钙钛矿太阳能电池无机空穴传输材料的研究进展

doi:10.15541/jim20230105

无机材料学报 ›› 2023, Vol. 38 ›› Issue (9): 991-1004.DOI: 10.15541/jim20230105 CSTR: 32189.14.10.15541/jim20230105

所属专题：【能源环境】钙钛矿(202506)；【能源环境】太阳能电池(202506)

钙钛矿太阳能电池无机空穴传输材料的研究进展

陈雨¹^,²(), 林埔安¹^,², 蔡冰²(), 张文华¹^,²()

1.云南大学材料与能源学院西南联合研究生院, 昆明 650500
2.中国工程物理研究院化工材料研究所, 成都 610200

收稿日期:2023-03-02 修回日期:2023-05-30 出版日期:2023-09-20 网络出版日期:2023-06-16
通讯作者: 蔡冰, 博士. E-mail: bingcai@caep.cn;
张文华, 教授. E-mail: wenhuazhang@ynu.edu.cn
作者简介:陈雨(1993-), 男, 博士研究生. E-mail: 434980565@qq.com
基金资助:
国家自然科学基金(61904166)

Research Progress of Inorganic Hole Transport Materials in Perovskite Solar Cells

CHEN Yu¹^,²(), LIN Puan¹^,², CAI Bing²(), ZHANG Wenhua¹^,²()

1. Southwest Joint Research Institute, School of Materials and Energy, Yunnan University, Kunming 650500, China
2. Institute of Chemical Materials, China Academy of Engineering Physics, Chengdu 610200, China

Received:2023-03-02 Revised:2023-05-30 Published:2023-09-20 Online:2023-06-16
Contact: CAI Bing, PhD. E-mail: bingcai@caep.cn;
ZHANG Wenhua, professor. E-mail: wenhuazhang@ynu.edu.cn
About author:CHEN Yu (1993-), male, PhD candidate. E-mail: 434980565@qq.com
Supported by:
National Natural Science Foundation of China(61904166)

摘要/Abstract

摘要：

有机−无机杂化钙钛矿太阳能电池(PSCs)因高能量转换效率(PCE)和低制造成本而受到了广泛关注。尽管认证PCE已经高达26%, 但在高温、高湿度和持续光照下PSCs的稳定性仍然明显落后于传统太阳能电池, 这成为其商业化道路中最大的阻碍。开发和应用高稳定性的无机空穴传输材料(HTMs)是目前解决器件光热稳定性的有效方法之一, 引入无机HTMs可以有效屏蔽水和氧对钙钛矿吸光层的侵蚀, 从而避免形成离子迁移通道。本文概述了应用于有机−无机杂化钙钛矿太阳能电池的无机HTMs的分类和光电特性, 介绍了相关研究进展, 总结了针对无机HTMs器件的性能优化策略, 包括元素掺杂、添加剂工程和界面工程, 最后展望了无机HTMs未来的发展方向。下一步需要更深入地研究无机HTMs的微观结构及其与PSCs性能的关系, 从而实现更高效、更稳定的PSCs器件。

关键词: 无机空穴传输材料, 钙钛矿太阳能电池, 稳定性, 能量转换效率, 综述

Abstract:

Organic-inorganic hybrid perovskite solar cells (PSCs) have attracted widespread attention due to their high power conversion efficiency (PCE) and low manufacturing cost. Although the certified PCE has reached 25.8%, the stability of PSCs under high temperature, high humidity, and continuous light exposure is still significantly inferior to that of traditional cells, which hinders their commercialization. Developing and applying highly stable inorganic hole transport materials (HTMs) is currently one of the effective methods to solve the photo-thermal stability of devices, which can effectively shield water and oxygen from corroding the perovskite absorption layer, thereby avoiding the formation of ion migration channels. This paper outlines the approximate classification and photoelectric properties of inorganic HTMs, introduces relevant research progress, summarizes performance optimization strategies for inorganic HTMs devices, including element doping, additive engineering, and interface engineering, and finally prospects the future development directions. It is necessary to further study the microstructure of inorganic HTMs and their relationship with the performance of PSCs to achieve more efficient and stable PSCs.

Key words: inorganic hole transport materials, perovskite solar cells, stability, power conversion efficiency, review

中图分类号:

TQ174

陈雨, 林埔安, 蔡冰, 张文华. 钙钛矿太阳能电池无机空穴传输材料的研究进展[J]. 无机材料学报, 2023, 38(9): 991-1004.

CHEN Yu, LIN Puan, CAI Bing, ZHANG Wenhua. Research Progress of Inorganic Hole Transport Materials in Perovskite Solar Cells[J]. Journal of Inorganic Materials, 2023, 38(9): 991-1004.

图/表 9

图1 (a)正式(n-i-p)型结构; (b)反式(p-i-n)型结构

Fig. 1 (a) Formal (n-i-p) structure and (b) inverted (p-i-n) structure

表1 无机空穴传输材料的基本性质(Spiro-OMeTAD作为对比)

Table 1 Properties of inorganic hole transport materials (Spiro-OMeTAD for comparison)

Material	Hole concentration, N/cm^-3	Hole mobility, μ/(cm²·V^-1·s^-1)	Conductivity, σ/(S·cm^-1)
Sprio-OMeTAD with Li-TFSI, etc.	7.13×10^15[19]	0.779^[19]	1.53×10^-3[13]
NiO	5.3×10^18[20]	0.12^[20]	1.66×10^-4[21]
Cu:NiO	7.3×10^19[22]	~0.2^[22]	1.25×10^-3[23]
Ni_0.8Li_0.05Mg_0.15O	6.46×10^18[24]	-	2.23×10^-3[24]
CuGaO₂	3.098×10^19[25]	-	4.625×10^-3[25]
Zn:CuGaO₂	1.328×10^20[25]	-	1.39×10^-2[25]
CuCrO₂	-	0.1-1.0^[26]	2.9×10^-2[27]
In:CuCrO₂	7.1×10^18[27]	0.75^[27]	6.9×10^-2[27]
CuScO₂	-	-	2.11×10^-3[28]
CuSCN	-	1.2×10^-3[21]	-
Co₃O₄	-	1.49×10^-2[29]	-
Co₃O₄-SrCO₃	-	6.33×10^-2[29]	-

图2 代表性的无机空穴传输材料的最高占据分子轨道(HOMO)(或价带)和最低未占据分子轨道(LUMO)(或导带)能级(Spiro-OMeTAD作为对比)[18]

Fig. 2 Highest occupied molecular orbital (HOMO) (or valence-band) and lowest unoccupied molecular orbital (LUMO) (or conduction-band) energy levels relative to the vacuum of representative inorganic hole transport materials (HOMO and LUMO of Spiro-OMeTAD for comparison)[18]

图3 镍基氧化物的物理形貌、合成工艺和相关性能

Fig. 3 Physical morphology, synthesis process and related properties of nickel-based oxide materials (a) Comparison of conductivity mapping results for NiO (left) and Li0.05Mg0.15Ni0.8O (right) films[21]; (b) J-V curve of NiOx-based PSCs with molecular doping of F6TCNNQ[34]; (c) Synthetic process of the SRE NiOx (top), Ni species changed with different synthetic processes (bottom-left) and spectrum changes in Ni species caused by SRE (bottom-right), and (d) champion J-V curves of PSCs[35]; (e) Schematic diagram of synthesis process and (f) high-resolution transmission electron microscopy (TEM) image of NiCo2O4 nanocrystals, as well as (g) J-V curves of the champion PSCs[37]. Colorful figures are available on website

图4 铜基氧化物的物理形貌和相关性能

Fig. 4 Morphology and related properties of copper-based oxide materials (a) Cross-sectional SEM image and (b) stability performance of the device with different HTL (Spiro-OMeTAD and Cu2O)[26]; (c) Preparation technology, device structure, energy level diagram and (d) J-V curves of Cu2O and CuO films[40]; (e) TEM image of CuGaO2 nanocrystals and (f) stability of the device[45]; (g) J-V curves, structure diagram (PC61BM: [6,6]-phenyl-C61-butyric acid methyl ester) and (h) stability of device based on mp-CuGaO2[39]; (i) Schematic diagram of nanocrystalline structure and (j) stability of devices based on CuCrO2[46]; (k) TEM image of CuScO2 nanocrystals and (l) J-V curves of PSCs[28]. Colorful figures are available on website

图5 其他氧化物和非氧化物的物理形貌和相关性能

Fig. 5 Physical morphology and related properties of other oxides and non-oxides (a) High-resolution TEM image of Co3O4 and (b) J-V curves of PSCs[47]; (c) Time-resolved photoluminescence (TRPL) spectra and (d) J-V curves of PSCs based on Co3O4-SrCO3[50]; (e) PL absorption spectra and (f) J-V curve of PSCs based on CuSCN HTL[16]; (g) Diagram of device structure, (h) J-V curves and (i) light stability of capped PSCs (under constant illumination and different temperature) based on CuSCN HTL and 2D Cs2PbI2Cl2 capping layers[55]

图6 元素掺杂对于器件性能的影响

Fig. 6 Effect of element doping on device performance (a) J-V curves and (b) PL spectra of PSCs based on Cu:NiOx HTL[23]; (c) J-V curves of PSCs and (d) electrical conductivity of Cs:NiOx film[27]; (e) SEM image of In doped CuCrO2 film and (f) J-V curves of PSCs[57]; (g) Mott-Schottky curves and (h) J-V curves of PSCs based on the Zn doped CuGaO2[25]

图7 添加剂工程对于器件性能的影响

Fig. 7 Effect of additive engineering on device performance (a) SEM images of NiO film with different ammonium stabilizers and different concentrations and (b) J-V curves of PSCs[30]; (c) Schematic structure, (d) J-V curves and (e) I-t curves of PSCs based on NiO film with boric acid[59]; (f) J-V curves, (g) long-term stability and (h) maximum power output stability of PSCs based on ionic liquid-assisted synthesis of NiO NPs[60]; BCP: Bathocuproin; VMPP: Output voltage at maximum power. Colorful figures are available on website

图8 界面工程对于器件性能的影响

Fig. 8 Effect of interface engineering on device performance (a) J-V curves of devices based on surface modification with different concentrations of CsBr, and stability of PSCs[63]; (b) J-V curves and (c) MPP stability of PSCs based on GUAI surface modification at different concentrations (in molar) with inset showing environmental stability[64]; (d) High-resolution TEM images of Au@NiOx NPs, (e) corresponding structure diagram and (f) J-V curves of PSCs[65]; (g) MPP stability of devices with TMSBr surface modification[66]; CsBr-2.5: 2.5 mg/mL CsBr; RS: reverse scan; FS: forward scan; T80: the time maintaining 80% initial PCE. Colorful figures are available on website

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钙钛矿太阳能电池无机空穴传输材料的研究进展

Research Progress of Inorganic Hole Transport Materials in Perovskite Solar Cells

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