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8th International Conference on Physics and its Applications (ICOPIA) IOP Publishing
Journal of Physics: Conference Series 776 (2016) 012010 doi:10.1088/1742-6596/776/1/012010

Perovskite/polymer solar cells prepared using solution process

E. S. Rosa1, Shobih1, N. M. Nursam1 and D. G. Saputri2

1
Research Center for Electronics and Telecommunication Indonesian Institute of
Science
Kampus LIPI Gedung 20 Jalan Sangkuriang Bandung 40135 West Java Indonesia
2
Faculty of Mathematics and Natural Science Sebelas Maret University
Jl. Ir. Sutami No. 36A, Solo 57126 Central Java Indonesia

E-mail: [email protected]

Abstract. We report a simple solution-based process to fabricate a perovskite/polymer tandem

solar cell using inorganic CH3NH3PbI3 as an absorber and organic PCBM (6,6 phenyl C61-
butyric acid methyl ester) as an electron transport layer. The absorber solution was prepared by
mixing the CH3NH3I (methyl ammonium iodide) with PbI2 (lead iodide) in DMF (N,N-
dimethyl formamide) solvent. The absorber and electron transport layer were deposited by spin
coating method. The electrical characteristics generated from the cell under 50 mW/cm2 at 25
°C comprised of an open circuit voltage of 0.31 V, a short circuit current density of 2.53
mA/cm2, and a power conversion efficiency of 0.42%.

1. Introduction
In recent years, novel research in the field of halide perovskites nano crystals have drawn much
attention as a new class of light absorber layers for solar cells [1]. The perovskites exhibit a
semiconductor-to-metal transition with the increase in the dimensionality [2,3]. By increasing the
dimension from 2D to 3D, the band gap will be decreased and the electrical properties will change [2].
Solar cells based on perovskite materials were first reported in 2009 by Miyazaka et.al. They applied
3D organometallic halide perovskites in a liquid electrolyte configuration dye-sensitized solar cell
(DSSC) with a power conversion efficiency (PCE) of 3.8% [3,4].
The general formula of organometallic halide perovskites is CH3NH3PbX3, where X can be Cl, Br, or
I. Perovskite is basically a semiconductor that offers a wide range of band gap tuning by modifying the
halide content and the organic part [5]. Methyl ammonium lead iodide (CH3NH3PbI3) was initially
utilized as a sensitizer, in the form of nanoparticles decorating the surface of a mesoporous metal
oxide, in a liquid-state dye-sensitized solar cells[6]. CH3NH3PbI3 has a band gap of 1.55 eV, close to
the theoretical bandgap for an optimum photovoltaic performance (i.e. 1.4 eV) [7]. This coupled with a
good extinction coefficient, which is one order of magnitude higher than standard dyes, enables
excellent external quantum efficiency spectra (EQE) in the solar cells. This corresponds to an optimum
photon absorption in the visible range (400 to 800 nm) and part of the near-infrared of the solar
spectrum. Furthermore, when CH3NH3PbI3 is heated above 55–60 °C, it undergoes a phase transition
from tetragonal to cubic, which is expected to narrow the band gap of the material [7].
The great deal of interest and research activities involving perovskite solar cells have resulted in a
tremendous progress in the PCE, with more than 17% of improvement was attained within a very short
time scale [8]. However, the breakthroughs have been mostly achieved in a dye-sensitized solar cell

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8th International Conference on Physics and its Applications (ICOPIA) IOP Publishing
Journal of Physics: Conference Series 776 (2016) 012010 doi:10.1088/1742-6596/776/1/012010

architecture that typically requires high-temperature processing due to the use of metal oxides as the
charge transporting materials [8]. As an alternative, organic photovoltaic (OPV) structure has gained
much consideration as it can be fabricated through simple and low-temperature processing, including
being adaptable for flexible photovoltaic applications [4,8]. The combination of a perovskite and OPV
concept therefore holds a great potential and deserves further studies.
Herein, we report the fabrication of perovskite/polymer solar cells using CH3NH3PbI3 as an absorber
and PCBM (6,6 phenyl C61-butyric acid methyl ester) as an electron transport layer. The device
comprised of a glass/ITO/PEDOT:PSS/ CH3NH3PbI3/PCBM/Ag, wherein the perovskite and polymer
layer were deposited by spin coating. Spin-coating is a well-known, rapid technique used for
producing uniform, high-quality thin films on various substrates. This coating method has been widely
used in the fabrication of organic electronics and optical device coatings, among many others [4]. In
this research, we prepared a thin film of the low temperature solution-processed organometallic
trihalide perovskite (CH3NH3PbI3) absorber by mixing CH3NH3I (methyl ammonium iodide) with PbI2
(lead iodide) in DMF (N,N-dimethyl formamide) solvent. The performance of the solar cell was
subsequently evaluated by calculating the power conversion efficiency under solar simulator.

2. Methodology
All chemicals in this work were commercially available and used without further purification. The
substrate used was 12.5 mm × 12.5 mm indium tin oxide (ITO) coated glass with a sheet resistance of
12 Ω/square. ITO is a transparent conductive oxide that serves to drain the photogenerated holes. To
avoid any short circuit on the cell, it is therefore necessary to form an ITO pattern by partially etching
the ITO layer. A black paint was sprayed on the ITO surface that has been covered with an adhesive
tape mask with a certain pattern. The substrate was then dried at room temperature overnight, and the
mask was then removed once it dried. The next step was the etching process, aiming at eliminating the
undesired ITO layer. Etching process was performed by dipping the substrate into 50% HCl solution
for 5 minutes, followed by washing in DI water and drying at room temperature. The remaining paint
was then removed by consecutively immersing the substrate into tinner solution, isopropyl alcohol,
and DI water for 10 min each in an ultrasonic bath.
The next step was the coating of the hole transporting layer, which was made of poly(3,4-
ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS). PEDOT:PSS coating was carried out
using spin coating method at a rotation speed of 1000 rpm for 60 s. The PEDOT:PSS layer was then
dried in a vacuum oven at 120 °C for 60 min.
The organometallic halide perovskites were then prepared by mixing CH3NH3I with PbI2 (molar ratio
1:1) in 1 mL DMF. The solution was stirred at room temperature for 24 h. The solution mixture was
subsequently spin coated on top of the PEDOT: PSS layer at 2500 rpm for 30 s and then annealed in a
vacuum oven at 100 °C for 45 minutes.
The polymer solution was prepared by dissolving 20 mg PCBM in 1 mL chlorobenzene and stirred for
60 s. The PCBM solution was then deposited onto the perovskite layer by spin coating at 1000 rpm for
30 s, and annealed in a vacuum oven at 100 °C for 10 min. Finally, a 60 nm-thick silver electrode was
deposited by thermal evaporation onto the polymer layer. The size of the active area of each cell was
5.0 mm × 6.0 mm. Characterization
The ultraviolet–visible (UV-vis) absorption spectra of the CH3NH3PbI3 layer were recorded using UV-
vis spectrophotometer (Hewlett Packard 8453 Agilent Technologies). The surface morphology of the
samples was observed using a scanning electron microscopy (SEM) in an FEI Quanta 250. The
photovoltaic performance of solar cells was measured under solar simulator comprising of a Xenon
lamp (Oriel, Newport, USA, AM 1.5) and a National Instrument source meter, which was integrated to
a Lab-view software. The irradiation intensity was set to 50 mW/cm2 at 25 °C.

3. Results and Discussion

The basic device configuration of the fabricated perovskite/polymer tandem solar cell is illustrated in
Fig. 1, which consists of ITO coated glass substrate deposited consecutively with PEDOT:PSS as the

2
8th International Conference on Physics and its Applications (ICOPIA) IOP Publishing
Journal of Physics: Conference Series 776 (2016) 012010 doi:10.1088/1742-6596/776/1/012010

hole transport material, CH3NH3PbI3 as the absorber, PCBM as electron transport material, and
finally Ag metal layer as the electrode. Such structure is so called an inverted perovskite architecture,
as the electron and hole transporting layer are the opposite of those used in the inorganic-based
perovskite solar cells. The crystal structure of the organometal halide CH3NH3PbI3 and the molecular
structure of the PCBM is shown in Fig. 2a and 2b, respectively.

Figure 1. Device configuration of perovskite/polymer solar cells comprising of CH3NH3PbI3/PCBM

layer.

Figure 2. (a) Crystal structure of CH3NH3PbI3 and (b) molecular structure of PCBM.

Figure 3. SEM image of the CH3NH3PbI3 surface layer at ×256 magnification.

3
8th International Conference on Physics and its Applications (ICOPIA) IOP Publishing
Journal of Physics: Conference Series 776 (2016) 012010 doi:10.1088/1742-6596/776/1/012010

Fig. 3 shows the SEM image of the CH3NH3PbI3 surface layer at ×256 magnification. An irregular
dendrite-like shape with a length in the range of hundreds of micrometers was formed on top of the
substrate. There were some areas thawere not fully covered by the dendrite layers, indicating that the
perovskite layer was non-uniform and uneven. The low surface coverage with some uncoated areas
could lead to light penetrating through the surface layer and, therefore reducing the light absorption.
This phenomenon was similar to the report from Salim et al. [8]. They reported that one of the main
challenges to obtain good performance in planar perovskite devices is the fabrication of high quality
films with controlled morphology, high surface coverage and minimum pinholes [8].
The UV-vis absorption spectrum of the CH3NH3PbI3 layer prepared from the mixture of CH3NH3I and
PbI2 precursor is shown in Fig. 4. It can be seen that the perovskite layer exhibited a narrow range of
optical absorption from 300 to 440 nm. The first peak absorption with the highest absorption intensity
of 0.80 a.u. was located at 320 nm. The second peak was located at ~410 nm with an intensity of 0.65
a.u. This optical profile indicates that the perovskite layer tends to absorb ultraviolet light more than
the blue light. Using the transformed Kubelka-Munk function, (αhν)2 vs. hν, for a direct semiconductor
[9], the bandgap energy for the obtained CH3NH3PbI3 was estimated to be ~2.8 eV.

Figure 4. Absorption spectrum of the CH3NH3PbI3 layer prepared from the precursor
solution of the mixed CH3NH3I and PbI2.

The photovoltaic performance of the perovskite/polymer solar cells based on CH3NH3PbI3/PCBM

was characterized under illumination of 50 mW/cm2. The J-V curve and the corresponding electrical
parameters are presented in Fig. 5 and Table 1, respectively. As seen in Table 1, an open circuit
voltage (Voc) of 0.31 V and a short circuit current density (Jsc) of 2.53 mA/cm2 were obtained,
resulting in a power conversion efficiency of 0.42%. The values of these parameters were lower
compared to the reported values in the literature [10]. By using same cell configuration with this
experiment, Jeng et al. for example, found greater values for all of the electrical characteristic
parameters, with Voc, Jsc, FF, PCE, Rs, and Rsh reached 0.60 V, 10.32 mA/cm2, 0.63, 3.90%, 1.82 Ω
cm2, and 3930 kΩ, respectively [10].

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8th International Conference on Physics and its Applications (ICOPIA) IOP Publishing
Journal of Physics: Conference Series 776 (2016) 012010 doi:10.1088/1742-6596/776/1/012010

Figure 5. J-V curve of the perovskite/polymer solar cells based on CH3NH3PbI3/PCBM

under solar illumination with an intensity of 50 mW/cm2.

Table 1. Electrical Characteristics of the perovskite/polymer solar cells based on CH3NH3PbI3/PCBM

under illumination with an intensity of 50 mW/cm2.

Voc Jsc Fill Rseri Rshunt PCE

(volt) (mA/cm2) factor (Ω cm2) (kΩ) (%)

0.31 2.53 0.27 132.70 0.47 0.42

There are several factors that could be the reason for the poor performance exhibited by the
CH3NH3PbI3/PCBM tandem solar cell fabricated in this work. It can be observed in in Fig. 4 that the J-
V curve formed a relatively linear line, which was far from the ideal square-shape curve. This
corresponded to a low fill factor value (FF = 0.27), which was the result of a high series resistance (Rs
= 132.7 Ω cm2) and low parallel or shunt resistance (Rsh = 0.47 kΩ). The high Rs could be linked to the
thickness of each active layer and the bad contact between the cathode and anode layer in the cell. The
high Rs and the low Rsh could also contribute to the low Jsc. The low Jsc might be mainly caused by the
thickness of perovskite layer, which was allegedly greater than the charge carrier diffusion length [11].
When the perovskite layer is too thick, the photogenerated charge carriers can recombine before they
reach the respective electrode contact. Therefore, the thick perovskite layer can also contribute in the
low Rsh.
Meanwhile, the low Voc might be attributed to the non-uniform and uneven layers in the cell. This
condition could result in interpenetrating layers, so that the energy level of each layer involved in the
cell is disturbed [12]. The high resistance was likely to be caused by the humidity during spin coating
process of perovskite and PCBM. A recent report by Huang et al. shows that a uniform perovskite
layer could be formed when the spin coating was performed under controlled atmosphere, i.e. with an
argon flow in a glove box [13]. Another factor that could contribute to the high resistance was the
presence of holes in the surface of the perosvkite layer. The presence of these holes could cause
recombination charge at the interface between the perovskite and PCBM [14]. Overall, it was
perceived that the poor quality of the perovskite layer has contributed to the low values of the
electrical parameters and, thus, low power conversion efficiency was obtained. Optimization of the
perovskite layer to obtain a uniform coverage with minimum pinholes will be the focus of our future
work based on the findings on the present report.

5
8th International Conference on Physics and its Applications (ICOPIA) IOP Publishing
Journal of Physics: Conference Series 776 (2016) 012010 doi:10.1088/1742-6596/776/1/012010

4. Summary
A perovskite/polymer tandem solar cell was prepared using a solution-based processing, wherein
CH3NH3PbI3 and PCBM layer was used as an absorber and electron transport layer, respectively. The
absorber solution was prepared by mixing CH3NH3I with PbI2 in DMF solvent. The electrical
characteristics comprised of an open circuit voltage of 0.31 V, a short circuit current density of 2.53
mA/cm2, and a power conversion efficiency of 0.42%. Our results in this work demonstrate that
perovskite/polymer tandem solar cell could be produced using a simple and facile fabrication process
using wet chemical route. Although further improvement is still required, we believe that the
fabrication of low-cost perovskite solar cells with excellent performance can be realized in the future.

5. Acknowledgment
This project was financially supported by Research Center for Electronics and Telecommunication
Indonesian Institute of Sciences (PPET LIPI) through DIPA Tematik Program 2015.

6. References

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