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) In this work, we fabricated the perovskite solar cells with
PCBM film thickness was investigated for the performance of the geometry: ITO/ZnO/Perovskite/PCBM/Ag using mix
inverted structure perovskite solar cells. The charge
transportation study was carried by Mott-Schottky analysis. The halide precursor ink. The photovoltaic parameters of device
result shows the charge transportation status of different electron with different PCBM thickness were investigated. The detail
thickness. A thicker PCBM layer could provide better diode charge transportation behaviour of PCBM was evaluated by
property, while the thinner layer would lead to higher short Mott-Schottky analysis by an impendence analyser.
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 Ag (100nm)
film and the design of device structure are needed to be
optimized.
PCBM (Various thickness)
Index Terms — PCBM, inverted perovskite solar cells, mix
halide.

Perovskite (300nm)
I. INTRODUCTION
The perovskite solar cell has rapidly drawn the research
attention in last 3 years. The world record for perovskite solar PEDOT:PSS(30nm)
cells have hit over 20% in last year [1]. Perovskite promises
the capability of high efficiency, low energy input; potential of ITO
fabricating flexible and semitransparent devices. All of these
advantages make perovskite solar cell a promising candidate Fig.1 Schematic diagram of inverted perovskite solar cell.
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 II. EXPERIMENT
layers (ETLs) are usually made by metal oxide semiconductor, The patterned ITO glass substrates were first ultrasonicated
like TiO2, ZnO, SnO2, etc[2-4]. However, these metal oxide with Hellmanex III, DI water, acetone and isopropanol, and
ETLs require high temperature to form the layer. Therefore, dried in N2 dessicator. PEDOT:PSS (Al 4083, Clevios) was
people start to work with inverted perovskite solar cells, which spin coated on ITO substrate at 4000 rpm for 30s. The Mix
normally has the organic hole transportation layers (HTLs) halide perovskite solution was made by PbCl2 (0.8M) and
underneath the perovskite layer, and use Organic ETLs to CH3NH3I (2.4M) in N,N-Dimethylformamide (DMF). The
transport the electrons. This device geometry was previously precursor was stirred at 70 °C for overnight. The perovskite
widely used in organic solar cells, known as the “normal ink was then coated on the substrates at 2500rpm for 30s.
geometry”. This geometry requires lower temperature to form After 2 hours drying the film, the perovskite films were then
the charge transportation layers. The flexible devices have annealed at 100 °C for 1hr and 120 °C for 0.5hr. After
been fabricated at PET substrates for this geometry[5]. annealing the perovskite film, the PCBM solution (2% in
In inverted perovskite device structure, the hole Chlorobenzene) was coated on the substrate at different rpm.
transportation layer: PEDOT:PSS usually has better Finally, 100nm Ag contact was evaporated at 1e-5 mbar. The
conductivity, which allows to extract carriers more effectively. perovskite solar cell structure was ITO/ Poly(3,4-
However, the charge transportation behaviour of the PCBM ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS)
layers, what could be the optimized recipe for the ETLs has /Perovskite/ [6,6]-phenyl C71 butyric acid methyl ester
not been investigated. (PC71BM)/Ag as shown in Fig. 1.

978-1-5090-2724-8/16/$31.00 ©2016 IEEE 1670

 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)

978-1-5090-2724-8/16/$31.00 ©2016 IEEE 1671

 However, based on the Mott Schottky analysis still we performance. The perovskite film quality and the geometry
cannot fully explain the I-V parameters’ variation. There are design need to be further studied to improve the device
still some reasons affect the performance: performance.

1) The Space charge effect

REFERENCES
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 [1] W.S. Yang, J.H. Noh, N.J. Jeon, Y.C. Kim, S. Ryu, J. Seo,
the perovskite film to generate more electron hole pairs. S.I. Seok, High-performance photovoltaic perovskite layers
2) Work function mismatch between Ag and PCBM fabricated through intramolecular exchange, Science, 348
Low work function metal, like Al, is more commonly used as (2015) 1234-1237.
electrode in inverted geometry of perovskite solar cells. There [2] J. Song, E. Zheng, J. Bian, X.-F. Wang, W. Tian, Y.
Sanehira, T. Miyasaka, Low-temperature SnO2-based electron
would be a work function mismatch formed Schottky barrier.
selective contact for efficient and stable perovskite solar cells,
This would affect the change transportation. Guerrero et al
Journal of Materials Chemistry A, 3 (2015) 10837-10844.
showed that the flat band voltage of the devices using Al as
[3] M.M. Lee, J. Teuscher, T. Miyasaka, T.N. Murakami, H.J.
the cathode is higher than that of Ag [8]. This would decrease Snaith, Efficient Hybrid Solar Cells Based on Meso-
the open circuit voltage and FF when using Ag as the cathode. Superstructured Organometal Halide Perovskites, Science,
This effect would be more severe when using thinner PCBM 338 (2012) 643-647.
layer. [4] D. Bi, G. Boschloo, S. Schwarzmuller, L. Yang, E.M.
Johansson, A. Hagfeldt, Efficient and stable CH3NH3PbI3-
3) The morphology of the perovskite film sensitized ZnO nanorod array solid-state solar cells,
The perovskite film surface is not flat. The ETL layer should Nanoscale, 5 (2013) 11686-11691.
be thick enough to cover the rough surface of perovskite layer [5] J. You, Z. Hong, Y. Yang, Q. Chen, M. Cai, T.-B. Song,
to decrease the shunting of the devices. When the PCBM layer C.-C. Chen, S. Lu, Y. Liu, H. Zhou, Y. Yang, Low-
thickness decreases, the leakage of the devices would increase. Temperature Solution-Processed Perovskite Solar Cells with
This would lead to the decrease of the FF. A better perovskite High Efficiency and Flexibility, ACS Nano, 8 (2014) 1674-
film would improve all three parameters of the devices. This 1680.
could be studied by comparing different perovskite methods. [6] J. Xu, A. Buin, A.H. Ip, W. Li, O. Voznyy, R. Comin, M.
It needs to be further studied. Yuan, S. Jeon, Z. Ning, J.J. McDowell, P. Kanjanaboos, J.P.
Sun, X. Lan, L.N. Quan, D.H. Kim, I.G. Hill, P.
Maksymovych, E.H. Sargent, Perovskite-fullerene hybrid
materials suppress hysteresis in planar diodes, Nature
IV. CONCLUSION communications, 6 (2015) 7081.
In summary, the PCBM ETL used in inverted perovskite [7] D. Wang, M. Wright, N.K. Elumalai, A. Uddin, Stability
solar cells would affect the performance. A thinner PCBM of perovskite solar cells, Solar Energy Materials and Solar
Cells, 147 (2016) 255-275.
layer would improve the JSC significantly. However, a thicker
[8] A. Guerrero, J. You, C. Aranda, Y.S. Kang, G. Garcia-
layer would improve the flat band voltage and form a better
Belmonte, H. Zhou, J. Bisquert, Y. Yang, Interfacial
diode, then further improve the VOC and FF. For this
Degradation of Planar Lead Halide Perovskite Solar Cells,
perovskite fabrication method, a thicker ETL showed better
ACS Nano, (2015).
performance. There are other factors would affect the device

978-1-5090-2724-8/16/$31.00 ©2016 IEEE 1672