纳米金属氧化物在钙钛矿电池中的应用研究进展

doi:10.15541/jim20160026

摘要/Abstract

摘要：

近几年来, 钙钛矿电池发展迅速, 其单电池效率从最初的3.8%迅速提升至目前20.1%, 接近硅基太阳能电池的光电转换效率。TiO₂、ZnO、Al₂O₃等诸多无机纳米金属氧化物材料作为重要的载流子输运材料与钙钛矿生长骨架也被广泛地应用于钙钛矿电池。依据钙钛矿电池功能结构的差异, 本文分别介绍了此类材料作为钙钛矿电池中的致密层及介孔层的制备方法, 并在此基础上介绍了基于表面修饰、掺杂、复合等氧化物的改性手段调节材料理化性能与氧化物/钙钛矿界面特性, 进而改进钙钛矿电池性能的方法。并阐述了进一步提高钙钛矿电池光电转换效率需要关注的重点问题及展望。

关键词: 纳米金属氧化物, 钙钛矿电池, 致密层, 介孔层, 综述

Abstract:

In recent years, the power conversion efficiency of perovskite solar cells (PSCs) has increased dramatically from 3.8% to 20.1%, approaching to that of recent silicon-based solar cells. Inorganic metal oxides, including TiO₂, ZnO, Al₂O₃, etc., have been widely used as charge transport layers and perovskite supporting scaffords in PSCs. Regarding the cell structures of PSCs, this review discusses the syntheses methods of inorganic compact layers and mesoporous layers made from these inorganic metal oxides, and the modifications (including surface modifications, doping and composites) of these inorganic functional layers, which aim at improving the charge transport properties of these layers and changing the interfacial characteristics with perovskites to enhance the PSCs’ cell performances. Besides, the important issues of such functional layers made from inorganic metal oxides are also discussed.

Key words: nano metal oxides, perovskite solar cells, compact layers, mesoporous layers, review

中图分类号:

TQ174

王伟琦, 郑惠锋, 陆冠宏, 刘阳桥, 孙静, 高濂. 纳米金属氧化物在钙钛矿电池中的应用研究进展[J]. 无机材料学报, 2016, 31(9): 897-907.

WANG Wei-Qi, ZHENG Hui-Feng, LU Guan-Hong, LIU Yang-Qiao, SUN Jing, GAO Lian. Recent Progress on Applications of Nano Metal Oxides in Perovskite Solar Cells[J]. Journal of Inorganic Materials, 2016, 31(9): 897-907.

图/表 8

图1 杂化电池能带关系示意图

Fig. 1 Schematic energy diagram of hybrid solar cells

图2 量子点敏化、平板和介观结构钙钛矿电池结构示意图[14]

Fig. 2 Schematic illustration of quantum dot-sensitized, planar and mesoporous perovskite solar cell architectures[14]

表1 常见TiO2致密层制备方法优缺点

Table 1 Pros and cons of common TiO2 compact layer preparation methods

Method	Thickness	Pinholes	Flexible	Costs
Wet chemisty	Thick	Many	Suitable	Low
Spray pyrolysis	Thick	Few	Unsuitable	Low
ALD	Thin	Few	Suitable	High
Sputtering	Thin	Few	Suitable	High

图3 在FTO玻璃上制备的TiO2致密层表面扫描电镜照片[31]

Fig. 3 Top-view FE-SEM images of TiO2 compact layers fabricated on FTO substrates by different preparation methods[31](a) ALD; (b) Spray pyrolysis; (c) Spin coating. The average thickness of TiO2 is about 50nm in each sample

图4 生长在(a)ZnO; (b)ZnO/C3-SAM表面的钙钛矿AFM照片; 生长在(c)ZnO; (d)ZnO/C3-SAM表面的钙钛矿SEM照片与(e)生长于ZnO表面(上图)、ZnO/SAM表面(下图)的钙钛矿XRD衍射花样[53]

Fig. 4 AFM images of CH3NH3PbI3 perovskite on (a) bare ZnO and (b) ZnO/C3-SAM. SEM images of CH3NH3PbI3 perovskites on (c) bare ZnO and( d) ZnO/C3-SAM. (e) XRD patterns of perovskite films on ZnO (black line) and ZnO/SAM substrates (red line)[53]

图5 (a)电池扫描电镜断面结构图照片和(b)电池各层能带结构示意图[57]

Fig. 5 (a) SEM cross-sectional image of the device and (b) Energy diagram (relative to the vacuum level) of each functional layer in the device [57]

图6 基于TiO2“纳米碗”电子传输层的钙钛矿电池制备流程示意图[78]

Fig. 6 Schematic fabrication procedure for the TiO2 NB array film based C-PSCs[78](a) PS monolayer; (b) PS monolayer filled with TiO2 sol; (c) TiO2 NB array film; (d) perovskite filled and topped TiO2 NB array; (e) the wrought C-PSC

图7 (左)含介孔TiO2颗粒和(右)含介孔Al2O3颗粒钙钛矿电池载流子传输示意图[17]

Fig. 7 Schematic illustrating the charge transfer and charge transport in a perovskite-sensitized TiO2 solar cell (left) and a noninjecting Al2O3-based solar cell (right) [17]A representation of the energy landscape is shown below, with electrons shown as solid circles and holes as open circles

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