A low-cost, high-efficiency solar cell based on dye-
sensitized colloidal TiO 2 films. Nature 353 (6346), 737–740.
Pourradi, H., Ghani, K., Mahdavi, M., 2019. Fully Ambient Air Processed Perovskite Solar
Cell Based on Co (Co, Cr)2O4/TiO2 P-N Heterojunction Array in Photoanode. J. Phys.
Chem. C 123 (7), 4044–4055.
Ryu, J., Lee, J.W., Yu, H., Yun, J., Lee, K., Lee, J., Hwang, D., Kang, J., Kim, S.K., Jang, J.,
2017. Size effects of a graphene quantum dot modified-blocking TiO2 layer for
efficient planar perovskite solar cells. J. Mater. Chem. A 5 (32), 16834–16842.
Saliba, M., Matsui, T., Seo, J.-Y., Domanski, K., Correa-Baena, J.-P., Nazeeruddin, M.K.,
Zakeeruddin, S.M., Tress, W., Abate, A., Hagfeldt, A., 2016. Cesium-containing triple
cation perovskite solar cells: improved stability, reproducibility and high efficiency.
Energy Environ. Sci. 9 (6), 1989–1997.
Sidhik, S., Cerdan Pasaran, A., Esparza, D., Lopez Luke, T., Carriles, R.N., De la Rosa, E.,
2018. Improving the optoelectronic properties of mesoporous TiO2 by cobalt doping
for high-performance hysteresis-free perovskite solar cells. ACS Appl. Mater.
Interfaces 10 (4), 3571–3580.
Singh, T., Miyasaka, T., 2018. Stabilizing the efficiency beyond 20% with a mixed cation
perovskite solar cell fabricated in ambient air under controlled humidity. Adv.
Energy Mater. 8 (3), 1700677.
Tang, Z., Uchida, S., Bessho, T., Kinoshita, T., Wang, H., Awai, F., Jono, R., Maitani, M.
M., Nakazaki, J., Kubo, T., 2018. Modulations of various alkali metal cations on
organometal halide perovskites and their influence on photovoltaic performance.
Nano Energy 45, 184–192.
Tavakoli, M.M., Tavakoli, R., Nourbakhsh, Z., Waleed, A., Virk, U.S., Fan, Z., 2016. High
efficiency and stable perovskite solar cell using ZnO/rGO QDs as an electron transfer
layer. Adv. Mater. Interfaces 3 (11), 1500790.
Tiedje, T.O.M., Yablonovitch, E.L.I., Cody, G.D., Brooks, B.G., 1984. Limiting efficiency
of silicon solar cells. IEEE Trans. Electron Devices 31 (5), 711–716.
Torabi, N., Behjat, A., Zhou, Y., Docampo, P., Stoddard, R.J., Hillhouse, H.W., Ameri, T.,
2019. Progress and challenges in perovskite photovoltaics from single-to multi-
junction cells. Mater. Today Energy 12, 70–94.
Uddin, A., Upama, M.B., Yi, H., Duan, L., 2019. Encapsulation of organic and perovskite
solar cells: a review. Coatings 9 (2), 65.
Uratani, H., Yamashita, K., 2017. Charge carrier trapping at surface defects of perovskite
solar cell absorbers: a first-principles study. J. Phys. Chem. Lett. 8 (4), 742–746.
Wang, J.T.-W., Ball, J.M., Barea, E.M., Abate, A., Alexander-Webber, J.A., Huang, J.,
Saliba, M., Mora-Sero, I., Bisquert, J., Snaith, H.J., 2014a. Low-temperature
processed electron collection layers of graphene/TiO2 nanocomposites in thin film
perovskite solar cells. Nano Lett. 14 (2), 724–730.
Wang, L., Lu, X., Lei, S., Song, Y., 2014b. Graphene-based polyaniline nanocomposites:
preparation, properties and applications. J. Mater. Chem. A 2 (13), 4491–4509.
Wang, S., Jin, J., Qi, Y., Liu, P., Xia, Y., Jiang, Y., He, R.X., Chen, B., Liu, Y., Zhao, X.Z.,
2019. δ-CsPbI3 Intermediate Phase Growth Assisted Sequential Deposition Boosts
Stable and High-Efficiency Triple Cation Perovskite Solar Cells. Adv, Funct. Mater.,
p. 1908343
Yang, W.S., Noh, J.H., Jeon, N.J., Kim, Y.C., Ryu, S., Seo, J., Seok, S.I., 2015a. High-
performance photovoltaic perovskite layers fabricated through intramolecular
exchange. Science 348 (6240), 1234–1237.
Yang, Y., Ri, K., Mei, A., Liu, L., Hu, M., Liu, T., Li, X., Han, H., 2015b. The size effect of
TiO2 nanoparticles on a printable mesoscopic perovskite solar cell. J. Mater. Chem. A
3 (17), 9103–9107.
H.R. Mohseni et al.
Yao, K., Li, F., He, Q., Wang, X., Jiang, Y., Huang, H., Jen, A.K.Y., 2017. A copper-doped
nickel oxide bilayer for enhancing efficiency and stability of hysteresis-free inverted
mesoporous perovskite solar cells. Nano Energy 40, 155–162.
Ye, W., Xiang, J., Huang, F., Zhong, D., 2018. Towards large-area perovskite solar cells:
the influence of compact and mesoporous TiO2 electron transport layers. Mater. Res.
Express. 5 (8), 085506.
Yi, C., Luo, J., Meloni, S., Boziki, A., Ashari-Astani, N., Grätzel, C., Zakeeruddin, S.M.,
Röthlisberger, U., Grätzel, M., 2016. Entropic stabilization of mixed A-cation ABX3
metal halide perovskites for high performance perovskite solar cells. Energy Environ.
Sci. 9 (2), 656–662.
Yoo, J.J., Wieghold, S., Sponseller, M.C., Chua, M.R., Bertram, S.N., Hartono, N.T.P.,
Tresback, J.S., Hansen, E.C., Correa-Baena, J.-P., Bulović, V., 2019. An interface
stabilized perovskite solar cell with high stabilized efficiency and low voltage loss.
Energy Environ. Sci. 12 (7), 2192–2199.
66
Solar Energy 213 (2021) 59–66
Yue, Y., Umeyama, T., Kohara, Y., Kashio, H., Itoh, M., Ito, S., Sivaniah, E., Imahori, H.,
2015. Polymer-assisted construction of mesoporous TiO2 layers for improving
perovskite solar cell performance. The J. Phys. Chem. C 119 (40), 22847–22854.
Zhao, J., Li, Y., Yang, G., Jiang, K., Lin, H., Ade, H., Ma, W., Yan, H., 2016. Efficient
organic solar cells processed from hydrocarbon solvents. Nat. Energy 1 (2), 1–7.
Zheng, H., Xu, X., Xu, S., Liu, G., Chen, S., Zhang, X., Chen, T., Pan, X., 2019. The
multiple effects of polyaniline additive to improve the efficiency and stability of
perovskite solar cells. J. Mater. Chem. C 7 (15), 4441–4448.
Zheng, H., Zhu, L., Hu, L., Yang, S., Chen, S., Alsaedi, A., Hayat, T., Huang, Y., Pan, X.,
Dai, S., 2018. Promoting perovskite crystal growth to achieve highly efficient and
stable solar cells by introducing acetamide as an additive. J. Mater. Chem. A 6 (21),
9930–9937.