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Journal of Materials Chemistry A Accepted Manuscript

ARTICLE

Graphene Oxide as Efficient Hole Transporting Material for High-

Performance Perovskite Solar Cells with Enhanced Stability
Received 00th January 20xx,
Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x
www.rsc.org/
Qing-Dan Yanga,b,c‡, Yuanhang Chengb,c, Ho-Wa Lib,c, Zhiqiang Guanb, Binbin Yub,c Jia Lid‡*, and Sai-
Wing Tsangb,c*
In recently developed high effcieincy metal organometal halide perovskite solar cells, both the electron and hole interlayer
materials have been shown palying key roles in determining the perovksite crystal growth, devie performance and
stability. However, interlayer materials which can facilitate both high efficiency and stability with low-cost are still limited.
Here, we demonstrate that by contolling the thickness of solution-processed graphene oxide (GO), one can achive a
balance of high work-function and conductivity. Using the optmized GO as hole transporting material (HTM) in perovskite
solar cells, a high PCE of 16.5% with no hysteresis can be achieved with excellent light-soaking photocurrent stability in
comparison to the commonly used organic-based HTM. Under high humidity and continuous light soaking, the
encapsulated perovskite devices retain over 80% of their initial efficiency for over 2,000 hours. Detailed studies on the GO
binding energy and the charge transfer efficiency with perovskite, the crystal morphology have shed light on the origin of
the improvement in photovoltaic devices. Benefited from the merits of low-temperature, solution-processability and low-
cost, GO and the proposed fabrication techniques pave a way towards the potential scalable production of perovskite solar
cells with high PCE and excellent stability.

To realize PV effect of PSCs, two kinds of device architectures

Introduction
Since the first observation of photovoltaic (PV) effect from
hybrid halide perovskites, the emerging field of perovskite
solar cells (PSCs) has become one of the most promising
1-3
technologies for the next-generation thin-film photovoltaics.
As a light harvester, perovskites (e.g., MAPbI3, MA: CH3NH3)
are featured with the combination of low-cost manufacturing
4,5
and competitive PV efficiency, which can be ascribed to the
ease of solution-based fabrication process and the excellent
photophysical properties, such as high absorption coefficient,
long charge-carrier lifetimes, long charge diffusion lengths and
6-8
photon recycling effect. Over the past years, PSCs has
exhibited a rapid raise of power conversion efficiency (PCE) up
9 crystallization, and conditions of crystal boundary of
to over 22%.
have been proposed according to the transporting behaviors
of photo-generated carriers, i.e., the n-i-p structure inherited
10-13
from dye-sensitized solar cells and the inverted p-i-n
structure by mimicking the design concept of organic solar
14,15
cells. Although conventional n-i-p structure dominates
most of the champion PCE, inverted p-i-n PSCs have also
attracted extensive attention due to its better compatibility
16
with scalable and low-temperature fabrication process. One
typical inverted PSCs can be fabricated with the configuration
of transparent anode electrode/hole transporting layer
(HTL)/perovskite/electron transporting layer (ETL)/cathode
17
electrode. It has been well evidenced that the HTL plays a
very crucial role in the inverted PSCs. First, the morphology,
perovskite are strongly dependent on the employed HTL, on
18
which the perovskite directly grows. Second, it requires the
appropriate electrical and electronic properties of the
interface between HTL and perovskite to facilitate carrier
extraction and collection while minimize the charge
19
recombination. Third, the reliability and chemical
compatibility of hole transporting material (HTM) should also
be taken into account to guarantee the long-term device
20
stability. In addition, there are other factors beyond the
above are needed to be considered when HTM is used in
inverted PSCs, such as hydrophobic properties, UV light cutoff
21
and costs of raw materials and processing. Consequently, to

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achieve good PV performance of inverted PSCs in terms of
lower $/Watt and better device stability for commercial uses,
it is of vital importance to rationally design the HTL with
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appropriate material and processing to minimize the energy
mismatch in a reliable and cost-effective HTL/perovskite
22
interface for efficient carrier extraction.
In fact, it is very challenging for a single HTM to satisfy all of
the desirable requirements mentioned above. In inverted
PSCs, the most popular HTM is poly (3, 4-
23
ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS).
Owing to the appropriate energy level, good mobility and good
transparency in visible and near infrared regions, PEDOT:PSS
has demonstrated the continuous success in delivering high
PCE. However, the organic PEDOT:PSS is sensitive to oxygen
and especially to moisture in comparison to its inorganic
24
counterparts. Furthermore, PEDOT:PSS has high acidity and
hygroscopic properties, leading to the detrimental effects to
25
device stability. To overcome these problems, many efforts
have been focused on searching alternative HTM to
PEDOT:PSS. Inorganic materials such as CuSCN and NiOx are
introduced into the inverted PSCs with decent PV
26,27
performance. However, CuSCN-based PSCs showed poor
device stability, and NiOx-based PSCs usually required high-
temperature treatment, vacuum-based processing or
complicated doping protocol, which increased the processing
28
cost and complexity for the device manufacturing. Recently,
a new organic HTM, namely Trux-OMeTAD, was designed by
introducing triarylamine and aliphatic side-chains onto the C3h
29
Truxene-core. The excellent PV performance, in terms of PCE
as high as 18.6% and good stability were achieved, yet
complicated synthesis process and relatively high cost may
hinder application of Trux-OMeTAD in scalable production of
PSCs. Obviously, PSCs is still suffering from the lack of well-
qualified HTM. Thus, it is an urgent need to develop low-cost
and simply processed interfacial materials, which can well
balance with high transparency, good passivation properties,
high conductivity, adequate work function (WF) and, more
importantly, better stability.
Recently graphene oxide (GO) has been applied in various thin
30-32
film electronic devices as interlayer materials. GO can be
simply prepared by using solution-based process with cost-
33
effective raw materials. It is self-stable and has no reaction to
perovskites film in PSCs. However, it is still challenging using
GO in PSCs as to obtain high WF and conductivity. The high WF
can lead to Ohmic contact and enhance the build-in potential
for higher open circuit voltage (VOC). On the other hand, high
conductivity can guarantee high charge collection efficiency
and high short-circuit current density (JSC). Intrinsically, GO has
a high degree of oxygen contents, which results in high WF,
but such high oxygen contents GO has extremely low
34
conductivity which cannot be used as HTL in PSCs. To achieve
optimal PV performance, WF and conductivity must be
delicately balanced in GO for PSCs. In order to increase the
conductivity of GO, various chemical driven reduction
35
approaches were adopted to decrease the oxygen contents.
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Although encouraging PV performance has been obtained by
using such reduced GO (RGO), the reduction processes would
lower the WF and result in poor photovoltaic performance. In
addition, the reduction process complicates the device
Journal of Materials Chemistry A Accepted Manuscript
fabrication and certain reducing agents and surfactants are
32
toxic and explosive, leading to its inappropriateness in
scalable production. Alternatively, as adopted in this work, the
reduction reaction of GO can be done in thin film with
moderate annealing at a low temperature in air. By carefully
controlling the time, it can potentially enhance the
conductivity without affecting the high WF of as prepared GO
film. This is believed that such simple fabrication process to
balance the WF and conductivity can facilitate the application
of GO as HTL in PSCs in low-cost. One pioneer work has shown
that using GO as an alternative for PEDOT:PSS in PSCs can lead
30
to improved PCE. However, the reported highest efficiency in
30,36,37
GO-based PSCs is only 12% and no further study on the
stability of GO-based PSCs. In fact, there is still lack of detailed
study on the origin of such improvement of PV performance in
GO-based PSCs.
Here, we report that by optimizing the thickness of GO thin
film as HTL in planar inverted PSCs, a high PCE up to 16.5% can
be achieved. Compared to conventional PEDOT:PSS HTL, GO-
based devices have significant improvement in continuous
light soaking and shelf-lifetime stabilities. The devices retain
over 80% of initial PCE after 2000-hours stability test. The
improvement is contributed by the higher work-function of GO
and larger perovskite crystals. Furthermore, state-stay PL and
transient photocurrent results support that the GO/perovskite
interface has better hole-extraction efficiency than the
PEDOT:PSS/perovskite interface.
Results and discussion
2
Inverted PSCs with the active area of 0.1 cm were prepared
with the configuration of glass/indium tin oxide
(ITO)/HTL/perovskite/fullerene (C60)/BCP/Au. The schematic
of device configuration is shown in Figure 1a. Notably, two
different HTMs, i.e., GO and PEDOT:PSS, are used for
comparison. Similar to PEDOT:PSS, the GO HTM can also be
deposited on ITO glass at room temperature using the solution
process. This is attributed to the numerous polar functional
groups (as shown in figure S1) bonded on GO sheets, which
allows GO to be easily dispersed into various polar solvents
such as dimethyl sulfoxide (DMSO) or deionized (DI) water.
Particularly, in this work, GO suspensions in DI water with
concentration of 0.3 mg/ml is prepared and the GO film is
deposited on ITO glass substrate by spin coating method. The
surface morphology of GO and PEDOT:PSS films on ITO
substrate is characterized by using atomic force microscopy
(AFM), which is shown in Figure 1b. As one can see, the GO
film has a root mean square (RMS) roughness in sub-
nanometer scale of 0.59 nm, which is smaller than that of
PEDOT:PSS film (1.53 nm). It can be speculated that the
smoother surface of GO film will provide a good contact with
perovskite layer, leading to the optimal growth of perovskite
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with larger grain size and high-quality crystallization. After the
films deposition, WFs of GO and PEDOT:PSS are analysed by
using ultra-violet photoelectron spectra (UPS), as shown in
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Figure 1c. Clearly, the prepared GO has higher WF (5.2 eV)
compared with PEDOT:PSS (4.9 eV), implying that GO is more
appropriate to form an Ohmic contact with the perovskite
active layer and the higher VOC can be expected. Figure 1d
shows the energy level diagram of PSCs using GO or
PEDOT:PSS as HTL. It has been well evidenced that minimizing
the energy level mismatch between the HTL and the
perovskite will minimize photovoltage loss and promote
36
carrier extraction and collection efficiency.
Fig. 1 (a) Device architecture of perovskite solar cells with PEDOT:PSS or GO as hole
transporting layer, (b) AFM images of GO and PEDOT:PSS film on ITO glass with scan
size of 2µm×2µm, (c) UPS spectra of PEDOT:PSS and GO spin-coated on ITO glass
substrate, (d) schematic energy diagrams of perovskite solar cells.
To further investigate the GO/perovskite interface,
photoluminescence (PL) spectroscopy and transient
photocurrent measurement were used to investigate the
quenching and charge collection efficiencies of perovskite on
GO, respectively. Figure 2a exhibits the PL spectra of
perovskite thin films deposited on different thickness of GO
and PEDOT:PSS, respectively. Obviously, compared to
PEDOT:PSS as the HTL, the perovskite PL intensity is
dramatically reduced with GO as the HTL. This indicates that
the photogenerated holes in perovskite are easier to be
transferred to the GO, as expected that GO has better energy
level matching with the perovskite. On the other hand, with
PEDOT:PSS as the HTL, the photogenerated holes are more
confined in the perovskite layer due to the interfacial energy
barrier and therefore high PL intensity. The transient
photocurrent results are consistent with the PL results as
shown in Figure 2b. A faster photocurrent decay in perovskite
was observed with GO as the HTL. It suggests that the
photogenerated holes in the perovskite are easier to transfer
to GO which has a higher work function than PEDOT:PSS as
measured by photoemission spectroscopy. Meanwhile, it is
also indicating GO can more effectively extracting the carriers
from perovskite layer and reducing the carrier recombination
because of the rapid carrier collection prevents charge
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accumulation at the interface of perovskite with the GO charge
extraction layer. It is also can be found that, with increasing
the GO thickness, the carrier extraction efficiency decreasing
which might be caused by the poor conductivity of thicker GO
Journal of Materials Chemistry A Accepted Manuscript
layer.
Fig. 2 (a) Steady state PL spectra of perovskite layer on PEDOT:PSS and different
thickness of GO covered quartz substrates, (b) transient photocurrent of perovskite
solar cell on PEDOT:PSS and different thickness of GO modified ITO glass.
The current density-voltage (J-V) characteristics under AM1.5G
2
illumination at 100 mW/cm of the planar inverted PSCs using
PEDOT:PSS or GO as HTL are shown in Figure 3a. The
photovoltaic parameters determined from these PSCs are also
summarized in Table 1. The PEDOT:PSS-based device exhibits a
2
PCE of 11.9% with a VOC of 0.96 V, a JSC of 18.8 mA/cm , and an
FF of 65.7%. When PEDOT:PSS is replaced by GO, the PCE is
remarkably increased to 16.5% with a VOC of 1.00 V, a JSC of
2
21.6 mA/cm , and an FF of 76.2%. It is well known that the
morphology of the perovskite absorber layer plays a very
crucial role in determining the performance of the perovskite
solar cells. The formation of a high quality and crystallized
perovskite is strongly dependent on the substrate where it will
grow and the processing parameters. Figure 3b shows the SEM
images of the perovskite films deposited on PEDOT:PSS and
GO substrates, respectively. A dense and uniform perovskite
layer with grain sizes in range of 500-1000 nm is formed on top
of the GO layer. In contrast, the perovskite domains are much
smaller when perovskite grows on the PEDOT:PSS substrate,
which well agrees with the work reported by Huang et al.21
Indeed, it has been verified that compact and well-crystallized
perovskite film with grain size larger than a few hundred
nanometers are necessary to achieve a high PCE of PSC, owing
to the fact that larger grains can effectively suppress the
charge recombination due to their reduced concentration of
grain boundaries.21 Therefore, the larger perovskite crystals
obtained in GO-based devices are attributed to the improved
PV performance. The different growth mechanisms of
perovskite on GO and PEDOT:PSS are caused by various
surface properties of GO and PEDOT:PSS, such as wettability or
morphology. It has been reported that graphene can act as an
effective template to nucleate small organic molecules at the
grain boundaries of graphene and form a large crystal.38
Accordingly, it can be extrapolated that it is the suppressed
nuclei formation of CH3NH3PbI3 on top of GO substrate that
leads to a smaller growth rate compared to the perovskite film
grows on PEDOT:PSS substrate. The crystal quality of
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perovskite films grow on GO and PEDOT:PSS substrates are Table 1. Summarized performance of perovskite solar cells based on PEDOT:PSS and GO
also studied by x-ray diffraction (XRD) and the corresponding with different GO thicknesses.
XRD patterns are shown in Figure 3c. The perovskite films grow
Buffer layer VOC (V) JSC (mA/cm2) FF (%) PCE (%) RS (Ω·cm2)
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on GO and PEDOT:PSS exhibit similar diffraction patterns,

PEDOT:PSS 0.96 18.8 65.7 11.9 9.46

Journal of Materials Chemistry A Accepted Manuscript

indicating a tetragonal perovskite structure. Notably, the GO- GO (2nm) 1.00 21.6 76.2 16.5 5.46
based perovskite film, shows stronger and narrower XRD GO (4 nm) 0.92 15.8 63.2 9.2 8.42
peaks; the (110) peak shows a full width at half maximum GO (6 nm) 0.92 14.0 63.1 8.1 9.61
(FWHM) value of 0.13, which is 19% smaller than that of GO (10 nm) 0.89 4.9 53.1 2.3 27.82
PEDOT:PSS/CH3NH3PbI3 (FWHM=0.16), and the result is
consistent with the larger perovskite grains observed by SEM
in Figure 3b.

Fig. 4 J-V curve of perovskite solar cells with different thickness of GO buffer layer.

To further investigate the origin of such improvement of PV

Fig.3 (a) J-V characteristic of GO and PEDOT:PSS devices under AM1.5G 1 sun
illumination with forward and reverse scan, (b) SEM images and (c) XRD patterns of
perovskite layers on PEDOT:PSS and GO modified ITO glass substrate, insert figure is
enlarged (110) diffraction peak of perovskite film.
As mentioned above, the intrinsic GO has low conductivity due
to a high level of oxygen contents. To achieve the optimal PV
performance based on the good balanced between WF and
conductivity in GO, thickness of GO films are carefully tailored
by layer-by-layer deposition to optimize the conductivity for
PSCs with higher PCE. The PV performance of devices with
various GO thicknesses are shown in Figure 4 and summarized
in Table 1. As expected, PV performance of PSCs can be
significantly improved when GO thickness decreases from 10
nm to 2 nm. This observation can be ascribed to the following
two reasons: the first one is thinner GO film will lead to higher
conductivity and smaller device series resistance (the
corresponding series resistance of perovskite solar cell with
different thickness of GO interlayer calculated from J-V curves
have been shown in table 1), and the other one is the thinner
GO film would help to minimize carrier recombination. As a
result, the dramatically enhanced JSC and FF can be anticipated
with thinner GO HTL. Besides the conductivity, thinner GO film
will also result in the higher optical transmittance, leading to
more sufficient generation of carriers. In short, good PV
performance of GO-based PSCs can be achieved by combining
the purposively designed high WF with the optimized
conductivity and transparency of GO film achieved by simply
tuning the film thickness.
performance, the measurement of external quantum
efficiency (EQE) has been performed. Figure 5a shows the EQE
results of different PSCs based on GO and PEDOT:PSS, the
integrated current for these two different interlayer materials
2
are 18.5 and 20.8 mA/cm , respectively, which are match well
with the JSC extracted from the J-V curve. The EQE spectrum of
GO-based device has demonstrated the similar profile with
that of PEDOT:PSS-based device. Interestingly, the EQE
intensity in the range of 700-800 nm is significantly enhanced
when GO is used as HTL. To have more in-depth understanding
of the enhanced JSC, device optical reflectance measurement
has been performed to get more insight into the optical
absorption of the active layer in devices. As shown in Figure
5b, the employment of GO can effectively reduce the
reflectance in UV (350-450nm) and visible regions (650-800
nm), and the reduced reflectance implies the enhanced optical
absorption and better utilization of incident photons for higher
JSC. A viable HTM in application also should facilitate stable
device performance. We sought to test the stability of GO-
based PSCs with steady state photocurrent to evaluate the
photo-stability and the shelf aging test to explore the lifetime
of PSCs under ambient humidity. The measurement of steady
state photocurrent aims at identifying the actual power output
and accurately characterizing the device efficiency. As shown
in Figure 5c, the photocurrent quickly rises to maximum for
devices using either GO or PEDOT:PSS as HTL, and the steady
state current is the same as that measured from the J-V
scanning. It is worth noting that the photocurrent of
PEDOT:PSS-based device dramatically decreases when
extending the light illumination to several hundred seconds. In
sharp contrast, the photocurrent of GO-based device remains

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nearly invariant even when the illumination duration is
prolonged to 3000 seconds. Obviously, GO-based device has
better photo-stability than the device employing PEDOT:PSS as
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HTL during the continuous light illumination.
Fig. 5 (a) EQE spectra of the GO and PEDOT:PSS based devices, (b) measured device
reflectance (R) and calculated device absorbance (A) using A = 1 – R, (c) steady state
current density of perovskite solar cells measured at maximum power point with
constant bias voltage of 0.85 V for GO based (black curve) and 0.72 V for PEDOT:PSS
(red curve).
Fig. 6 (a) Normalized PCE, VOC, JSC and FF of perovskite solar cells based on GO
(black) and PEDOT:PSS (red) as a function of time; J-V characteristics of
encapsulated (b) PEDOT:PSS and (c) GO based device at 0 to 78 days
To further demonstrate the potential of GO in the
improvement of device stability, the long-term aging test
under ambient humidity with RH ~60% has been conducted.
The devices used in stability test are encapsulated inside a
glovebox immediately after the fabrication. After the initial J-V
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measurements, the devices are continuously illuminated and
then stored in dark under standard laboratory conditions.
Figure 6a shows parameters of PCE, FF, JSC and VOC of the GO-
based and PEDOT:PSS-based devices over a long-term
Journal of Materials Chemistry A Accepted Manuscript
storage/operation. It can be seen that PCE of PEDOT:PSS-
based device rapidly decreases to 40% of the initial PCE after
just 1400 hours. Surprisingly, the GO-based device show much
better long-term stability. Its PCE decreases by only 10% after
nearly 2000 hours. Such a remarkable difference suggests that
GO can efficaciously enhance the perovskite solar cells
stability. The VOC remains almost unchanged during the
storage and operation testing process. The degradation mainly
comes from the JSC and FF. To understand the origin of
degradation, J-V characteristics of the two devices are
measured after different durations of operation/storage, as
shown in Figure 6b and c. It can be seen that while the J-V
characteristic of the PEDOT:PSS based device decays
continuously; the J-V characteristic of the GO based perovskite
solar cells show little changes after ~ 80 days of storage and
operation.
Conclusions
In summary, we demonstrated high efficiency and stability
perovskite solar cells with simple solution and room-
temperature processed GO as hole transporting materials. By
combining the high WF and the optimized thickness of GO thin
film, GO-based PSCs has achieved promising PCE of 16.5% and
excellent device stability, which is superior to the reference
device with the commonly used PEDOT:PSS as HTM. The
improvement of PV performance is attributed to the larger
grain size of perovskite growing on GO film, enhanced charge
collection efficiency with better interfacial energy alignment,
and higher optical absorption of the active layer. More
importantly, the stability of PSCs using GO as HTL has been
significantly improved in comparison to the PSCs employing
conventional PEDOT:PSS. All of the achieved results have
demonstrated that GO, without any other post-treatment
processing, has the competent capability to play as efficient
and reliable interfacial material to facilitate low-cost and
highly stable perovskite solar cells.
Experimental section
Graphene oxide was prepared from graphite powder by
modified Hummer method, which has been reported in
39
elsewhere. Briefly, 0.45 g of KNO3 and 17 mL of concentrated
H2SO4 were added to 0.5 g of graphite powder cooling in an ice
bath. The mixture was slowly added with 2.25 g of KMnO4 for 1
hour with continuously stirring. The solution was left to stir for
an extra 2 hours in the ice bath, and then removed and kept
for 5 days with stirring continuously to insert sufficient
functional groups, such as –COOH and -OH. After that, black
viscous liquid was obtained and added to 50 mL aqueous
solution of 5 wt % HCl over 1 hour with continuously stirring.
After the mixture was stirred for a further 2 hours, 1.5 g of
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H2O2 (30 wt % aqueous) was added and then the mixture was
left to stir for another 2 hours. Then the material was washed
by DI water several times till PH value of the slurry close to 7,
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then the products was freeze dried for two days. In this work,
the GO concentration of 0.3 mg/ml was prepared by adding DI
water into the as-synthesized solid.
Device fabrication: The perovskite solar cells were fabricated
on ITO substrate (15 Ω/sq). The substrates were cleaned
sequentially with detergent, DI water, isopropanol, and
acetone in an ultrasonic bath for 10 minutes and then dried by
nitrogen gas. Before coating the hole transporting layers, ITO
substrates were finally cleaned under UV-ozone treatment for
10 minutes. A HTL (PEDOT:PSS or GO) was deposited onto the
substrates by spin-coating method with spin speed of 4000
rpm for 40 seconds. The layer of PEDOT:PSS was dried on a
o
hotplate at 150 C for 15 minutes in air. Compared to
PEDOT:PSS layer, the GO film were dried at 50 C for 10
o Adv. Energy Mater., 2016, 6, 1600401-1600407.
minutes in air.
Perovskite precursor solution and film preparation: The
precursor solution was prepared by dissolving PbI2 (462
mg/ml) in anhydrous dimethylformamide (DMF) while stirring
at 70 oC overnight. MAI was dissolved in anhydrous
isopropanol at a concentration of 35 mg/ml. PbI2 layer was
spin coated on top of PEDOT:PSS and GO modified ITO
substrates at 4000 rpm for 40 s, after that the PbI2 films were
o
annealed on hotplate at 70 C for 10 minutes immediately
after spin-coating. The MAI solution was then added onto the
PbI2 films loading for 90 seconds before spin-coating at 4000
rpm for 40 seconds. Finally, the perovskite films were solvent
o
annealed (in DMF) at 100 C for 1 hour. After that the
perovskite films were transformed from the glove box into a
vacuum chamber and C60 (20 nm), BCP (5 nm) and Au (80 nm)
layers were sequentially deposited on the CH3NH3PbI3 film by
-4
thermal evaporation under base pressure of 10 Pa. The active
2
area of the devices was 0.10 cm .
Acknowledgements
This work is supported by the Hong Kong Innovation and
Technology Commission (Project No: ITS/186/16), and the
National Natural Science Foundation of China (Project No.
61574120), and the Guangdong province Natural Science
Foundation of China (Project No. 2015A030313001).
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We demonstrated highly efficient and stable perovskite solar cells with simple
solution and room-temperature processed GO as hole transporting materials.
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Journal of Materials Chemistry A Accepted Manuscript