杂化钙钛矿材料在太阳电池中的应用与发展

doi:10.15541/jim20140617

摘要/Abstract

摘要：

杂化钙钛矿是近年来发展非常迅速的一类新型光电材料。自从2009年日本学者首次研究钙钛矿敏化太阳电池, 经过五年的发展, 有机铅卤化物钙钛矿太阳电池光电转换效率从最初的3.1%跃升到19.3%。本文介绍了有机铅卤化物钙钛矿的结构及其在有机/无机杂化钙钛矿太阳电池中的应用, 并从有机铅卤化物钙钛矿太阳电池的发展历程、器件结构、制备方法等方面做了总结。最后简要讨论了钙钛矿太阳电池的长期稳定性、环境问题, 并就未来发展趋势进行展望。

关键词: 太阳电池, 钙钛矿, 有机铅卤化物, 光电效率, TiO2/ZnO光阳极膜, 空穴传输材料, 综述

Abstract:

The hybrid perovskite is a new kind of photoelectric material. The development in a highly-efficient perovskite solar cell with long-term durability, following the first attempt at a perovskite sensitizer in 2009, has attracted many researchers attention. The power conversion efficiencies of organolead halide perovskite solar cells have been improved from 3.1% to 19.3% in 2014. In this paper, the structure of organolead halide perovskite and its application in the inorganic-organic hybrid perovskite solar cells are reviewed. The development, device structure and preparation method of the organolead halide perovskite solar cell are summarized. Finally, the long-term stability, environmental problems and development tendency of perovskite solar cells are briefly described.

Key words: solar cell, perovskite, organolead halide, photoelectric efficiency, TiO2/ZnO photo anode films, hole-transporting materials, review

中图分类号:

TQ174

王艳香, 罗俊, 郭平春, 赵学国, 杨志胜, 朱华, 孙健. 杂化钙钛矿材料在太阳电池中的应用与发展[J]. 无机材料学报, 2015, 30(7): 673-682.

WANG Yan-Xiang, LUO Jun, GUO Ping-Chun, ZHAO Xue-Guo, YANG Zhi-Sheng, ZHU Hua, SUN Jian. Application and Development of Hybrid Perovskite Materials in the Field of Solar Cells[J]. Journal of Inorganic Materials, 2015, 30(7): 673-682.

图/表 12

图 1 单胺(a)和二胺(b)有机阳离子的<100>取向层状钙钛矿结构示意图[2]

Fig. 1 Schematic representation of single-layer(100)-oriented perovskites with (a) monammonium (b)diammonium organic cations[2]

图 2 有机铅卤化物钙钛矿的结构示意图[12]

Fig. 2 Structural representation of organolead halide perovskite[12]

图3 TiO2基有机铅卤化物钙钛矿受光激发和电子传输的示意图(a)和钙钛矿敏化太阳电池的入射光电转换效率图谱(b)[5]

Fig. 3 A schematic illustration of organolead halide perovskite sensitized TiO2 undergoing photoexcitation and electron transfer (a) and the incident photon to electron conversion efficiency (IPCE) spectra for perovskite sensitized solar cells (b)[5]

图 4 CH3NH3Pb(I1-xBrx)3的紫外-可见光吸收光谱(a), TiO2/ CH3NH3Pb(I1-xBrx)3双层纳米复合物在FTO玻璃基板上的三维图像(b)和 CH3NH3Pb(I1-xBrx)3的带隙与Br的组成成分(x)的二次函数关系(c)[16]

Fig. 4 a) UV/Vis absorption spectra of CH3NH3Pb(I1-xBrx)3; b) Pictures of 3D TiO2/CH3NH3Pb(I1-xBrx)3 bilayer nanocomposites on FTO glass substrates; c) Quadratic relationship of the band gaps of CH3NH3Pb(I1-xBrx)3 as a function of Br composition (x)[16]

表1 不同铅卤化物钙钛矿的性能

Table 1 Properties of different lead halide perovskites

Composition	Bandgap/eV	Structure at room temperature
CH₃NH₃PbI₃	1.50-1.61	Tetragonal^{[5, 15, 31]}
CH₃NH₃PbBr₃	2.32	Cubic^[16]
CH₃NH₃PbCl₃	3.10	Cubic^[17]
CH₃NH₃PbI_3-_xCl_x	1.55-1.64	Tetragona^{[7, 32-34]}
HC(NH₂)₂PbI₃	1.47	Tetragona^[28-30]

图5 (a)实际器件, (b)器件的断面结构图, (c)器件断面部分的SEM形貌图和(d)FTO/TiO2/钙钛矿/空穴层接触界面的结构图[15]

Fig. 5 (a) Real solid-state device; (b) Cross-sectional structure of the device; (c) Cross-sectional SEM image of the device; (d) Active layer-underlayer-FTO interfacial junction structure[15]

图 6 几种太阳电池技术的历史发展进程以及钙钛矿太阳电池结构的未来几种发展方向[40]

Fig. 6 Historic evolution of several kinds of solar cell technology and future directions for the structure of the perovskite solar cells[40]

表2 不同器件结构的钙钛矿太阳电池光阳极膜类型

Table 2 Types of photo anode films in a perovskite solar cell with different device structures

Device structure	The types of photo anode films	Scaffold	Hole-selective contact
Mesoporous structure	Compact TiO₂	Meso-TiO₂	Spiro-OMeTAD^{[7-8, 15]}
			Polymers^{[32, 48-52]}
			Inorganic^{[53, 54]}, molecules^[55]
Meso-superstructured	Compact TiO₂	Meso-Al₂O₃	Spiro-OMeTAD^{[7, 45-46]}
Meso-superstructured	Compact TiO₂	Meso-ZrO₂	Spiro-OMeTAD^{[7, 45-46]}
Planar heterojunction structure	Compact TiO₂/ZnO	—	Spiro-OMeTAD^{[47, 56]}

图 7 制备钙钛矿有效层的四种常用方法

Fig. 7 Four general methods to prepare perovskite active layers (a) One step precursor deposition method; (b) Sequential deposition method[30]; (c) Dual source vapour deposition[47]; (d) Vapor-assisted solution process[59]

图 8 空穴传输材料的结构示意图(a)和空穴传输材料的能级示意图(b)

Fig. 8 Structural representation of hole transporting materials (HTMs) (a) and energy level diagram of hole transporting materials (HTMs) (b)

图 9 器件结构和能带图

Fig. 9 Device architecture and energy level diagram (a) Schematics cross-sectional view of the perovskite solar cell conﬁguration: FTO glass, compact TiO2 underlayer, mesoporous TiO2 with inﬁltrated CH3NH3PbI3, CuSCN HTM and gold; (b) Energy level diagram of the TiO2/CH3NH3PbI3/CuSCN/Au device showing ideal electron injection and hole extraction[54]

图 10 (A)基于完全可印刷介观太阳电池的三层层状钙钛矿横截面示意图和(B)三层结构的能带图[68]

Fig. 10 (A) Schematic illustration showing the cross section of the triple-layer perovskite-based fully printable mesoscopic solar cell and (B) energy band diagram of the triple-layer device[68]

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