Effect of PCBM film thickness on the performance of inverted
Perovskite solar cells
Dian Wang, Naveen Kumar Elumalai, Md Arafat Mahmud, Mushfika Baishakhi Upama, Matthew Wright,
Kah Howe Chan, Cheng Xu, Ashraf Uddin
School of Photovoltaic and Renewable Energy Engineering, University of New South Wales, 2052, Sydney,
Australia
Abstract —The effect of electron transportation layer (ETL)
PCBM film thickness was investigated for the performance of
inverted structure perovskite solar cells. The charge
transportation study was carried by Mott-Schottky analysis. The
result shows the charge transportation status of different electron
thickness. A thicker PCBM layer could provide better diode
property, while the thinner layer would lead to higher short
circuit current. For this perovskite fabrication method, the
thicker film worked better. This study reveals the optimization of
PCBM depends on various factors, like cathode, and perovskite
films. To further improve the efficiency of devices, the perovskite
film and the design of device structure are needed to be
optimized.
Index Terms — PCBM, inverted perovskite solar cells, mix
halide.
I. INTRODUCTION
The perovskite solar cell has rapidly drawn the research
attention in last 3 years. The world record for perovskite solar
cells have hit over 20% in last year [1]. Perovskite promises
the capability of high efficiency, low energy input; potential of
fabricating flexible and semitransparent devices. All of these
advantages make perovskite solar cell a promising candidate
to replace the current commercially available Si solar cells.
The perovskite solar cell originally comes from the Dye
sensitized solar cells (DSSC). The electron transportation
layers (ETLs) are usually made by metal oxide semiconductor,
like TiO2, ZnO, SnO2, etc[2-4]. However, these metal oxide
ETLs require high temperature to form the layer. Therefore,
people start to work with inverted perovskite solar cells, which
normally has the organic hole transportation layers (HTLs)
underneath the perovskite layer, and use Organic ETLs to
transport the electrons. This device geometry was previously
widely used in organic solar cells, known as the “normal
geometry”. This geometry requires lower temperature to form
the charge transportation layers. The flexible devices have
been fabricated at PET substrates for this geometry[5].
In inverted perovskite device structure, the hole
transportation layer: PEDOT:PSS usually has better
conductivity, which allows to extract carriers more effectively.
However, the charge transportation behaviour of the PCBM
layers, what could be the optimized recipe for the ETLs has
not been investigated.
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In this work, we fabricated the perovskite solar cells with
the geometry: ITO/ZnO/Perovskite/PCBM/Ag using mix
halide precursor ink. The photovoltaic parameters of device
with different PCBM thickness were investigated. The detail
charge transportation behaviour of PCBM was evaluated by
Mott-Schottky analysis by an impendence analyser.
Ag (100nm)
PCBM (Various thickness)
Perovskite (300nm)
PEDOT:PSS(30nm)
ITO
Fig.1 Schematic diagram of inverted perovskite solar cell.
II. EXPERIMENT
The patterned ITO glass substrates were first ultrasonicated
with Hellmanex III, DI water, acetone and isopropanol, and
dried in N2 dessicator. PEDOT:PSS (Al 4083, Clevios) was
spin coated on ITO substrate at 4000 rpm for 30s. The Mix
halide perovskite solution was made by PbCl2 (0.8M) and
CH3NH3I (2.4M) in N,N-Dimethylformamide (DMF). The
precursor was stirred at 70 °C for overnight. The perovskite
ink was then coated on the substrates at 2500rpm for 30s.
After 2 hours drying the film, the perovskite films were then
annealed at 100 °C for 1hr and 120 °C for 0.5hr. After
annealing the perovskite film, the PCBM solution (2% in
Chlorobenzene) was coated on the substrate at different rpm.
Finally, 100nm Ag contact was evaporated at 1e-5 mbar. The
perovskite solar cell structure was ITO/ Poly(3,4-
ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS)
/Perovskite/ [6,6]-phenyl C71 butyric acid methyl ester
(PC71BM)/Ag as shown in Fig. 1.
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 The photovoltaics parameters are obtained from a calibrated The hysteresis of inverted perovskite solar cells was known
solar simulator using Keithley 2400 source meter at to be much smaller than the normal geometry[6]. In our
100mW/cm2. The current-voltage (I-V) characteristics of devices, the hysteresis is also very small in our devices. And
fabricated cells are measured as shown in Fig. 2. regarding to the stability of the devices, the thinner PCBM
The Mott Scholtty tests were extracted from the Autolab layer devices have worse stability. One possible reason could
PGSTAT-30 equipped with a frequency analyzer. The be: the thin PCBM layer would lead to the higher water vapor
thicknesses of the different films got from a depth transport rate[7]. This issue needs to be further studied.
profiler(Alpha-Step D-600, Tencor). Capacitance–Voltage Measurements
TABLE I Mott-Schottky Analysis provided the flat band voltage of
SUMMARY OF IV PARAMETER FOR DIFFERENT PCBM the devices, which directly connected with built-in potential.
THICKNESS The Mott Schottky test result is given in Fig.3. The devices
with thinner PCBM layer showed lower flat band voltage. At
Device Voc PCE
PCBM Thick- 3000 rpm, the VFB was only 0.26V. It gradually increased to
Jsc
ID (mV) (mA/cm ) 2 FF (%)
(%)
recipe ness 0.6V, when the thickness increased to 0.61V. The rise of the
(rpm) (nm) flat band voltage was consistent with improve of the V OC at
D2-6 920.45 13.01 54.38 6.51 1000 120 different thickness.
D4-3 897.36 14.77 46.84 6.21 2000 80

D5-3 856.51 16.10 45.77 6.31 3000 50

III. RESULT AND DISCUSSION

The efficiency of photovoltaics devices can be calculated
as:
= × × (1)

The geometry of the perovskite solar cells is given in Fig.1.

By changing the thickness of the PCBM layer, the efficiency

Fig.3. Mott Schottky plots of devices with different

thickness PCBM at different spin speed: 3000rpm (a);
2000rpm (b); 1000rpm (c).
Fig. 2. The I-V characteristics cells for different ETL
thickness According to the literature[8], under the illumination or
bias condition, the perovskite/PCBM interface and
PCBM/cathode interface would form dipole layer. At
of the devices didn’t vary much. When increasing the spin
equilibrium, there would be no current flowing. The electric
speed of the PCBM solution, the thickness of the PCBM film
potential between the both interfaces would be same, equal to
decreases. The short circuit current of the devices would
VOC. At this condition, the thinner the PCBM layer, the bigger
increase from 13.01mA/cm2 to 16.10mA/cm2, with the film
the electric filed is. Therefore, it would be easier for charger
thickness decrease. However, the open circuit voltage dropped
transport from the thinner PCBM. This is explained the higher
from 920.45mV to 856.51mV; and fill factor decreased as
current of thinner PCBM devices. The electric filed in ETL is
well. All these factors combine together. The overall
defined as
efficiency didn’t change much.
=− / (2)

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 However, based on the Mott Schottky analysis still we
cannot fully explain the I-V parameters’ variation. There are
still some reasons affect the performance:
1) The Space charge effect
When the ETL thickness decreased, the unabsorbed light
would be reflected from the metal electrode. Some of it would
pass through the ETL again, the light would be absorbed by
the perovskite film to generate more electron hole pairs.
2) Work function mismatch between Ag and PCBM
Low work function metal, like Al, is more commonly used as
electrode in inverted geometry of perovskite solar cells. There
would be a work function mismatch formed Schottky barrier.
This would affect the change transportation. Guerrero et al
showed that the flat band voltage of the devices using Al as
the cathode is higher than that of Ag [8]. This would decrease
the open circuit voltage and FF when using Ag as the cathode.
This effect would be more severe when using thinner PCBM
layer.
3) The morphology of the perovskite film
The perovskite film surface is not flat. The ETL layer should
be thick enough to cover the rough surface of perovskite layer
to decrease the shunting of the devices. When the PCBM layer
thickness decreases, the leakage of the devices would increase.
This would lead to the decrease of the FF. A better perovskite
film would improve all three parameters of the devices. This
could be studied by comparing different perovskite methods.
It needs to be further studied.
IV. CONCLUSION
In summary, the PCBM ETL used in inverted perovskite
solar cells would affect the performance. A thinner PCBM
layer would improve the JSC significantly. However, a thicker
layer would improve the flat band voltage and form a better
diode, then further improve the VOC and FF. For this
perovskite fabrication method, a thicker ETL showed better
performance. There are other factors would affect the device
978-1-5090-2724-8/16/$31.00 ©2016 IEEE
performance. The perovskite film quality and the geometry
design need to be further studied to improve the device
performance.
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