铅卤钙钛矿太阳能电池界面工程的近期进展

周瑾璟; 钟敏

doi:10.13801/j.cnki.fhclxb.20220303.001

铅卤钙钛矿太阳能电池界面工程的近期进展

doi: 10.13801/j.cnki.fhclxb.20220303.001

周瑾璟,
钟敏^,

中国计量大学　材料与化学学院, 杭州 310018

基金项目: 国家自然科学基金(21471140; 21101143)

详细信息

作者简介:
钟敏，工学博士，中国计量大学材料与化学学院教授，硕士生导师。 2000年9月~2005年6月，浙江大学材料科学与工程系材料学专业硕博连读并博士毕业，主要研究方向：有机/无机纳米复合光电功能薄膜材料及器件。先后参与了国家自然科学基金（69890230）、863重大项目（2001AA320202）和教育部跨世纪优秀人才培养计划项目研究。 2005年9月至今，中国计量大学材料与化学学院纳米材料化学制备室负责人，主要从事钙钛矿太阳能电池、太阳能燃料等可再生能源材料及器件、纳米材料领域的研究工作。先后主持国家自然科学基金面上项目一项，国家自然科学基金青年科学基金一项，国家自然科学基金国际合作与交流项目两项。获得国家发明专利三项。发表被SCI（EI）收录论文三十余篇。多次代表浙江省重点学科材料物理与化学学科参加国际国内的学术会议交流研究成果。2014年6月10日~9月10日应邀在美国纽约市立大学皇后学院物理系做访问学者，访学内容涉及第三代太阳能电池。(钟敏课题组网页链接：https://clxy.cjlu.edu.cn/info/1188/5572.htm)

通讯作者:
钟敏，博士，教授，硕士生导师，研究方向为钙钛矿太阳能电池　E-mail: zhongmin@cjlu.edu.cn

中图分类号: TB34; TM914.4
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出版历程
- 收稿日期: 2022-01-26
- 修回日期: 2022-02-24
- 录用日期: 2022-02-26
- 网络出版日期: 2022-03-08
- 刊出日期: 2022-03-23

Recent progress of interface engineering for lead halide perovskite solar cells

ZHOU Jinjing,
ZHONG Min^,

College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China

摘要

摘要: 铅卤钙钛矿太阳能电池因其优良的光电转换效率以及相对低廉的制备成本而受到广泛关注。然而铅卤钙钛矿太阳能电池的长期稳定性限制了其商业化的进程。界面非辐射复合导致铅卤钙钛矿太阳能电池产生能量损失、影响器件稳定性，是造成器件性能恶化的主要原因。界面工程作为一种有效的策略被用于抑制界面非辐射复合，在制备高效稳定的铅卤钙钛矿太阳能电池方面取得了切实的成效。本文阐述了铅卤钙钛矿太阳能电池的工作原理以及界面上的非辐射复合过程，分析了界面非辐射复合产生的原因，总结了近期n-i-p正式结构铅卤钙钛矿太阳能电池中界面工程的研究进展，讨论了其作用机制。基于目前铅卤钙钛矿太阳能电池中的界面工程发展现状，对其未来的发展方向进行了展望。
- 铅卤钙钛矿太阳能电池 /
- 界面工程 /
- 效率 /
- 稳定性 /
- 非辐射复合 /
- 能级排列 /
- 缺陷钝化
Abstract: Lead halide perovskite solar cells have attracted extensive attention on account of their excellent photoelectric conversion efficiency and relatively low fabrication cost. However, the poor long-term stability becomes a barrier that hinders the commercialization of lead halide perovskite solar cells. It is reported that interfacial non-radiative recombination in lead halide perovskite solar cells is the main cause that leads to energy loss, affects device stability and then deteriorates the device performance. To solve this issue, interface engineering is applied as a valid strategy to suppress interfacial non-radiative recombination and fabricate efficient and stable lead halide perovskite solar cells, achieving tangible results. In this review, the working principle of lead halide perovskite solar cells and interfacial non-radiactive recombination process are explained in detail. The origin of interfacial non-radiative recombination is also analyzed, which highlights the important role of interface engineering for lead halide perovskite solar cells. Meanwhile, the recent research advances of interface engineering in lead halide perovskite solar cells with normal n-i-p structure are summarized with the discussion of the modification mechanism. What’s more, based on the development status of the interface engineering in lead halide perovskite solar cells, we prospect the development directions for the interface engineering in lead halide perovskite solar cells in the future.
- lead halide perovskite solar cells /
- interface engineering /
- efficiency /
- stability /
- non-radiative recombination /
- energy level alignment /
- defects passivation

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图 1 ABX₃型钙钛矿的晶体结构示意图

Figure 1. Schematic diagram of the crystal structure of ABX₃ perovskite

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图 2 钙钛矿太阳能电池的常见结构示意图：(a) n-i-p型介孔结构；(b) n-i-p型平面结构；(c) p-i-n型平面结构；(d)无电子传输层(ETL)结构；((e), (f)) 无空穴传输层(HTL)结构

Figure 2. Schematic diagram of the regular structure of perovskite solar cells: (a) n-i-p mesoporous structure; (b) n-i-p planar structure; (c) p-i-n planar structure; (d) Electron transport layer (ETL)-free structure; ((e), (f)) Hole transport layer (HTL)-free structure

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图 3 n-i-p型钙钛矿太阳能电池的工作原理图：(a)激子的产生与分离；(b)电荷扩散；(c)电荷提取；(d)电荷传输；(e)钙钛矿光吸收层内部的载流子复合；(f)界面陷阱态导致的电荷复合

Figure 3. Schematic diagram of the working principle of n-i-p perovskite solar cell: (a) Generation and separation of excitons; (b) Charge diffusion; (c) Charge extraction; (d) Charge transfer; (e) Carriers recombination in perovskite light absorber; (f) Charge recombination induced by interface trap states

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图 4 MAPbI₃中点缺陷的能级位置^[26]

Figure 4. Energy level positions of point defects in MAPbI₃^[26]

I_i—I⁻ interstitials; MA_Pb—MA⁺ on Pb sites; V_MA—MA⁺ vacancies; V_Pb—Pb²⁺ vacancies; I_MA—I⁻ on MA sites; I_Pb—I⁻ on Pb sites; MA_i—MA⁺ interstitials; Pb_MA—Pb²⁺ on MA sites; V_I—I⁻ vacancies; Pb_i—Pb²⁺ interstitials; MA_I—MA⁺ on I sites; Pb_I—Pb²⁺ on I sites

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图 5 钙钛矿薄膜表面的缺陷示意图^[32]

Figure 5. Schematic diagram of defects on the surface of perovskite thin films^[32]

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图 6 金属卤化物钙钛矿(MHP)太阳能电池常用材料的能级示意图^[40]

Figure 6. Schematic energy-level diagram of commonly used materials in planar n-i-p metal halide perovskite (MHP) solar cells^[40]

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图 7 ZnO修饰前(a)和修饰后(b)的ITO/SnO₂界面处的能带弯曲变化示意图^[48]

Figure 7. Schematics of the the interfacial energy band bending of ITO/SnO₂ interface before (a) and after (b) ZnO modification^[48]

W_m—Metal work function; W_s—Semiconductor work function

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图 8 MXene修饰后电池内部的能级排列示意图^[50]

Figure 8. Schematics of the energy level alignment after the MXene modification^[50]

qφ_m—Work function; E_EA—Electronic affinity; E_VAC—Vacuum level; E_C—Conduction band minimum; E_Femi—Femi level; E_V—Valence band maximum

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图 9 ZnSe修饰后钙钛矿太阳能电池的能级示意图^[55]

Figure 9. Energy level diagram of the ZnSe-modified PSC^[55]

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图 10 聚苯乙烯(PS)缓冲层释放应力示意图：(a)具有PS缓冲层的预制钙钛矿薄膜；(b)具有PS缓冲层的退火钙钛矿薄膜；(c)没有PS缓冲层的预制钙钛矿薄膜；(d)没有S缓冲层的退火钙钛矿薄膜^[67]

Figure 10. Schematic illustration of the polystyrene (PS) buffer layer to release the stress: (a) As-prepared perovskite films with PS; (b) Annealed perovskite films with PS; (c) As-prepared perovskite films without PS; (d) Annealed perovskite films without PS^[67]

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图 11 器件结构示意图以及Lewis碱配体MTDAA缺陷钝化示意图^[79]

Figure 11. Device structure in this work and a schematic diagram of defect passivation by Lewis base ligands MTDAA^[79]

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图 12 在黑暗中(a)和光照下(b)费米能级分裂的能带排列示意图^[93]

Figure 12. Schematic illustration of the energy band alignment regarding Fermi level splitting in the dark (a) and under light illumination (b)^[93]

E_fn—Electron quasi-Fermi level; E_fp—Hole quasi-Fermi level

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图 13 使用PTU(N-苯基硫脲)和PU(N-苯基脲)修饰的器件能级图^[98]

Figure 13. Energy-level diagram of PSCs with PTU (N-phenylthiourea) and PU (N-phenylurea)^[98]

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图 14 (a) 1-[N-(2-羟乙基)-4'-哌啶基]-3-(4'-哌啶基)丙烷(PPPDE)在FTO表面的静电自组装示意图；PPPDE修饰前(b)与修饰后(c) ITO/钙钛矿界面处的能级示意图^[107]

Figure 14. (a) Electrostatic self-assembly of 1-[N-(2-Hydroxyethyl)-4’-piperidyl]-3-(4’-piperidyl) (PPPDE) on the FTO surface; Energy level diagram of the ITO/perovskite interface before (b) and after (c) the PPPDE modification^[107]

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