Article

DOI:10.1557/s43578-022-00537-x

A simplistic approach to evaluate the power conversion

efficiencies for hybrid charge transport layers in open‑air
fabricated perovskite solar cells
Zameer Abbas1,b), Francis Agada1,2,b), Afzal Hussain Kamboh3, Asad Muhammad Khan1,
Umar Farooq1, Muhammad Bilal4, Muhammad Arshad5, Ahson Jabbar Shaikh1,a) 
1 
Department of Chemistry, COMSATS University Islamabad - Abbottabad Campus, Abbottabad 22060, KPK, Pakistan
2
 Department of Chemistry, Federal University Lokoja, Lokoja 260101, Nigeria
3
 Pakistan Council of Renewable Energy Technologies (PCRET), Islamabad 44000, Pakistan
4
 Department of Environmental Sciences, COMSATS University Islamabad, Abbottabad Campus, Abbottabad 22060, KPK, Pakistan
5
 Institute of Environmental Sciences and Engineering, School of Civil and Environmental Engineering, National University of Sciences and Technology,
Islamabad 44000, Pakistan
a) 
Address all correspondence to this author. e-mail: ahsonjabbar@hotmail.com; ahson@cuiatd.edu.pk
b) 
These authors have contributed equally to this work.
Received: 4 January 2022; accepted: 7 March 2022

Three perovskite solar cells with a general architecture of FTO/GO-CuI/Perovskite/ZnO/Ag electrode were
fabricated with different ratios of graphene oxide and copper iodide as hybrid hole transport layers in
an open-air environment for the comparison purposes and to find better hole transport material. The
obtained power conversion efficiencies were extrapolated to find the power conversion efficiencies
of other compositions of these materials including graphene oxide and copper iodide only-based
devices. Hence, enhanced information was obtained by just making three devices only, which allowed
us to save a lot of time and resources as compared to making devices in the standard conditions. The
power conversion efficiency was increased with the decrease in concentration of graphene oxide, hence
copper iodide showed better hole transport characteristics. This simplistic approach to evaluate power
conversion efficiencies for hybrid charge transport layers can be utilized for any combination of hole or
electron hybrid transport layers in perovskite solar cells.

Introduction in which they optimized the thickness of graphene layer, where

The principle of modern solar technology is based on p- and
n-type of semiconductor materials [1]. Many p-type semicon-
ductor materials like graphene oxide (GO), copper iodide (CuI),
copper sulfide (CuS), copper oxide(s) (­ Cu2O, CuO), and copper
thiocyanate (CuSCN) have been utilized as hole transport mate-
it was observed that increase in the thickness of graphene layer
from 2 to 10 nm results in the decrease in PCE from 16.3% to
2.3% [5]. GO is generally considered to be a suitable material as
hole transport layer (HTL), as PCE and stability of devices have
shown to be improved upon its use [6]. In recent years, many
other researchers have also used GO as a hole transport material
    Journal of Materials Research   2022   www.mrs.org/jmr

rials (HTMs) to improve the stability and power conversion effi-

ciency (PCE) of perovskite solar cells (PSCs). Graphene oxide was
first reported by Wu et al. as a hole conductor in perovskite solar
cells for which they observed improvement in the performance
of the device from 9.2 to 12.4% [2]. Ahmad et al. fabricated three
solar cell devices with an architecture of ITO/GO/PEDOT:PSS/
MAPbI3/PCBM/Carbon tape under open-air conditions, where
they attained PCE of 2.1–5.2% [3]. Niu et al. fabricated a GO-
doped PEDOT:PSS hole transport layer and reported a good PCE
of up to 14% [4]. Yang et al. fabricated graphene-based PSC device
which also resulted in the improvement in PCE of PSCs [7–9].
Many copper-based inorganic semiconductors such as CuI,
CuSCN, and C ­ u2O have interesting properties as HTL, such as
cost effective fabrication, band alignment suitable for active layer
of perovskite, high resistance against chemicals, and high hole
mobility [10–12]. CuI among them has a great significance as
HTL material because of its suitable valence band position [13]
and high power conversion efficiency [14, 15]. Sun et al. fabri-
cated copper iodide-based devices with architecture of ITO/CuI/

Vol.:(0123456789)

© The Author(s), under exclusive licence to The Materials Research Society 2022

CH3NH3PbI3/fullerene/bathocuproine/Ag at room temperature
for which they attained PCE of up to 16.8% [16]. Huangfu et al.
fabricated CuI-based PSCs at low temperature, where they ana-
lyzed the effect of thickness of CuI layer on the PCE of device,
revealing that thicker film of CuI has higher conductivity and
wider band gap [17]. In another example, excellent stability
and PCE was achieved by replacing spiro-OMeTAD with cop-
per iodide as a hole transport layer in perovskite solar cell [18].
Quantum dots (QDs) have many desirable properties
including simple synthesis method(s), solution processing,
tunable absorption bandgap due to quantum confinement, and
its multiple exciton generation makes them suitable candidates
for the solar cells [19]. Zinc oxide QDs have conduction band
(LUMO) at desirable energy level, i.e., -4.17 eV, a favorable
bandgap of 3.3 eV, and its transmittance is high in visible light
wavelength. At low temperatures, ZnO may represent diverse
nanostructures by crystallization [20]. Alkali metal-doped ZnO
QDs are also reported as an electron transport layer in PSCs
with high PCE, negligible hysteresis, and remarkable stability
in an open-air environment (after 800 h, 91% preservation was
observed) [21]. Zinc oxide nanorods have also been utilized for
perovskite solar cells, where 5.0% PCE was obtained [22]. In
another example, ZnO nanorods were used as an ETL in flex-
ible perovskite solar cells and a PCE of 2.6% was attained. Other
examples of low temperature processed ZnO NPs as ETLs in
perovskite solar cell include planar PSCs with a PCE of 15.7%
obtained by optimizing the thickness of films, where flexible
PSCs were also produced [23].
In recent years, many groups have utilized hybrid ETLs
or HTLs, which can be any combination of organic and inor-
ganic materials, to further improve and enhance the stability
and efficiency of perovskite solar cells, as compared to single
material-based HTL [24, 25]. For example, Lee et al. fabricated
a device where GO and PEDOT:PSS composites were used as a
hole transport layer and a good PCE was obtained as compared
to the devices with single GO or PEDOT:PSS HTLs [26]. In a
similar type of work, addition of GO to PEDOT:PSS as hybrid
HTL showed improved stability [27, 28], and suppression of
leakage current and reduction in recombination via efficient
hole transport and electron blocking mechanism, resulting in
30% improvement of PCE [29]. Interestingly, copper iodide
along with PEDOT:PSS has also shown improved PCE and sta-
bility for perovskite solar cells [30], which led us to consider
the possibility of using GO-based and CuI-based hybrid hole
transport layers, which are not reported earlier to the best of our
understanding. It is important to mention that copper iodide
along with reduced graphene oxide and other materials has been
recently reported for visible light photocatalytic activity [31] and
bacterial disinfection [32]. Although, hybrid HTMs or ETMs
improve the charge transporting ability, stability, and PCE of
PSCs, however, it is quite important to understand the HOMO
© The Author(s), under exclusive licence to The Materials Research Society 2022
Article
and LUMO energy levels as well as bandgap of these materials
for the proper selection of materials required for the fabrica-
tion of solar cells. Other factors which are important are energy
alignment in the device architecture, the solvent suitability, and
interfacial properties of the materials used. The energy level
diagram as shown in Fig. 7 of this manuscript was considered
along with the solubility of materials for the work reported in
this manuscript.
Historically, perovskite solar cells have been fabricated
under inert conditions, as perovskite layer is sensitive to water,
which makes them unsuitable to make and use in atmospheric
conditions. Fabricating PSCs in an inert environment condi-
tions have shown that high-quality and high-performance per-
ovskite solar cells can be made [33], however, such fabrication
of PSCs under inert atmosphere is not only costly, but also a
time-consuming process. As of recent, there are few groups
that have been working on fabrication of perovskite devices in
an ambient atmosphere, where the use of selected materials as
ETLs and HTLs also enhances the stability of perovskite solar
cells [34, 35]. Although the fabrication of PSC devices in open-
air environment comes at a cost of sensitivity of the perovskite
layer, hence lower PCE, however, the benefits of this process are
less associated costs, rapid process, quick analysis specially for
the comparison purposes, and easy to move forward to indus-
trial scale fabrication in future, based on the experiences at the
lab scale [36, 37]. As an example, one of the recent successful
fabrication of perovskite solar cells in open-air was reported by
Zahou et al. where perovskite thin film was fabricated by using
vapor-assisted solution method with well-defined grain struc-
ture, grain size up to micro level, and very small surface rough-
ness [38]. Another such example of non-inert atmospheric fab-
rication was reported by Luo et al. using low-pressure chemical
vapor deposition method, which is an industrial-scale method
to fabricate high-quality and uniform large-scale thin film of
perovskite [39]. Multi-flow air knife method was also used to
fabricate high-quality and large area with high-performance
perovskite solar cells in an ambient-air condition [40].
In this current study, a new hybrid hole transport layer was
formulated based on graphene oxide and copper iodide, and
successfully utilized it for the fabrication of devices in ambient
atmospheric conditions. An inverted architecture of perovskite-
    Journal of Materials Research   2022   www.mrs.org/jmr
based devices was focused due to the solubility concerns of ETL
and HTL. The effect of varying concentrations of HTL materials
in hybrid layer on the performance of perovskite solar cells was
investigated which revealed consequent change in the efficiency
of devices, which also allowed us to find efficiencies of devices
with other ratios of the HTL materials including pure HTLs, and
also allowed us to quickly analyze the best materials suitable for
the PSCs. Hence, open-air fabrication for cost effective PSCs
with a new combination of HTLs allowed us to investigate an
easy method for the selection of best materials applied as ETLs
2
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or HTLs. This methodology has the potential to pave a vital role UV–Vis and fluorescence spectroscopy
for the large-scale fabrication of perovskite solar cells. UV–Visible absorption spectroscopy and steady-state fluores-
cence emission spectroscopy were used to analyze the conju-
gation and optical properties of our synthesized samples. Fig-
Results and discussion ure 1(a) shows the UV–Visible absorption spectra of graphene
The synthesized graphene oxide sheets and zinc oxide nanopar- oxide (GO) giving two absorption peaks. The absorption peak
ticles were characterized by different techniques like UV–Vis appeared at 230 nm is due to the π → π* transition of aromatic
spectroscopy, fluorescence spectroscopy, Fourier-Transform C–C bonds, and shoulder peak observed at 304 nm is due to
infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scan- the n → π* transition of carbonyl groups, matching with the
ning electron microscopy (SEM), dynamic light scattering literature values [41], confirming the successful formation of
(DLS), and zeta-potential (ζ), graphene oxide. The direct band gap of graphene oxide is shown

0.8
2.5 a GO b ZnO
375 nm
0.7
230 nm

Absorbance (a.u.)
Absorbance (a.u.)

2.0 0.6

1.5 0.5

0.4
1.0
304 nm
0.3
0.5
0.2

0.0 0.1
200 300 400 500 200 300 400 500 600 700
Wavelength (nm) Wavelength (nm)
0.7 0.09
c Direct band gap of GO
0.08
d Direct band gap of ZnO
0.6
0.07
( hv)2 (eV2cm-2)

0.5
( hv)2 (eV2cm-2)

0.06
0.4 0.05
0.04
0.3
0.03
0.2
0.02
0.1 0.01
Eg= 4.49 eV Eg= 4.55 eV
0.00
0.0
-0.01
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Energy (eV) Energy (eV)
14000 18000
e 350 nm GO f ZnO
340 nm
16000
12000
375 nm
PL Intensity (a.u.)
PL Intensity (a.u.)

14000
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10000
12000
8000
10000
6000
8000

4000 6000

2000 4000
300 350 400 450 500 300 350 400 450 500
Wavelength (nm) Wavelength (nm)

Figure 1:  GO and ZnO NPs (a, b) UV–Vis absorption spectrum, (c, d) Tauc’s plot, and (e, f ) fluorescence emission spectrum.

© The Author(s), under exclusive licence to The Materials Research Society 2022 3
 Article

in Fig. 1(c), which was calculated by using Tauc’s equation,
providing the bandgap ­(Eg) at 4.49 eV. Similarly, the UV–Vis
spectroscopy of zinc oxide nanoparticles shows the character-
istic sharp peak of zinc oxide nanoparticles at the wavelength
of 375 nm, as shown in Fig. 1(b), which is the absorption of
intrinsic bandgap (valence band → conduction band) of ZnO
­(O2p → ­Zn3d) transition [42]. These values confirm the forma-
tion of ZnO NPs. The direct band gap of ZnO nanoparticles was
calculated to be 4.55 eV with the help of Tauc’s equation and is
shown in Fig. 1(d).
The steady-state fluorescence emission spectra of graphene
oxide is shown in Fig. 1(e), which was obtained by exciting the
sample at 265 nm. A broad emission dominant spectrum at
340 nm shows the recombination of holes and electrons from
the excited state (π* → π) of ­sp2 hybridized atoms of graphene
oxide. Figure 1(f) shows the fluorescence emission spectra for
zinc oxide nanoparticles, also excited at 265 nm. Zinc oxide NPs
exhibit two fluorescence peaks at 340 nm due to near band exci-
tonic emission, and at 375 nm due to ionized oxygen vacancies
[43].
Fourier transform infrared (FT‑IR) spectroscopy
and X‑Ray diffraction studies
The FT-IR spectrum of graphene oxide is provided in Fig. 2(a),
which shows a broad intense peak around 3000–3600 ­cm−1,
due to the stretching and bending vibrations of hydroxyl
groups (-OH). The peak observed at 1745  ­c m −1 is due to
stretching vibration of carbonyl (C = O) groups. The peak
with medium intensity at 1625  ­c m −1 shows the stretching
vibrations of C = C bonds. The peak with a medium intensity
at 1041 ­cm−1 is due to the C-O stretching vibrations, which
shows the presence of alcohol groups in the sample. Since,
many oxygen containing groups are observed, which confirm
the formation of graphene oxide from graphite, the functional
groups and FT-IR spectra of our samples are also matched
with the literature values of graphene oxide [44]. Figure 2(b)
shows FT-IR spectra of zinc oxide nanoparticles. The spec-
trum shows a broad peak at 3545 ­cm−1, which represents the
stretching mode of –OH from the atmospheric water mol-
ecules. The small peak at 2340 ­cm−1 is due to the atmospheric
­C O 2 molecules. The peak at 475 ­c m −1 is the characteristic

5
10 a GO b ZnO NPs

5 0
Transmittance (%)

Transmittance (%)

0 -5
-5
-10 2340 cm-1
CO2
-10 1745 cm-1
1041 cm-1
-C=O 1625 cm-1
-15 C-OH -15
C=C
3545 cm-1
-20 -20 -OH

-25 3500 cm-1

475 cm-1
-OH -25
Zn-O
-30
4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1 ) Wavenumber (cm-1 )

100 1400
c ICSD= 01-075-1621 GO d ICSD = 65121 ZnO
(001) 1200
80
(101)

1000
Intensity (a.u.)
Intensity (a.u.)

60 800
(100)
(002)

600
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40
(110)

(112)
(103)
(102)

400
(201)
(200)

20 200

0
0
-200
10 20 30 40 50 60 70 80 30 40 50 60 70
2 (degree) 2 (degree)

Figure 2:  GO and ZnO NPs (a, b) FT-IR spectra (c, d) XRD pattern.

© The Author(s), under exclusive licence to The Materials Research Society 2022 4
 Article

absorption peak of Zn–O bond, revealing the presence of ZnO
nanoparticles. The values of functional groups and spectra
also match with the literature values [45].
The crystallite morphology and phase formation of synthe-
sized samples are confirmed by X-ray diffraction studies. Fig-
ure 2(c) shows XRD pattern of graphene oxide, which matches
with standard ICSD file number 01-075-1621, showing only one
characteristic peak at 2θ value of 10.09° with d-spacing of 8.01 Å.
A broad curve appeared at 2θ value of 25°, which represents
the amorphous nature of graphitic structure. Figure 2(d) shows
XRD pattern of zinc oxide, which exhibits hexagonal crystal
system. From the full width half maximum (FWHM) of XRD
peaks, we calculated an estimated crystallite size of ZnO NPs
by Scherer equation, which was found to be 29.68 nm and the
pattern was matched to the reference card (ICSD-65121). The
high intensity and narrow width of the peaks are clear indicative
of good crystallization of zincite ZnO, with (100), (002), (101),
(102), (110), (103), (200), (112), and (201) planes.
Scanning electron microscopy, dynamic light
scattering, and zeta‑potential analysis
The SEM image of synthesized graphene oxide sheets was
observed at a magnification of 40,000 × with a scale bar of
0.5 μm, as is shown in Fig. 3(a). The image displays separated
sheets of graphene oxide. These sheets are separated as their

a b

600 60
c 162 ± 20 nm
GO sheets d ZnO NPs
9±7 nm
500 50

400 40
Counts

Counts

300 30

200 20

100 10

0 0
0 200 400 600 800 1000 1200 1400 1600 0 10 20 30 40
Sheet Size (nm) Particle Size (nm)
80
e 296 nm GO 12 f 192 nm ZnO NPs
70

60 10
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Intensity (%)

Intensity (%)

50
8
40
6
30

20 4
10
2
0 1 2 3
10 10 10 101 102 103
Size (nm) Size (nm)

Figure 3:  GO sheets and ZnO NPs (a, b) SEM images, (c, d) size distribution plot of a and b, respectively, and (e, f ) hydrodynamic size distribution.

© The Author(s), under exclusive licence to The Materials Research Society 2022 5

carbon atoms are ­sp3 hybridized after oxidation, containing
oxygen functional groups in graphene sheets, such as carbox-
ylic acid, and hydroxyl and epoxy functional groups. This SEM
image also shows un-controlled oxidation at different levels, as
seen from different sizes and morphologies of GO sheets. The
separated graphitic layer in graphene oxide also shows higher
oxygen content, where functional groups are responsible for
separation between GO sheets [46]. The corresponding aver-
age size distribution of graphene oxide sheets are examined and
drawn in a histogram plot for size distribution, and is shown in
Fig. 3(c). The graph shows average sheet size of GO with normal
distribution at 162 ± 20 nm, based on the counting of sheets [47].
The morphological study of zinc oxide was also observed by
scanning electron microscopy. The SEM image of synthesized
zinc oxide NPs was observed at ×40,000 magnification with a
scale bar of 0.5 μm (500 nm), as is shown in Fig. 3(b). The SEM
images show spherical shape of zinc oxide NPs with uniform
size distribution and resemblance to the images shown in the
literature [48]. The corresponding average size distribution of
particles were also examined and drawn through histogram
plot for size distribution as is shown in Fig. 3(d). The graph
shows the average size particles with normal distribution curve
of 9 ± 7 nm, based on the counting of particles [49].
Dynamic light scattering (DLS) and zeta-potential analy-
sis were used to analyze size distribution and stability of the
synthesized GO and ZnO nanoparticles, performed at 25 °C at
a concentration level of 0.01 wt% dispersed in distilled water.
The hydrodynamic size distribution of graphene oxide is shown
in Fig. 3(e). The average size observed for graphene oxide was
296 nm and zeta-potential was observed at − 40 ± 6.49 mV. The
zeta-potential graph is provided in the supplementary informa-
tion. This zeta-potential value shows that synthesized graphene
oxide has very good stability at room temperature. The DLS
measurement for ZnO NPs is shown in Fig. 3(f). The average
hydrodynamic size of the nanoparticles was observed at 192 nm
and zeta-potential was observed at − 12.8 ± 3.26 mV. The zeta-
potential graph is provided in the supplementary information.
These values show that our synthesized sample has relatively low
stability in water at room temperature.
Binding studies for graphene oxide and copper iodide
as hybrid hole transport layers
UV–Vis absorption analysis
We were interested to know the binding effects [50, 51], if any
of graphene oxide and copper iodide, as both were used as a
hybrid for the hole transport layer in our devices. For this
purpose, UV–Vis absorption experiment was carried out at
room temperature with the same ratios of these two materi-
als, as used for the fabrication of perovskite solar cell devices.
© The Author(s), under exclusive licence to The Materials Research Society 2022
Article
The solutions were prepared at room temperature, where GO
was dispersed in distilled water and CuI was dispersed in
acetonitrile, which were then combined in appropriate ratios
and sonicated for 30 min before the UV–Vis analysis. The
changes in the UV–Visible absorbance spectra allowed us to
monitor binding interactions between these two moieties.
Graphene oxide and copper iodide were analyzed separately
and then the hybrid solutions with increasing concentration
of GO and decreasing concentration of CuI were analyzed,
as shown in Fig. 4(a). We observed a bathochromic shift of
GO peak after the addition of CuI from 230 to 225 nm, which
could either be the binding effect or possibly the solvent effect.
However, increasing the concentration of GO and simultane-
ously decreasing the concentration of CuI also resulted in a
hypochromic shift of the GO, which indicates the binding of
these two moieties. The shoulder peak at 304 nm of GO disap-
peared with increasing concentration of CuI, which is another
notable observation in the spectra, representing potentially
the interaction of copper iodide with the functional groups
of graphene oxide. Further, it is also clearly observed that the
broadness of GO peak has transformed to narrow peak and
the peaks of CuI at around 290 nm are vanished, also clearly
indicating the binding of two moieties. It is pertinent to men-
tion here that the peak at ~ 355 nm is due to the acetonitrile,
which was used as a solvent for CuI, as CuI was not soluble in
water. Additional two UV–Vis experiments were also carried
out to further confirm their binding, where the first experi-
ment was performed with a fixed CuI and increasing GO con-
centration to study the effect of GO on CuI, and the second
experiment was performed with fixed GO and increasing CuI
concentration to study the effect of CuI on GO, as shown in
Fig. 4(b) and (c), respectively. For the fixed CuI experiment,
increasing the concentration of GO resulted in the increase
in intensity, i.e., hyperchromic effect of GO peak at 227 nm.
At the same time, we can observe another characteristic peak
associated to GO appearing at ~ 303 nm with increasing con-
centration of GO. Similarly, with the fixed GO concentration,
increasing the concentration of CuI resulted in the increase in
the absorption spectra with no significant changes in the peak
of GO, including the shoulder peak. In this case [Fig. 4(c)],
the increase in absorbance intensity was relatively less as
    Journal of Materials Research   2022   www.mrs.org/jmr
compared to previous spectra [Fig. 4(b)], where significant
increase in intensity with addition of GO was observed. This
shows that GO has much higher molar absorptivity constant
as compared to CuI. These two supported UV–Vis titration
experiments also confirmed our previous assessment that
binding between the two moieties occurs resulting in the for-
mation of hybrids. Additional evidence for the binding was
also achieved by fluorescence experiments and fluorescence
titration experiments were performed for the fixed GO and
increasing CuI concentrations. This selection was opted, as
6
 Article

2.0
a Pure CuI 1.6 b blank c GO+0 L CuI
Pure GO CuI+185 L 1.5 GO+375 L CuI
1.4

Absorbance (a.u.)
Absorbance (a.u.)

Absorbance (a.u.)
GO:CuI; 50:50 CuI+375 L GO+750 LCuI
1.5 1.2
GO:CuI; 60:40 CuI+750 L GO+1125 L CuI
1.2
GO:CuI; 80:20 1.0 CuI+1125 L GO+1500 L CuI
1.0 0.8 CuI+1500 L
0.9
0.6

0.5 0.4 0.6

0.2
0.0 0.3
0.0
200 250 300 350 400 450 500 200 300 400 500 600 200 250 300 350
Wavelength (nm) Wavelength (nm) Wavelength (nm)

1x104 2.4
d 340 nm
e R2 = 0.9960
Fluorescence Intensity (a.u.)

4 Pure (GO) 2.2

1x10
200 L (CuI)
400 L (CuI) 2.0
1x104 600 L (CuI)
800 L (CuI) 1.8
1000 L (CuI)
8x103
1200 L (CuI)

I0/I
1.6
6x103
1.4
4x103
1.2
3
2x10 1.0

0 0.8
300 325 350 375 400 425 450 0 200 400 600 800 1000 1200
Wavelength (nm)
CuI ( L)

Figure 4:  GO-CuI hybrids (a) UV–Vis spectrum with varying ratios of GO and CuI, (b) UV–Vis spectrum with increasing concentration of GO, (c) UV–Vis
spectrum with increasing concentration of CuI, (d) Fluorescence spectrum with increasing concentration of CuI, and (e) Stern–Volmer plot of (d).

we already knew the fluorescent nature of GO. The details of it will be a combination of static and dynamic quenching if
these experiments are provided in the section below. the observed Stern–Volmer plot is curved. In our case, the
fluorescence quenching is most probably static as the observed
Stern–Volmer plot is linear as shown in Fig. 4(e). However,
Fluorescence spectroscopic analysis
due to lack of time-resolved fluorescence spectroscopy, we
The steady-state fluorescence emission spectroscopy is a very are not very sure about it. The Stern–Volmer plot analyzes
sensitive technique used for the detection of electronic inter- the relationship between fluorescence quenching (or enhance-
actions and optical properties of materials [52, 53]. With the ment) and the concentration of analyte. The Stern–Volmer
excitation wavelength of 265 nm, we observed a strong fluo- plots Io/I against the concentration of analyte quencher on
rescence of GO at 340 nm. On continuous increase in addi- X-axis. Considering the static binding of our materials, the
tion of copper iodide solution, a progressive decrease in the slope of the Stern–Volmer plot is considered as the binding
emission intensity i.e., quenching of GO was observed due constant of the materials. With the correlation coefficient
to the binding of GO with CuI. This quenching of fluores- value of 0.9960, the binding constant between GO and CuI
    Journal of Materials Research   2022   www.mrs.org/jmr

cence is shown in Fig. 4(d). Since, the π-electrons of graphene is found to be 2.3 × ­103 ­M−1. Hence, the steady-state fluores-
oxide are responsible for this fluorescence, therefore it is safe cence emission (PL) spectra and UV–Vis spectroscopy both
to claim that the phenomena of fluorescence quenching is confirmed the binding of graphene oxide with copper iodide
occurring due to the interaction of π-electrons of graphene or vice versa.
oxide with copper iodide. The lesser number of available It is already known in the literature that graphene oxide
π-electrons results in lower emission after addition of CuI. interacts with copper cations through its negatively charged
The fluorescence quenching is considered either static (inter- functional groups, resulting in the hybrids with increased con-
action in the ground state) or dynamic (the interaction occurs ductivity [54]. Those results were confirmed by our studies using
in the excited state of fluorescent material, i.e., GO; and CuI), UV–Vis and fluorescence spectroscopy techniques. In the litera-
if the corresponding Stern–Volmer plot is straight. However, ture, sulfate anions were used, which in our studies were iodide

© The Author(s), under exclusive licence to The Materials Research Society 2022 7

anions. Further, as seen later in our studies, the increase in con-
ductivity of hybrid layer with continuous increase in the copper
ions result in the increase in PCE of our devices.
Dynamic light scattering, zeta‑potential and SEM
analysis
Figure 5(a) and (b) shows the size and zeta-potential of GO and
CuI, along with the size and zeta-potential of GO-CuI hybrids,
whereas Fig. 5(c) shows the SEM image of GO-CuI hybrids. It
can be clearly observed in Fig. 5(a) that the hydrodynamic size
of GO-CuI hybrid has been increased after binding, compared
to either GO or CuI individually. Similarly, the zeta-potential
of GO-CuI hybrid as shown in Fig. 5(b) is an average of the
zeta-potential of GO and CuI, when mixed in 50:50 ratio. These
results confirm that these two moieties interact with each other.
The relevant size and zeta-potential graphs are provided in the
supplementary information of this article. The SEM image does
not show any significant difference from the GO, as it is difficult
to visualize copper or iodide ions attached to the GO.
J–V characterization and power conversion efficiency
of fabricated perovskite solar cells
The perovskite solar cells were developed in an open-air envi-
ronment. Figure 6 shows J–V curve graphs as plots of voltage
(V) against current density (mA ­cm−2) for fabricated devices
and their corresponding device architecture, respectively. These
Figure 5:  (a) Size and (b) zeta-potential stability comparison of GO, CuI, and GO-CuI hybrids; (c) SEM image of GO-CuI hybrids.
© The Author(s), under exclusive licence to The Materials Research Society 2022
Article
J–V curves were obtained for the three devices with hybrid
HTL ratios of 50:50, 60:40, and 80:20 for graphene oxide and
copper iodide, respectively, as shown in Fig. 6(a), (c), and (e),
respectively. Essentially, the effects of ratios of hybrids on the
performance of devices were observed. Further, zinc oxide was
used as an electron transport layer, and perovskite as a light
absorbing material. The first device with architecture (FTO/
GO-CuI (50:50)/Perovskite/ZnO/Ag electrode) as shown in
Fig. 6(b), provided an open circuit voltage (Voc) of 0.54 V, short
­ Acm−2, fill factor (FF) of 50%, and a
circuit current (Jsc) of 10.2 m
power conversion efficiency (PCE) of 2.79%. The second device
with architecture (FTO/GO-CuI (60:40)/Perovskite/ZnO/Ag
electrode) as shown in Fig. 6(d), provided an open circuit volt-
age (Voc) 0.51 V, short circuit current (Jsc) of 10.1 m ­ Acm−2, fill
factor (FF) of 50%, and a power conversion efficiency of 2.56%.
Similarly, the third device with architecture (FTO/GO-CuI
(80:20)/Perovskite/ZnO/Ag electrode) as shown in Fig. 6(f),
provided an open circuit voltage (Voc) of 0.53 V, short circuit
current (Jsc) of 7.91 mA ­cm−2, fill factor (FF) of 50%, and a
power conversion efficiency of 2.14%. We observed that change
in concentration of hybrids does not affect the fill factor (FF)
generally, however, the power conversion efficiency decreases
with the decrease in concentration of copper iodide or increas-
ing concentration of graphene iodide, providing the clue that
copper iodide acts as a better HTL material when compared
to graphene oxide. In other words, the efficiency of these solar
cells was enhanced by increasing the concentration of CuI and
    Journal of Materials Research   2022   www.mrs.org/jmr
8
 Article

15
a GO-CuI (50:50)

Current Density (mA/cm2)

10

Voc= 0.54 V
5 Jsc= 10.2 mAcm-2
F.F= 0.50
P.C.E= 2.79%

0
0.0 0.2 0.4 0.6
Voltage (V)
12
c GO-CuI (60:40)
10
Current Density (mA/cm2)

4 Voc= 0.5 V
Jsc = 10.1 mAcm-2
2 F.F= 0.5
PCE=2.56%
0
0.0 0.2 0.4 0.6
Voltage (V)

10
e GO-CuI (80:20)
Current Density (mA/cm2)

4 Voc= 0.53
Jsc= 7.91

2 F.F= 0.51
PCE= 2.14%

0
0.0 0.2 0.4 0.6
Voltage (V)

Figure 6:  J–V curves for GO-CuI-based perovskite solar cells at (a) 50:50, (c) 60:40, and (e) 80:20 ratios of hybrid hole transport layers; and their
corresponding device architectures (b, d, and f ).

decreasing the concentration of graphene oxide. The standard of GO is in the range of 1­ 0–2−10–6 S/cm depending on the vari-
formulas used for the calculation of power conversion efficiency ous factors [55], whereas the conductivity of CuI is ~ 156 S ­cm−1
    Journal of Materials Research   2022   www.mrs.org/jmr

of solar cells are provided in the supplementary information (SI)
of this article. One of the possible reasons for this decrease in
efficiency with increasing GO concentration can be attributed
to the increase in the thickness of graphene oxide layer, as previ-
ously, Dan Li et al. showed that an increase in the thickness of
graphene oxide layer decreases the performance of the devices
[29]. It is evident that increasing the GO concentration in the
hybrids causes increase in the thickness of the HTL layer. Fur-
ther, a quick literature review reveals that conductivity of these
hole transport materials is widely different, as the conductivity
[56], which contributes to better efficiency of CuI as compared
to graphene oxide. However, the absorbing capacity of GO
layer makes it highly comparable to copper iodide. The gradual
improvement in the hole mobility of the hole transport layer
occurs by increasing the concentration of copper iodide due
to its inherent properties of higher conductivity. Further, it has
been already proved that a transport layer with high mobility
and low thickness is required for the improved performance of
the devices [57]. Other reasons that are attributed to higher effi-
ciency of CuI-based solar cells is due to the binding of Cu ions to

© The Author(s), under exclusive licence to The Materials Research Society 2022 9
 Article

the GO functional groups, resulting in increase in conductivity

and better hole extraction by hybrids.
The other possible reason for the differences in the efficiency
of devices can be figured out from the energy level diagram. This
energy level diagram is shown in Fig. 7. This diagram shows
that upon illumination of the device with a solar simulator, the
perovskite layer absorbed incoming photons. Its electrons were
excited from the HOMO level to the LUMO level, leaving the
holes behind. ETL and HTL transported these electrons and
holes to the anode (Ag electrode) and cathode (FTO electrode),
respectively. ZnO nanoparticles layer effectively transported
the electrons, whereas the hybrid GO-CuI layer transported the
Figure 7:  Schematic of energy level diagram for our devices.
holes. The HOMO levels (valence band) of GO [9] and CuI [30]
are almost similar and compete the process of hole transfer, how-
ever, CuI has a little edge over GO with a difference of 0.1 eV.
hybrid was assumed to be an average of GO and CuI, as shown
This small difference also plays an important role toward higher
in the blue color. However, it was important to calculate the
power conversion efficiency with higher concentration of CuI.
band gap and estimate the HOMO–LUMO levels of the hybrids
as compared to GO and CuI. The direct band gap of GO-CuI
Assessment of the band gap and HOMO–LUMO levels hybrids and pure CuI was calculated from the obtained UV–Vis
of GO‑CuI hybrids spectra [Fig. 4(a)] by using Tauc’s equation. The corresponding
The HOMO and LUMO levels of the CuI, GO, and ZnO were Tauc’s plot are shown in Fig. 8. The calculated value for direct
considered from the literature [9, 30, 58] in Fig. 7. The HOMO of band gap of CuI was 3.78 eV, for GO-CuI (50:50) hybrid was

a Direct band gap of CuI b Direct Band Gap of GO:CuI; 50:50

0.20 0.4
( hv)2 (eV2cm-2)

0.3
( hv)2 (eV2cm-2)

0.15

0.10 0.2

0.05 0.1
Eg = 5.0 eV
Eg= 3.78 eV
0.00 0.0

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 1 2 3 4 5 6 7

Energy (eV) Energy (eV)

0.40
c Direct Band Gap of GO:CuI; 60:40 d Direct Band Gap of GO:CuI; 80:20
0.35 0.20
0.30
0.15
( hv)2 (eV2cm-2)

( hv)2 (eV2cm-2)

0.25
    Journal of Materials Research   2022   www.mrs.org/jmr

0.20
0.10
0.15
0.10
0.05
0.05
Eg = 4.94 eV Eg = 4.76 eV
0.00 0.00
-0.05
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Energy (eV) Energy (eV)

Figure 8:  Direct band gap calculations using Tauc’s equation for (a) CuI, (b) GO-CuI hybrid (50:50), (c) GO-CuI hybrid (60:40), and (d) GO-CuI hybrid
(80:20).

© The Author(s), under exclusive licence to The Materials Research Society 2022 10
 Article

5.0 eV, for GO-CuI (60:40) hybrid was 4.94 eV, and for GO-CuI
(80:20) hybrid was 4.76 eV, respectively. The direct band gap
calculated for GO is already discussed in Fig. 1 earlier.
The obtained band gaps were then used to calculate the
potentials for HOMO and LUMO using the following empiri-
cal equations.

EHOMO = c − Ee − 0.5 Eg (1a)

ELUMO = c − Ee + 0.5 Eg (1b)

ELUMO = EHOMO + Eg (2)

EHOMO and ELUMO are the HOMO and LUMO potentials,
respectively. Eg is the band gap of these materials calculated from
Figure 9:  Calculated energy level diagrams for GO, CuI, and hybrids,
Tauc’s plot as described above. Ee is the energy of free electrons representing the corresponding band gap and HOMO–LUMO levels.
on the hydrogen scale (4.5 eV) [59–62]. Finally, χ is the elec-
tronegativity of the nanocomposites, calculated through follow-
ing equation:
  1
χ = x(A)a x(B)b x(C)c
a+b+c
, (3)

where x(A), x(B), x(C), etc., are the electronegativities of indi-

vidual atoms present in the composites. a, b, and c are the num-
ber of atoms present in those composites [60]. The calculated
values of Eg and χ for all these materials are shown in Table 1.
When the HOMO levels were assessed as shown in Fig. 9,
it was evident that GO has the highest HOMO level among all,
confirming that the hole transfer mechanism was better asso-
ciated with the hybrids. Interestingly, increasing the concen-
tration of CuI in hybrids further lowered the energy level of Figure 10:  Energy level diagram for GO and hybrid (50:50) obtained by
HOMO, making it more stable structure and possibly aligned computations, representing the corresponding band gap and HOMO–
LUMO levels.
to the perovskite layer. The HOMO level of CuI was at a similar
level that of GO. The slightly different HOMO level of CuI is
associated to the UV–Vis absorbance of CuI that was observed conjugated double bond, benzene rings, hydroxyl, epoxy, and
in acetonitrile due to its non-solubility in water. Further, higher carboxylic acid functional groups was used for these calculations.
PCE of CuI and CuI hybrid-based devices is also associated to The structure of the representative graphene oxide is shown in
the better hole mobility of copper iodide as compared to the the supporting information of this manuscript. The initial optimi-
GO [63–66]. zation showed that copper ions preferably attach to the hydroxyl
In order to further confirm that the HOMO energy level of functional group of GO. That structure was further investigated
GO-CuI hybrid was lower than the HOMO energy level of GO, for the HOMO–LUMO energy levels and band gap calculations,
DFT computations were performed using the LanL2DZ/B3LYP as shown in Fig. 10. Interestingly, the computational results verified
basis set. A representative GO molecule containing isolated and our earlier calculations that the hybrid has a lower HOMO energy
    Journal of Materials Research   2022   www.mrs.org/jmr

TABLE 1:  Calculated
S. No Material Electronegativity (χ) Band gap (eV) HOMO (eV) LUMO (eV)
electronegativity, band gap,
HOMO, and LUMO energy levels for
1 Graphene ­oxide* 2.648 4.49 − 4.097 0.393
GO, CuI, and hybrids.
2 CuI 2.248 3.78 − 4.1419 − 0.3619
3 GO:CuI:: 50:50 2.5077 5.0 − 4.4923 0.5077
4 GO:CuI:: 60:40 2.5077** 4.94 − 4.4623 0.4777
5 GO:CuI:: 80:20 2.5077** 4.76 − 4.3723 0.3877

*
 The electronegativity of GO was calculated on the rough estimated formula of ­(C2HO); based on the approxi-
mate atomic composition of GO, synthesized through Hummers Method [46].
**The electronegativities for all three composites were based on similar calculations for simplicity purposes.

© The Author(s), under exclusive licence to The Materials Research Society 2022 11
 Article

5.0 5.0
a PCE b Data Comparison
4.5
4.5 Polynomial Fit
4.0
4.0 PCE of pure CuI based PSC: 3.997%
PCE of Solar Cells
y = Intercept + B1*x^1 + B2*x^2
3.5
Equation

Plot B
3.0

PCE (%)
3.5 Weight
Intercept
No Weighting
3.997 ± --
B1
B2
-0.02578 ± --
3.16667E-5 ± -- 2.5
3.0
Residual Sum of Squares 0

2.0
R-Square (COD) 1

GO-CuI 50:50

GO-CuI 60:40

GO-CuI 80:20
Adj. R-Square --

Pure GO [9]
2.5 1.5

Pure CuI

Pure GO
1.0
2.0 PCE of Pure GO based PSC: 1.723%
0.5
1.5 0.0
0 20 40 60 80 100 Device Concentration
Percentage of pure GO (%)

Figure 11:  (a) Extrapolation of PCE for pure GO-based and pure CuI-based hole transport layers (b) Column chart of devices with their PCE and
corresponding ratios of HTLs.

level, which is the main reason that hybrids have better alignment our open-air processed CuI-based devices have shown better
with the perovskite layer, hence better power conversion efficiency. PCE as compared to the literature values [30].
It is also important to mention here that other theoretical As a result of these studies, it is shown that PCE obtained
methods are also available for the determination of conduction by combining different HTL materials can lead us to compare
and valence bands of semiconductor nanoparticles [67]. These not only the efficiencies of these HTLs (or ETLs) with differ-
determinations are generally based on the Fermi energy level ent ratios of materials, but also, we can easily find the PCEs of
and band gap of the materials. So far from the above studies, we unknown ratios just by extrapolating the efficiencies obtained
conclude that the interaction of functional groups of graphene by measuring PCE of only three devices. Further, air processing
oxide toward copper ions changes the HOMO and LUMO levels of these solar cells allows us to quickly obtain the comparison
of graphene oxide, which mainly causes the improvement in the of these devices, hence a lot of time can be saved by understand-
power conversion efficiency of these devices. ing the mechanism and other information of these devices in a
Another interesting factor in these studies comes from the very short span of time. This allows us to optimize only the best
fact that power conversion efficiency of pure GO-based and CuI- devices for further processing.
based HTL perovskite solar cells can be obtained by plotting
a polynomial graph of PCE of devices against the percentage
composition of GO and CuI in GO-CuI hybrids, as shown in
Conclusions
Fig. 11(a). The PCE varies inversely with increasing concentra- In this research work, three perovskite solar cells were fabri-
tion of GO, therefore polynomial function was applied for the cated with different ratios of two hole transport materials as
curve fitting in Fig. 11(a). Similar results have been reported a hybrid hole transport layer. These devices were prepared in
earlier by Lee et al., where increase in the concentration of cobalt an open-air environment for comparison purposes. Various
(as dopant) up to a certain level in nickel oxide hole transport factors were considered, e.g., rather than investigating these
layer resulted in increase in the PCE of their devices [68]. The solar cells in standard conditions, our main aim was to find
extrapolated graph exhibited the power conversion efficiency better hole transport material among the two. Further, the
of 1.72% for the device with 100% graphene oxide as a HTL efficiency (PCE) of prepared devices can also be extrapolated
(with 0% CuI), whereas a PCE of 4.0% was obtained with the to find the PCEs of different compositions of these materials,
    Journal of Materials Research   2022   www.mrs.org/jmr

device having 100% copper iodide as HTL (with 0% graphene hence one can obtain much information by just making three
oxide). It is, however, pertinent to mention that in our previous devices only. The calculated efficiency of one device was sim-
published paper [9], the efficiency of GO only-based device was ilar to our previous published data. This methodology saves
1.35%, which confirms that only GO-based devices have lower a lot of time and resources as compared to making devices in
PCEs in the given conditions. Figure 11(b) shows the column the standard conditions. The hole transport materials used in
chart representing PCEs of all devices whether obtained experi- our studies were graphene oxide and copper iodide, respec-
mentally or calculated by extrapolating graphs, and the PCE of tively. In literature, both materials have been used as an effec-
GO only-based device from our already published paper [9], tive HTLs, however, as hybrid materials, they have never been
showing that CuI is a better hole transport material overall as reported before. Since both have different physicochemical
compared to the graphene oxide. For the comparative purposes, properties, hence without experimenting, it was difficult to

© The Author(s), under exclusive licence to The Materials Research Society 2022 12

know the better of them, considering that graphene oxide has
much higher absorbing capacity, and CuI has much better
electrical conductivity. Zinc oxide was used as an electron
transport material in our studies. Graphene oxide and zinc
oxide were synthesized using literature protocols and charac-
terized by various techniques, such as UV–Vis spectroscopy
and fluorescence spectroscopy for their optical analysis. The
bandgap was also calculated by using the Tauc’s equation.
DLS studies were performed for obtaining the hydrodynamic
radius and zeta-potential for their relative stability. Similarly,
SEM, XRD, and FT-IR analysis were performed to analyze
their size, surface morphology, crystallinity, and the presence
of functional groups. The hybrid formulations were prepared
and analyzed by UV–Vis and steady-state fluorescence titra-
tion experiments for their binding studies, representing effec-
tive binding of these hole transport materials. The Stern–Vol-
mer plot was also obtained for their binding constant. The
size and zeta-potential of the hybrids also show their effective
binding. The GO-CuI hybrids were prepared with different
ratios of HTL materials and solar cell devices were made.
These three devices had a general architecture of FTO/GO-
CuI/Perovskite/ZnO/Ag electrode with hybrids composi-
tion of 50:50, 60:40, and 80:20 for GO and CuI, respectively.
The composition effect of hybrid layer on the performance
of devices was analyzed. Open circuit voltage, short-circuit
current density, fill factor, and power conversion efficiency
were calculated and compared. The fill factor remained more
or less same for all these devices; however, the power conver-
sion efficiency was decreased with increasing concentration
of graphene oxide. As observed from UV–Vis and fluores-
cence spectroscopy techniques, the binding result in hybrids
which are more conductive, mainly causes increase in the
efficiency of our devices. The band gaps and HOMO–LUMO
energy levels of GO, CuI, and hybrids were analyzed using
two different methods, which confirmed that hybrids had
lower HOMO levels, which was the other reason for higher
PCE of hybrids. The comparison plot was obtained, and effi-
ciencies of devices were obtained for pure CuI-based and
pure GO-based devices. The calculated PCE of GO-based
device was similar to earlier published results. These studies
are quite important and can be utilized with any combination
of hole or electron transport layers for a quick analysis of the
solar cells for the hybrid layers.
Experimental
Materials
All chemicals were obtained commercially and were used as
received without further purification. These were used for the
synthesis of hole and electron transport materials and for the
device fabrication. Sulfuric acid ­(H2SO4) and hydrochloric
© The Author(s), under exclusive licence to The Materials Research Society 2022
Article
acid (HCl) were purchased from Scharlau, Spain. Isopropyl
alcohol ­(C3H8O), hydrogen peroxide ­(H2O2), graphite powder
(C), sodium nitrate (­ NaNO3), and potassium permanganate
­(KMnO4) were purchased from Daejung, Korea. Zinc acetate
dihydrate ­(ZnC4H6O4.2H2O), methanol (­ CH3OH), acetone
­(C3H6O), and acetonitrile ­(C2H3N) were purchased from BDH.
Potassium hydroxide (KOH), 1-butanol (­ C4H10O), fluorine-
doped tin oxide-coated glass (FTO-Glass), copper iodide (CuI),
silver metal (Ag), methyl ammonium iodide (MAI), lead chlo-
ride ­(PbCl2), DMF ­(C3H7NO), and DMSO ­(C2H6OS) were pur-
chased from Sigma Aldrich.
Synthesis
Graphene oxide (GO)
Graphene oxide (GO) was synthesized by using already-reported
well-known Hummer’s method [69] with minor modifications.
2 g of graphite powder was added to 50 mL of concentrated
­H2SO4, followed by addition of 1 g of ­NaNO3 to the above solu-
tion at 0 °C (ice bath) under continuous stirring. Afterward 7 g
of potassium permanganate ­(KMnO4) was slowly added into the
above solution to prevent the strong reaction and temperature
was maintained below 20 °C for 60 min with vigorous stirring.
The ice bath was then removed, and mixture was stirred for fur-
ther 2 h and temperature was allowed to increase up to 35 ± 5
°C. 90 mL of distilled water was added to the reaction mixture.
Due to heat of hydration, the temperature was raised up to 70 °C.
3% ­H2O2 was added to the above solution with continuous stir-
ring. Upon treatment with the peroxide, the color of the solution
changed from brown to yellow which indicates the formation of
graphene oxide. The resulting mixture of GO was then filtered
and washed five times with distilled water and one time with
30% HCl to remove the acid and metal (Mn) ions, respectively,
which was later dried at 45 °C in an oven for 15 h. The formation
of graphene oxide was confirmed by UV–Vis spectroscopy, which
shows two absorption peaks at 230 nm and 304 nm, respectively.
Zinc oxide nanoparticles
Zinc oxide nanoparticles were synthesized by using the already-
reported method [70], for which the schematic diagram is pro-
    Journal of Materials Research   2022   www.mrs.org/jmr
vided in the supplementary information of this article. Briefly,
3 g of zinc acetate dihydrate was dissolved in 120 mL of metha-
nol in a two-neck round bottom flask and kept stirring on the
hot plate under reflux. Another solution was prepared by add-
ing 1.5 g of KOH in 65 mL methanol and was added slowly at
an interval totaling one hour to the first solution under vigor-
ous stirring for 2 h. After which the heating and stirring were
stopped and the solution was allowed to cool at room tempera-
ture. Zinc oxide nanoparticles were separated through centrifu-
gation (5000 rpm, 10 min) and then washed with methanol and
13

1-butanol, respectively. Zinc oxides nanoparticle precipitates
were dried at 60 °C in an oven for 12 h. These nanoparticles
were dispersed in aqueous phase and analyzed through UV–Vis
spectroscopy, which confirmed the formation of zinc oxide nan-
oparticles with the standard peak at 374 nm.
Thin films and device fabrication
The fabrication of perovskite-based solar cells in an inert envi-
ronment is quite common, but the fabrication of perovskite-
based solar cells in open-air environment is also a challenging
task as perovskite material has very little stability in the ambi-
ent environment. In this research work, the perovskite solar
cells were fabricated in an open-air environment. The devices
were fabricated with inverted assembly structure like FTO/
Hybrid(HTL)/Perovskite/ZnO(ETL)/Ag electrode with the
difference in hybrids composition only to analyze the effect of
composition of hybrids on the efficiency of the devices. Figure 6
shows the device architecture with the corresponding J–V curves
of all three devices. The step-by-step fabrication of the device(s)
is shown in Figure S5(SI).
As a first step, etching and cleaning of FTO-coated glass was
carried out. One-fourth part of coated side of FTO-coated glass
with dimensions of 1 × 1 ­cm2 was etched by using sandpaper. A
potentiometer (TES 2360 LCR Multimeter) was used to ensure
the removal of FTO coating, which was done for the deposition
of metal contact at the end to complete the circuit. The FTO
glasses were cleaned with detergent, distilled water, acetone,
and isopropyl alcohol, respectively, to remove the different
contaminations like dust particles, organic waste, and metal-
lic impurities, if any. These cleaned FTO-coated glass pieces
were dried in an inert gas environment. The stock solutions for
ETL, hybrid HTL, and precursor of perovskite were prepared.
ZnO and GO solutions (10 mg/mL) were prepared in distilled
water, whereas CuI solution was prepared in acetonitrile, also
with a concentration of 10 mg/mL. The hybrids as HTL (GO-
CuI) solution were prepared in the ratios of 50:50, 60:40, and
80:20 v/v, respectively, and sonicated for 30 min each to make
homogenous hybrids. The perovskite precursor was prepared
following the literature protocol by dissolving 413 mg of methyl
ammonium iodide (MAI) in 1 mL DMF and 775 mg of P ­ bCl2
in 3 mL DMSO. These two precursors in the v/v ratio of 1:3
were mixed and stirred for 30 min in a closed vial wrapped in
an aluminum foil, by using PC-351 Corning hot plate. The thin
film of hybrids GO-CuI (50:50) was fabricated by spin-coating
of 1 mL solution of hybrids on etched FTO glass at 1000 rpm
for 10 s and 3000 rpm for next 40 s, and then annealed at 95 °C
(by gradually increasing the temperature) for 10 min. The same
procedure was carried out for 60:40 and 80:20 hybrids by using
the VTC-100 vacuum spin coater. The schematics of these steps
are also shown in the SI. In the next step, fabrication of the
© The Author(s), under exclusive licence to The Materials Research Society 2022
Article
perovskite thin film was carried out. 1 mL of perovskite solu-
tion was deposited and spin-coated at 1000 rpm for 10 s and
3000 rpm for next 50 s on the previously fabricated layer and
then annealed at 95 °C for 90 min with gradual increase in tem-
perature. After few minutes of heating, the color of the perovs-
kite thin film changed to black which indicated the formation
of the perovskite thin film. The schematic diagram describing
the formation of the thin film is also shown in SI. On top of
the perovskite layer, the deposition of the zinc oxide electron
transport layer was carried out. ZnO NPs solution was prepared
in chlorobenzene to protect the perovskite layer from water.
The ZnO NPs solution was spin-coated on top of the perovskite
layer at 3000 rpm for 60 s and annealed at 95 °C for 10 min,
where the temperature was gradually increased. The schematic
diagram for the fabrication of a ZnO thin film is also shown in
SI. After ZnO deposition, all these three devices were placed in
a thermal evaporator chamber having a pressure of 1­ 0–6 mbar.
The silver electrode was deposited on all three devices by ther-
mal evaporation to complete the fabrication process. All devices
were characterized using a solar simulator to calculate the effi-
ciency of the devices.
Characterizations
UV–Vis spectroscopy
The UV–Visible spectra were obtained by using SPECORD 200
PLUS spectrophotometer by Analytik Jena, Germany with a
wavelength range of 190–1100 nm, equipped with a halogen and
a deuterium lamp. The solutions were prepared at room tempera-
ture and sonicated for 5–10 min before the analysis. The spectral
analysis of zinc oxide nanoparticles, graphene oxide, and different
hybrid formulations were carried out using a quartz cuvette with
a path length of 10 mm and a spectral bandwidth of 1.4 nm. All
analyses were done at room temperature along with their respec-
tive solvents as reference. The absorption spectra of graphene oxide
and zinc oxide were observed at a concentration level of 0.01 wt.%
dispersed in distilled water. For the titration experiments [Fig. 4(b),
(c)], the concentration ratio of the stock solutions (10 mg/mL) for
each GO and CuI were diluted to the ratio of 1:511 mL in water. In
these two experiments, the concentration of either copper iodide
    Journal of Materials Research   2022   www.mrs.org/jmr
or graphene oxide was kept constant with increasing amount
(increment of 375μL with each addition) of the other.
Tauc’s plot
Tauc et al. investigated the optical and electronic properties of
amorphous semiconductor materials and found a method for
determining the optical band gap plotted appropriately with
respect to the energy by using optical absorbance data. The
optical strength of any semiconductor material depends on the
difference between photon energy and band gap as follows:
14

(αhv)1 /n = A ∗ (hv − Eg),
where α represents the absorption coefficient, h is planks con-
stant, A* represents the slope of the Tauc’s plot, and E­ g repre-
sents the band gap, whether allowed or forbidden, and direct
or indirect.
n = 1/2 for direct allowed transition, n = 3/2 for direct for-
bidden transition, n = 2 for indirect allowed transition, n = 3 for
indirect forbidden transition.
Generally, the Tauc’s plot are obtained by plotting (αhv)1 /n
vs (hν). The intercept at the energy axis provides the band gap
[71]. We plotted a graph of (αhv)2 ­(eV2cm−2) vs. energy (eV) of
photon by using Tauc’s relationship to examine the band gap of
ZnO and GO.
Fluorescence spectroscopy
The steady-state fluorescence emission spectra were obtained
by using FluoroMax Plus spectrofluorometer by Horiba Instru-
ments. The measurements were observed at room temperature
by using a quartz cuvette which was transparent from all sides.
The slit width was fixed at 3 mm with a band pass of 12.75 nm
for all the experiments. 250 ppm stock solution of graphene
oxide was prepared at room temperature in distilled water and
was further diluted to the ratio of 1:3 with distilled water and
sonicated for 5 min before obtaining the spectra. Similarly, 1 mL
of 0.01 M stock solution of zinc oxide was diluted to the ratio of
1:3 in distilled water for measurements. For the titration experi-
ments, GO prepared as above, and 0.01 M solution of copper
iodide in acetonitrile were titrated. The titration experiments
were carried out with a fixed volume (1.5 mL) and concentration
of graphene oxide against increasing concentration of copper
iodide ranging from 0 to 1.2 mL as tabulated in S.I. The excita-
tion wavelength was kept fixed at 265 nm.
FT‑IR spectroscopy
The Fourier transform infrared spectroscopy analysis was per-
formed at room temperature by using a Shimadzu IR Tracer-100
FT-IR spectrophotometer with wavenumber range from 350 to
7000 ­cm−1.
Dynamic light scattering and zeta‑potential analysis
The dynamic light scattering (DLS) and zeta-potential analysis
were performed using a zeta-sizer nano (model ZSP Malvern
Analytical technology, UK) along with the Malvern zeta-sizer
software (v7.13). All solutions were prepared in distilled water
and sonicated for 5–10 min before the analysis. The measure-
ments were taken in triplicate at 25 °C. The size was measured
using ­1730 non-invasive backscatter mode and the zeta-poten-
tial was observed by M3 phase light scattering mode analysis,
© The Author(s), under exclusive licence to The Materials Research Society 2022
Article
respectively. The accuracy of the instrument was ± 2% and
equipped with a 10 mW 633 nm He–Ne laser. For the zeta-
potential analysis, the sample was filled in a disposable folded
capillary cell (DTS1070) by using a disposable 5 mL syringe, to
avoid the formation of bubbles inside the cell.
Scanning electron microscopy
The surface morphology and estimated size of synthesized mate-
rials were analyzed by using high-performance JOEL JSM-6490
scanning electron microscope (SEM) with the magnification of
×40,000 and a bar scale of 500 nm. For SEM images, the synthe-
sized particles were drop casted on FTO-coated glass and were
air dried before analysis.
X‑ray diffraction
The crystalline structure of graphene oxide and zinc oxide nano-
particles were analyzed by using Scintag X1 Theta-Theta X-ray
Diffractometer from STOE, Germany. The scanning range was
set from 5° to 80°. The samples were layered on the FTO-coated
glass and dried at room temperature.
Current density–voltage analysis
The current density–voltage (J–V) characterization was per-
formed by using the source meter of Keithley (Model M2420).
The applied voltage was set from − 1.0 V to 1.0 V with 60 sweep
points. A solar simulator (Sciencetech AM 1.5G Filter Solar
Simulator) was used to measure the performance of perovskite
solar cells, by generating a spectrum of AM1.5 at power intensity
of 100 mW/cm2. A silicon-based photovoltaic solar cell (JIM-
100) was used as a reference to calibrate the lamp.
Acknowledgments 
The research described in this paper was partially financially
supported by the Higher Education Commission of Pakistan under
National Research Program for Universities with Reference No.
20-3369/R&D/HEC/14/978, which was awarded to Dr. A. J. Shaikh.
Francis Agada is thankful to Queen Elizabeth Commonwealth
Scholarship for his graduate studies, with reference no. FE-2019-100.
    Journal of Materials Research   2022   www.mrs.org/jmr
Author contributions 
ZA and FA performed bench work, ZA wrote the initial
draft; AHK provided all help related to fabrication of perovskite
solar cells, AMK provided help with the UV–Vis experiments;
MB and MA helped with the SEM images and XRD experi-
ments, AJS conceived the idea and was the major contributor
in writing the manuscript. All authors read and approved the
final manuscript.
15

Data availability  12. R. Rajeswari et al., Emerging of inorganic hole transporting
Data sharing not applicable to this article as no datasets were
generated or analyzed during the current study.
Declarations 
Conflict of interests  The authors declare that they have no compet-
ing interests.
Supplementary Information
The online version contains supplementary material avail-
able at https://​doi.​org/​10.​1557/​s43578-​022-​00537-x.
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