ECS Transactions, 69 (4) 3-7 (2015)

10.1149/06904.0003ecst ©The Electrochemical Society

CH3NH3PbI3 Perovskite Solar Cells on Inorganic Materials: CuSCN and Crystal

Silicon

S. Ito

Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo,

671-2280 JAPAN.

Organo-lead halide perovskites have attracted much attention for

solar cell applications due to their unique optical and electrical
properties. With either low-temperature solution processing or
vacuum evaporation, the overall conversion efficiencies of
perovskite solar cells with organic hole-transporting material were
quickly improved to over 20% during the last 3 years. However,
the organic hole-transporting materials used are normally quite
expensive due to complicated synthetic procedure or high-purity
requirement. Here, we demonstrate the application of an effective
and cheap inorganic p-type hole-transporting material, copper
thiocyanate, on lead halide perovskite-based devices. With low-
temperature solution-process deposition method, a power
conversion efficiency of 12.4% was achieved under full sun
illumination. Moreover, PECVE-free c-Si solar cells will be
presented for utilization of tandem device with perovskite solar
cells.

Perovskite Solar Cells with CuSCN Hole-Transporting Material

Organolead-halide perovskite solar cells have been emerged as the low-cost and high-
efficiency ones, which can be considered as the candidate of next-generation renewable
energy source [1-5]. Although the perovskite layer is very low in the price, the solar cell
need hole transporting materials (HTM) to perform high-efficiency photovoltaic effects,
and the organic HTMs need exquisite synthesis technique for the high purity, resulting in
the higher commercial price than another materials in perovskite solar cells (PbI2,
CH3NH3I, TiO2 and so on). In order to remover the issue, we have managed CuSCN to be
the inexpensive inorganic HTM in perovskite solar cells [6-10]. The CuSCN HTM can
perform over 12.4% conversion efficiency perovskite solar cells without glove box
(fabricated in air) [8-10].

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 ECS Transactions, 69 (4) 3-7 (2015)

Figure 1. Current–voltage curves of the <TiO2/CH3NH3PbI3/CUSCN> heterojunction

solar cells in the dark and under different intensity of photon flux (AM1.5G). [9].

Pre-heating of mesoporous TiO2 electrode just before PbI2 deposition has quite
important effect on the sequential deposition of CH3NH3PbI3 perovskite layer for the
utilization of solar cells [11]. The effects were disclosed by comparisons of the surface
morphologies and the photovoltaics with and without pre-heating.

Figure 2. Surface SEM images of PbI2 layer without (left) and with (right) preheating
[11].

However, the degradation of the perovskite and the sensitized film hampers the
prospects for practical applications. Actually, organic‒inorganic perovskites are
extremely sensitive to moisture in air. Grätzel and co-workers found that the device

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 ECS Transactions, 69 (4) 3-7 (2015)

fabrication should be carried out under controlled atmospheric conditions and with a
humidity of <1% [3]. In our experiments we also found a similar phenomenon that
perovskite solar cells with inorganic HTM tend to degrade in a high humidity
environment.
Carbon double bond-free printed solar cells have been fabricated with the structure
<F-doped SnO2 (FTO)/dense TiO2/ nanocrystalline TiO2/CH3NH3PbI3/Au> and
<FTO/dense TiO2/ nanocrystalline TiO2/CH3NH3PbI3/CuSCN/Au>, in which CuSCN
acts as a hole conductor [6]. The thickness of the CH3NH3PbI3 layer is controlled by a hot
air flow during spin coating. The best conversion efficiency (4.86%) is obtained with
<FTO/dense TiO2/nanocrystalline TiO2/thin CH3NH3PbI3 (hot-air dried)/ CuSCN/Au>.
However, a thick CH3NH3PbI3 layer on CuSCN is better for light-exposure stability (100
mWcm-2 AM 1.5) when not encapsulated. Without the CuSCN coverage, the black
CH3NH3PbI3 crystal changes to yellow during the light-exposure stability test, which is
due to the transformation of the CH3NH3PbI3 perovskite crystal into hexagonal PbI2.

Figure 3. Variation of photovoltaic characteristics for unencapsulated solar cells during

light exposure in air: line a) <FTO/TiO2/CH3NH3PbI3 (without hot-air drying)/Au>; b)
<FTO/TiO2/CH3NH3PbI3 (without hot-air drying)/ CuSCN/Au>; c)<FTO/TiO2/
CH3NH3PbI3 (with hot-air drying)/CuSCN/Au> [6].

Sb 2S3 layers were inserted at the interface between TiO2 and CH3NH3PbI3 perovskite
to create CH3NH3PbI3 solar cells using inorganic hole transporting material (CuSCN) [7].
The CH3NH3PbI3 layer was spin-coated by a one-drop method onto the nanocrystalline
TiO2 layer. The photoenergy conversion efficiencies were improved with Sb2S3 layers
(the best efficiency: 5.24%). During the light exposure test without encapsulation, the
CH3NH3PbI3 solar cells without Sb 2S3 deteriorated to zero efficiency in 12 h and were
completely changed from black to yellow because the perovskite CH3NH3PbI3 was
changed to hexagonal PbI2. With Sb2S3, on the other hand, the CH3NH3PbI3 solar cells
became stable against light exposure without encapsulation, which did not change the
crystal structure or the wavelength edges of absorption and IPCE. Therefore, it was
believed that degradation can occur at the interface between TiO2 and CH3NH3PbI3.

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 ECS Transactions, 69 (4) 3-7 (2015)

Figure 4. Variation of photoenergy conversion efficiencies of solar cells during light

exposure (AM1.5, 100 mW cm−2) without encapsulation in air for 12 h: (a) <FTO/TiO2/
CH3NH3PbI3/ CuSCN/Au> and (b) <FTO/TiO2/Sb2S3/CH3NH3PbI3/CuSCN/ Au>. The
inset pictures are the photographs of cells after the light exposure.

Moreover, the stability of perovskites under moisture was studied [12]. This research
wok systematically studies the corrosion of several Pb-halide perovskites (CH3NH3PbI3,
CH3NH3PbBr3, NH2CH=NH2PbI3 and NH2CH=NH2PbBr3) by air at room temperature
under light irradiation using mesoporous TiO2 or Al2O3 scaffold layers.

PECVE-Free c-Si Solar Cells for Tandem Device with Perovskite Solar Cells.

Two-terminal tandem solar cells using silicon and perovskite were fabricated by
mechanical stacking as a high-efficiency and low-cost photovoltaic device without
utilization of plasma-enhanced chemical vapor deposition (PECVD). CH3NH3PbI3
perovskite and p-type CZ-Si solar cells can be utilized to attain a high-bandgap top one
and a low-bandgap bottom one, respectively. For the tunneling junction between the
perovskite and silicon solar cells, highly transparent connection layers of evaporated-Au
and sputtered-ITO films were deposited. A two-terminal mechanically stacked tandem
solar cell with an optimized tunneling junction structure of <perovskite for the top
cell/Au (2.5 nm)/ITO (154 nm) stacked-on ITO (108 nm)/c-Si for the bottom cell> was
fabricated without plasma-enhanced chemical vapor deposition (PECVD), a conversion
efficiency of 13.7 %, Jsc of 12.3 mA cm-2, Voc of 1.56 V and FF of 71.3 %.

Acknowledgments

The part of this work has been supported by NEDO (Japan) and ALCA-JST (Japan).

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 ECS Transactions, 69 (4) 3-7 (2015)

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