Using elemental Pb surface as a precursor to fabricate large area CH3NH3PbI3 perovskite solar cells
Graphical abstract
Introduction
Lead halide perovskite crystals such as MAPbX3 (X = I, Br, Cl) evolved from dye-sensitized solar cells based on MAPbI3 which were first fabricated by Miyasaka group in 2009 [1]. Since then, lead halide perovskite crystals have been widely studied as light absorber in nanostructured heterojunction solar cells application [2], [3], [4], [5], [6]. Just 7 years later, the power conversion efficiency of perovskite solar cells have raised to above 20% [7]. Lead halide perovskite possess most of the crucial properties which required by the high performance and low cost solar cells. These properties include direct bandgap, high absorption coefficient, long carrier lifetime, low fundamental energy loss, ease fabrication and low production cost [8], [9].
In general, MAPbX3 crystals are synthesized by reaction of methylammonium iodide (MAX) with lead-containing precursor. PbI2 [10], [11], lead acetate [12], lead nitrate [13], lead oxide [14], [15], lead titanate [16], lead acetylacetone [17] and lead thiocyanate [18] have been developed to fabricate perovskite solar cells with high power conversion efficiencies. For fabricating a high quality perovskite thin film, variety of methods including spin coating [19], [20], [21], spray coating [22], vapor-assisted solution processing [23] and vapor deposition [24], [25] have been studied. Among these methods, spin coating lead compounds such as PbI2 and Pb(NO3)2 solution for perovskite solar cells fabrication has been widely used. However, this popular method randomly affects the perovskite thin film quality such as morphology and crystal size even at the same experimental condition. Better repeatability of preparing a large active area MAPbX3 thin film with high quality is still a challenge.
In our previous studies, we have successfully deplored a direct metal surface elemental reaction (DMSER) method to prepare various semiconductor thin films. Especially, a room temperature, in-situ elemental reaction method has been built for inorganic semiconductor thin films fabrication [26]. These films have been used for sun light harvest. In this study, we report a novel and facile method to fabricate high quality, large area perovskite thin film based on in-situ elemental reaction. According to this route, an elemental lead layer was deposited on substrate firstly and then in-situ reacted with a CH3NH3I solution or a mixed CH3NH3I and I2 solution at room temperature. This elemental Pb-based in-situ reaction allows for the fabrication of large area and uniform perovskite thin films. Based on the large area perovskite thin film, a large active area perovskite solar cell device has been assembled under ambient atmosphere with a 40 ± 3% relative humidity (RH). The subsequent performance tests have been carried out, and a power conversion efficiency of 3.08% was achieved in an un-optimized large area perovskite solar cell device (1.10 ± 0.05 cm2). In order to further study the elemental reaction based perovskite films, transient photovoltaic (TPV) was employed to measure the photoinduced charge carrier dynamics [27]. TPV results indicated that the photoinduced charge carrier life time of the Pb-based perovskite thin films was as good as the perovskite thin films which were fabricated by the conventional two-step deposition method in the literature [21]. To our knowledge, this is the first time of using elemental Pb as a precursor in perovskite solar cell researching. This idea of synthesis CH3NH3PbI3 thin film based on elemental Pb may provide a new way for large area and high performance perovskite solar cell fabrication.
Section snippets
Experimental
All reagents are purchased from China National Medicines Corporation Ltd. except special callouts.
Results and discussion
Previously, we have reported in-situ approaches to fabricate compound thin films of PbI2 [28], Ag2S [26], CuI [29], and Ag3CuS2 [30]. We found that using this in-situ approach facilitates the formation of compact and uniform compound thin films. In this work, the in-situ approach was used to prepare perovskite CH3NH3PbI3. Fig. 1 shows the fabrication process for the perovskite layers based on elemental Pb. First, an elemental lead layer was sputtered onto FTO-ZnO substrate. Then, the in-situ
Conclusion
The perovskite CH3NH3PbI3 material with highly purity and crystallization was successfully in-situ fabricated from elemental Pb thin film under high moisture condition (40% ± 3% RH). The thickness and area of the elemental Pb based perovskite thin film can be easily controlled. It benefits the fabrication of uniform and large area perovskite thin film for solar cell application. TPV measurements reveal that the elemental Pb-initiated perovskite thin film has a long minority carrier lifetime as
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Grant No. 21273192 and 61504117), Innovation Scientists and Technicians Troop Construction Projects of Henan Province (Grant No. 144200510014), Program for Innovative Research Team (in Science and Technology) in University of Henan Province (Grant No. 2012IRTSTHN021), Scientific Research Program of Xuchang University (No. 2015095), Program for Basis and Frontier Technology Research of Xuchang City (No.11).
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