L-3-(4-吡啶基)-丙氨酸钝化钙钛矿太阳电池界面缺陷

doi:10.15541/jim20200495

无机材料学报 ›› 2021, Vol. 36 ›› Issue (6): 629-636.DOI: 10.15541/jim20200495

所属专题：能源材料论文精选(2021)；【虚拟专辑】钙钛矿材料(2020~2021)；【虚拟专辑】太阳能电池(2020~2021)；【能源环境】钙钛矿；【能源环境】太阳能电池

L-3-(4-吡啶基)-丙氨酸钝化钙钛矿太阳电池界面缺陷

刘雯雯¹(), 胡志蕾¹, 王立¹, 曹梦莎¹, 张晶¹, 张婧¹, 张帅¹(), 袁宁一¹, 丁建宁²()

1.常州大学江苏省光伏科学与工程协同创新中心材料科学与工程学院, 常州 213164
2.江苏大学微纳科学与技术中心, 镇江 212013

收稿日期:2020-08-27 修回日期:2020-10-22 出版日期:2021-06-20 网络出版日期:2020-11-05
通讯作者: 张帅, 副教授. E-mail: shuaizhang@cczu.edu.cn; 丁建宁, 教授. E-mail: dingjn@cczu.edu.cn
作者简介:刘雯雯(1997-), 女, 硕士研究生. E-mail: 2356143925@qq.com
基金资助:
国家自然科学基金(51602031);国家自然科学基金(51603021);江苏省“青蓝工程”优秀青年骨干教师(2019);江苏省高等学校自然科学研究重大项目(19KJA430014);江苏省研究生科研与实践创新计划(SJCX20_0975)

Passiviation of L-3-(4-Pyridyl)-alanine on Interfacial Defects of Perovskite Solar Cell

LIU Wenwen¹(), HU Zhilei¹, WANG Li¹, CAO Mengsha¹, ZHANG Jing¹, ZHANG Jing¹, ZHANG Shuai¹(), YUAN Ningyi¹, DING Jianning²()

1. School of Materials Science and Engineering, Jiangsu Photovoltaic Science and Engineering Collaborative Innovation Center, Changzhou university, Changzhou 213164, China
2. Micro Center for Science and Technology, Jiangsu University, Zhenjiang 212013, China

Received:2020-08-27 Revised:2020-10-22 Published:2021-06-20 Online:2020-11-05
Contact: ZHANG Shuai, associate professor. E-mail: shuaizhang@cczu.edu.cn; DING Jianning, professor. E-mail: dingjn@cczu.edu.cn
About author:LIU Wenwen(1997-), female, Master candidate. E-mail: 2356143925@qq.com
Supported by:
National Natural Science Foundation of China(51602031);National Natural Science Foundation of China(51603021);The Qinlan Project(2019);Natural Science Foundation of the Jiangsu Higher Education Institutions(19KJA430014);Postgraduate Research & Practice Innovation Program of Jangsu Province(SJCX20_0975)

摘要/Abstract

摘要：

近年来钙钛矿材料因其优异的光电性能而成为光伏领域的研究热点, 但调控钙钛矿太阳电池内界面缺陷仍是亟需解决的关键问题之一。本研究在溶液两步法制备钙钛矿光吸收层的过程中引入有机小分子添加剂(L-3-(4吡啶基)-丙氨酸(L-3-(4-pyridyl)-alanine, (PLA))。测试结果显示引入PLA可提高器件的各光电性能参数, 含PLA器件的最优能量转换效率为21.53%, 而参照器件为20.10%。进一步研究表明引入PLA可延长荧光寿命, 降低器件的陷阱态密度(从5.59×10¹⁶cm^-3降至3.40×10¹⁶cm^-3), 促进界面电荷抽取, 抑制载流子复合。器件性能的提升是由于PLA促进PbI₂在钙钛矿薄膜晶界处富集及PLA在界面处锚定起到了钝化缺陷的作用。本研究可以为进一步调控钙钛矿太阳电池的缺陷提供借鉴。

关键词: 钙钛矿太阳电池, 多官能团添加剂, 陷阱态密度, 载流子复合

Abstract:

In recent years, perovskite materials become a research hotspot in the field of solar cells due to their excellent photovoltaic properties, but control of their interface defects still remains one of the key problems to be solved. In this study, an organic small molecule additive (L-3-(4-pyridyl)-alanine (PLA)) was introduced in the preparation of perovskite photoabsorption layer by two-step solution method. The characterizations showed that the introduction of PLA could comprehensively improve photoelectric performance of the device, with optimal energy conversion efficiency of 21.53%, in contrast to that of the reference device (20.10%). Further studies showed that PLA could reduce the trap state density of the device from 5.59×10¹⁶cm^-3 to 3.40×10¹⁶cm^-3, promote the interface charge extraction, and decrease the carrier recombination. The above improvements can be attributed to the PLA induced PbI₂ enrichment at grain boundaries and PLA anchoring at defects, which play an important roles in passivate defects. This study can provide guideline for further regulating the defects of perovskite solar cells.

Key words: perovskite solar cell, additive with multifunctional groups, trap state density, carrier recombination

中图分类号:

O649

刘雯雯, 胡志蕾, 王立, 曹梦莎, 张晶, 张婧, 张帅, 袁宁一, 丁建宁. L-3-(4-吡啶基)-丙氨酸钝化钙钛矿太阳电池界面缺陷[J]. 无机材料学报, 2021, 36(6): 629-636.

LIU Wenwen, HU Zhilei, WANG Li, CAO Mengsha, ZHANG Jing, ZHANG Jing, ZHANG Shuai, YUAN Ningyi, DING Jianning. Passiviation of L-3-(4-Pyridyl)-alanine on Interfacial Defects of Perovskite Solar Cell[J]. Journal of Inorganic Materials, 2021, 36(6): 629-636.

图/表 11

图1 (a)PLA的分子结构式和(b)PLA修饰的PSC器件结构示意图

Fig. 1 (a) Molecular structure of PLA and (b) schematic diagram of PSC device with PLA

图2 (a, c, e)参照及(b, d, f)PLA修饰FTO/TiO2/钙钛矿薄膜的(a,b)表面、(c,d)截面SEM照片和(e,f)晶粒尺寸分布图

Fig. 2 (a,b) Surface and (c,d) cross sectional SEM images, (e,f) grain size distributions of FTO/TiO2/perovskite films (a, c, e) without and (b, d, f) with PLA

图3 (a)钙钛矿薄膜的ATR-FT-IR光谱((b)为(a)中黑色虚线矩形区域的放大图), (c)薄膜的紫外-可见吸收光谱图和(d)XRD图谱

Fig. 3 (a) ATR-FT-IR spectra, ((b) magnified ATR-FT-LR spectra of rectangular area in (a)), (c) UV-Vis absorption spectra and (d) XRD patterns of FTO/TiO2/perovskite films with and without PLA

表1 PLA修饰及参照PSC器件光电性能参数的平均值和标准偏差

Table 1 Mean values and standard deviation (SD) of photovoltaic parameters for PSC devices without and with PLA

Device	J_SC(SD)/(mA·cm^-2)	V_OC(SD)/V	FF(SD)/%	PCE(SD)/%
Without PLA	23.84(0.74)	1.07(0.02)	76.80(1.15)	19.49(0.48)
With PLA	24.37(0.50)	1.07(0.02)	78.74(1.43)	20.55(0.39)

图4 PLA修饰及参照PSC器件的(a)JSC、(b)VOC、(c)FF和(d)PCE的统计分布图

Fig. 4 Statistical deviations of (a)JSC, (b)VOC, (c) FF, and (d) PCE for PSC devices without and with PLA

图5 最优(a)参照和(b)PLA修饰PSC器件的正反扫J-V曲线, (c)反扫J-V曲线的对比, (d)外量子效率谱图及JSC积分曲线

Fig. 5 Forward and reverse scan J-V curves of the optimal PSC devices (a) without and (b) with PLA, (c) comparison of the reverse J-V curves, and (d) external quantum efficiency spectra and integrated JSC curves for the optimal PSC devices without and with PLA

图6 PLA修饰及参照玻璃/钙钛矿薄膜的(a)稳态PL光谱, (b)TRPL衰减图谱(λexcitation=510 nm)和TRPL的拟合结果

Fig. 6 (a) PL spectra, (b) TRPL spectra (λexcitation=510 nm) and TRPL fitting results of glass/perovskite films with and without PLA

图7 (a)PLA修饰钙钛矿薄膜纯电子注入器件的结构示意图, (b)PLA修饰及参照钙钛矿薄膜纯电子注入器件的SCLC测试结果

Fig. 7 (a) Schematic diagram of electron-only perovskite film device with PLA, and (b) SCLC measurements of electron-only perovskite film devices with and without PLA

图S1 (a, c)参照和(b, d)PLA修饰FTO/TiO2/PbI2薄膜的(a,b)表面和(c,d)截面SEM照片

Fig. S1 (a,b) Surface and (c,d) cross sectional SEM images of FTO/TiO2/PbI2 film without PLA (a, c) and with PLA (b, d)

图S2 (a)光照和(b)暗态环境下参照和PLA修饰PSC的Nyquist图谱

Fig. S2 EIS plots of PSC without and with PLA (a) under illumination and (b) in dark

表S1 光照和暗态环境下参照及PLA修饰PSC器件的EIS拟合参数

Table S1 EIS fitting parameters of PSC without and with PLA under illumination and in dark

Device	R_S/ (Ω·cm^-2)	R₁/ (Ω·cm^-2)	R₂/ (Ω·cm^-2)
Without PLA (Illumination)	1.80	58.70	7.90
With PLA (Illumination)	1.43	15.74	40.49
Without PLA (Dark)	0.78	3.46×10⁵	2.27×10⁴
With PLA (Dark)	1.21	2.15×10⁴	4.50×10⁵

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L-3-(4-吡啶基)-丙氨酸钝化钙钛矿太阳电池界面缺陷

Passiviation of L-3-(4-Pyridyl)-alanine on Interfacial Defects of Perovskite Solar Cell

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