钙钛矿太阳能电池纳米纤维改性电子传输层研究

doi:10.15541/jim20230578

无机材料学报 ›› 2024, Vol. 39 ›› Issue (7): 828-834.DOI: 10.15541/jim20230578 CSTR: 32189.14.10.15541/jim20230578

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

钙钛矿太阳能电池纳米纤维改性电子传输层研究

肖梓晨¹^,²^,³(), 何世豪¹^,²^,³, 邱诚远¹^,²^,³, 邓攀¹^,²^,³, 张威¹^,²^,³, 戴维德仁¹^,²^,³, 缑炎卓¹^,²^,³, 李金华¹^,²^,³, 尤俊¹^,²^,³, 王贤保¹^,²^,³(), 林俍佑¹^,²^,³()

1.湖北大学功能材料绿色制备与应用教育部重点实验室, 武汉 430062
2.湖北大学高分子材料湖北省重点实验室, 武汉 430062
3.湖北大学材料科学与工程学院, 武汉 430062

收稿日期:2023-12-14 修回日期:2024-02-27 出版日期:2024-07-20 网络出版日期:2024-03-08
通讯作者: 王贤保, 教授. E-mail: wxb@hubu.edu.cn;
林俍佑, 副教授. E-mail: Liangyou_Lin@hubu.edu.cn
作者简介:肖梓晨(1999-), 女, 硕士研究生. E-mail: zichen_xiao@qq.com
基金资助:
湖北省自然科学基金(202211301201002);武汉市科技计划(202211301251333)

Nanofiber-modified Electron Transport Layer for Perovskite Solar Cells

XIAO Zichen¹^,²^,³(), HE Shihao¹^,²^,³, QIU Chengyuan¹^,²^,³, DENG Pan¹^,²^,³, ZHANG Wei¹^,²^,³, DAI Weideren¹^,²^,³, GOU Yanzhuo¹^,²^,³, LI Jinhua¹^,²^,³, YOU Jun¹^,²^,³, WANG Xianbao¹^,²^,³(), LIN Liangyou¹^,²^,³()

1. Key Laboratory for the Green Preparation and Application of Functional Materials, Ministry of Education, Hubei University, Wuhan 430062, China
2. Hubei Key Laboratory of Polymer Materials, Hubei University, Wuhan 430062, China
3. School of Materials Science and Engineering, Hubei University, Wuhan 430062, China

Received:2023-12-14 Revised:2024-02-27 Published:2024-07-20 Online:2024-03-08
Contact: WANG Xianbao, professor. E-mail: wxb@hubu.edu.cn;
LIN Liangyou, associate professor. E-mail: Liangyou_Lin@hubu.edu.cn
About author:XIAO Zichen (1999-), female, Master candidate. E-mail: zichen_xiao@qq.com
Supported by:
Natural Science Foundation of Hubei Province of China(202211301201002);Wuhan Municipal Science and Technology Bureau of China(202211301251333)

摘要/Abstract

摘要：

二氧化锡(SnO₂)由于具有高透光率、高电子迁移率、良好的紫外稳定性以及可低温加工等优势, 作为电子传输材料在钙钛矿太阳能电池(PSC)中得到广泛应用。然而, 用商业胶体溶液制备的SnO₂电子传输层仍然存在易团聚、缺陷多、能级不匹配等问题, 限制了器件性能和稳定性。本研究将一种高分子甲壳素纳米纤维(1,2-二苯甲酰氧基苯基甲壳素, DC)引入到SnO₂前驱液中来改善SnO₂薄膜质量, 系统研究了DC对前驱液、薄膜和器件性能的影响。实验结果表明, DC添加剂能够有效抑制纳米颗粒团聚, 使前驱液分散得更均匀。改善后的SnO₂薄膜的粗糙度更小, 能更好地被钙钛矿溶液浸润, 有利于SnO₂与钙钛矿层形成更紧密的接触。同时, SnO₂薄膜中的氧空位缺陷被有效钝化, 缺陷占比降低至30%, 进一步提升了薄膜质量。改进后SnO₂电子传输层与钙钛矿层的能级匹配性更好, 载流子提取和传输性能得到优化。DC改性后的PSC性能得到显著提升, 最优器件的光电转换效率达到19.11%。本工作不仅解决了SnO₂电子传输层在制备过程中的团聚问题, 而且为提高PSC能提供了理论指导与方法。

关键词: 二氧化锡, 电子传输层, 钙钛矿太阳能电池, 高分子, 光电转换效率

Abstract:

Tin dioxide (SnO₂) is widely used in perovskite solar cell (PSC) as an electron transport material due to its high transmittance, high electron mobility, good UV stability, and low-temperature processing. However, SnO₂ electron transport layer prepared from commercial colloidal solution still faces some challenges such as easy agglomeration, defects, and energy level mismatch, limiting its performance and stability. This study improved the quality of SnO₂ films by introducing a polymer chitin nanofiber (1,2-dibenzoyloxyphenylchitin, DC) into the SnO₂ precursor solution, and systematically studied the effect of DC on the precursor solution, film and device performance. Experimental results showed that DC additive could effectively inhibit the agglomeration of SnO₂ nanoparticles, ensuring a more homogeneous dispersion in the precursor solution. The improved SnO₂ films had smaller roughness and could be better wetted by perovskite solution, which is beneficial to closer contact with the perovskite layer. Simultaneously, the oxygen vacancy defects in the SnO₂ films were effectively passivated, and the proportion of defects was reduced to 30%, further improving the quality of the films. Based on the improved energy level matching between the SnO₂ electron transport layer and the perovskite layer, the carrier extraction and transport performance was optimized. The performance of DC-modified PSC was significantly improved, and the photoelectric conversion efficiency of the optimal device reached 19.11%. This work not only overcomes the agglomeration problem of the SnO₂ electron transport layer during the preparation process, but also provides theoretical guidance and method for improving the performance of perovskite solar cells.

Key words: tin dioxide, electron transport layer, perovskite solar cell, polymer, photoelectric conversion efficiency

中图分类号:

O649

肖梓晨, 何世豪, 邱诚远, 邓攀, 张威, 戴维德仁, 缑炎卓, 李金华, 尤俊, 王贤保, 林俍佑. 钙钛矿太阳能电池纳米纤维改性电子传输层研究[J]. 无机材料学报, 2024, 39(7): 828-834.

XIAO Zichen, HE Shihao, QIU Chengyuan, DENG Pan, ZHANG Wei, DAI Weideren, GOU Yanzhuo, LI Jinhua, YOU Jun, WANG Xianbao, LIN Liangyou. Nanofiber-modified Electron Transport Layer for Perovskite Solar Cells[J]. Journal of Inorganic Materials, 2024, 39(7): 828-834.

图/表 12

图S1 1,2-二苯甲酰氧基苯基甲壳素(DC)的分子结构

Fig. S1 Molecular structure of 1,2-dibenzoyloxyphenyl chitosan(DC)

图S2 基于10%、20%、50%添加比例的钙钛矿器件PCE统计数据

Fig. S2 PCE distribution histogram of the control, DC-10%, DC-20% and DC-50% modified PSCs

图1 SnO2和SnO2-DC的(a)前驱液粒径统计分布图, (b)薄膜表面DMF接触角照片和(c, d)原子力显微镜图像

Fig. 1 (a) DLS spectra of precursors, (b) DMF contact angles, and (c, d) AFM topographical images of SnO2 and SnO2-DC films Colorful figures are available on website

图S3 原始和DC改性SnO2薄膜的SEM照片

Fig. S3 Top-view SEM images of pristine and DC modified SnO2 films

图2 SnO2和SnO2-DC薄膜的光电特性

Fig. 2 Photoelectric properties of SnO2 and SnO2-DC films (a) Sn3d and (b) O1s XPS spectra of SnO2 and SnO2-DC films; UPS spectra of (c) SnO2 and (d) SnO2-DC films; Tauc plots of (e) SnO2 and (f) SnO2-DC films; Colorful figures are available on website

图3 薄膜的能级结构、界面传输和载流子复合特性

Fig. 3 Energy levels, interface transport, and carrier recombination characteristics of films (a) Energy diagram of FTO, SnO2, SnO2-DC, perovskite and spiro-OMeTAD; (b) Conductivities of SnO2 and SnO2-DC films; (c) PL and (d) TRPL spectra of SnO2 and SnO2-DC films; Colorful figures are available on website

表1 TRPL的拟合参数

Table 1 Fitting parameters of TRPL

ETL	A₁/%	τ₁/ns	A₂/%	τ₂/ns	τ_avg/ns
SnO₂	0.30	24.36	0.57	268.80	9.31
SnO₂-DC	0.27	22.11	0.56	273.59	8.60

图S4 基于原始和DC改性SnO2薄膜上制备的钙钛矿层SEM照片

Fig. S4 Top-view SEM images of the perovskite films on pristine and DC modified SnO2 films

图4 基于SnO2和SnO2-DC PSC器件的光电性能

Fig. 4 Photovoltaic performance of PSC based on SnO2 and SnO2-DC (a) Schematic structure; (b) Statistical distributions of PCE; (c) J-V curves; (d) EQE spectra; Colorful figures are available on website

表S1 图4(d)中各项参数的平均值和标准差

Table S1 Device performance parameters extracted from Fig. 4(d)

ETL	PCE/%	FF/%	V_oc/V	J_sc/(mA·cm^-2)	PCE_max/%	PCE_min/%	PCE_mean/%
SnO₂	14.74±1.43	69.77±4.47	1.03±0.02	20.46±0.84	18.13	12.45	14.74292
SnO₂-DC	16.37±1.55	72.55±4.20	1.05±0.02	21.38±0.68	19.11	14.33	16.37923

图S5 基于(a) SnO2和(b) SnO2-DC器件的正反扫J-V曲线

Fig. S5 J-V curves of PSCs from both forward and reverse scans

表S2 图S5中的各项光伏参数和滞后指数(HI)

Table S2 Photovoltaic parameters of PSCs measured under reverse or forward scan

ETL	Scan direction	PCE/%	FF/%	V_oc/V	J_sc/(mA·cm^-2)	HI
SnO₂	Reverse	17.08	74.5	1051.9	21.80	0.079
SnO₂	Forward	15.73	71.0	1036.9	21.36	0.079
SnO₂-DC	Reverse	18.31	77.1	1048.4	22.64	0.004
SnO₂-DC	Forward	18.23	75.1	1068.4	22.71	0.004

参考文献 24

[1]	The National Renewable Energy Laboratory. Best-research-cell- efficiencies Chart. [2023-12-14]. https://www.nrel.gov/pv/cell-efficiency.html.
[2]	RÜHLE S. Tabulated values of the Shockley-Queisser limit for single junction solar cells. Solar Energy, 2016, 130: 139.
[3]	LUO D, SU R, ZHANG W, et al. Minimizing non-radiative recombination losses in perovskite solar cells. Nature Reviews Materials, 2019, 5(1): 44.
[4]	KIM M C, AHN N, LIM E, et al. Degradation of CH₃NH₃PbI₃ perovskite materials by localized charges and its polarity dependency. Journal of Materials Chemistry A, 2019, 7(19): 12075.
[5]	ALTINKAYA C, AYDIN E, UGUR E, et al. Tin oxide electron- selective layers for efficient, stable, and scalable perovskite solar cells. Advanced Materials, 2021, 33(15): e2005504.
[6]	YANG W S, NOH J H, JEON N J, et al. High-performance photovoltaic perovskite layers fabricated through intramolecular exchange. Science, 2015, 348(6240): 1234.
[7]	KIM M R, MA D. Quantum-dot-based solar cells: recent advances, strategies, and challenges. Journal of Physical Chemistry Letters, 2015, 6(1): 85.
[8]	PARK S Y, ZHU K. Advances in SnO₂ for efficient and stable n-i-p perovskite solar cells. Advanced Materials, 2022, 34(27): e2110438.
[9]	LIU M, JOHNSTON M B, SNAITH H J. Efficient planar heterojunction perovskite solar cells by vapour deposition. Nature, 2013, 501(7467): 395.
[10]	HUANG A, LEI L, ZHU J, et al. Achieving high current density of perovskite solar cells by modulating the dominated facets of room- temperature DC magnetron sputtered TiO₂ electron extraction layer. ACS Applied Materials & Interfaces, 2017, 9(3): 2016.
[11]	DONG H, WANG J, LI X, et al. Modifying SnO₂ with polyacrylamide to enhance the performance of perovskite solar cells. ACS Applied Materials & Interfaces, 2022, 14(29): 34143.
[12]	ZHANG P, WU J, ZHANG T, et al. Perovskite solar cells with ZnO electron-transporting materials. Advanced Materials, 2018, 30(3): 1703737.
[13]	XIONG L, GUO Y, WEN J, et al. Review on the application of SnO₂ in perovskite solar cells. Advanced Functional Materials, 2018, 28(35): 1802757.
[14]	RAO H S, CHEN B X, LI W G, et al. Improving the extraction of photogenerated electrons with SnO₂ nanocolloids for efficient planar perovskite solar cells. Advanced Functional Materials, 2015, 25(46): 7200.
[15]	STOLTERFOHT M, CAPRIOGLIO P, WOLFF C M, et al. The impact of energy alignment and interfacial recombination on the internal and external open-circuit voltage of perovskite solar cells. Energy & Environmental Science, 2019, 12(9): 2778.
[16]	ZHAO D, ZHANG C, ZHAO M, et al. A comprehensive optimization strategy: potassium phytate-doped SnO₂ as the electron-transport layer for high-efficiency perovskite solar cells. Journal of Materials Chemistry C, 2022, 10(19): 7641.
[17]	YOU S, ZENG H, KU Z, et al. Multifunctional polymer-regulated SnO₂ nanocrystals enhance interface contact for efficient and stable planar perovskite solar cells. Advanced Materials, 2020, 32(43): e2003990.
[18]	GUO X, DU J, LIN Z, et al. Enhanced efficiency and stability of planar perovskite solar cells using SnO₂:InCl₃ electron transport layer through synergetic doping and passivation approaches. Chemical Engineering Journal, 2021, 407: 127997.
[19]	WEI J, GUO F, WANG X, et al. SnO₂-in-polymer matrix for high- efficiency perovskite solar cells with improved reproducibility and stability. Advanced Materials, 2018, 30(52): e1805153.
[20]	MENG Y, LIU C, CAO R, et al. Pre-buried ETL with bottom-up strategy toward flexible perovskite solar cells with efficiency over 23%. Advanced Functional Materials, 2023, 33(28): 2214788.
[21]	LIN L, JONES T W, WANG J T W, et al. Strategically constructed bilayer tin (IV) oxide as electron transport layer boosts performance and reduces hysteresis in perovskite solar cells. Small, 2020, 16(12): 1901466.
[22]	RAOUI Y, EZ-ZAHRAOUY H, KAZIM S, et al. Energy level engineering of charge selective contact and halide perovskite by modulating band offset: mechanistic insights. Journal of Energy Chemistry, 2021, 54: 822. DOI
[23]	YI Z, LI X, XIAO B, et al. Dual-interface engineering induced by silane coupling agents with different functional groups constructing high-performance flexible perovskite solar cells. Chemical Engineering Journal, 2023, 469: 143790.
[24]	XIONG Z, LAN L, WANG Y, et al. Multifunctional polymer framework modified SnO₂ enabling a photostable α-FAPbI₃ perovskite solar cell with efficiency exceeding 23%. ACS Energy Letters, 2021, 6(11): 3824.

钙钛矿太阳能电池纳米纤维改性电子传输层研究

Nanofiber-modified Electron Transport Layer for Perovskite Solar Cells

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张慧, 许志鹏, 朱从潭, 郭学益, 杨英. 大面积有机-无机杂化钙钛矿薄膜及其光伏应用研究进展[J]. 无机材料学报, 2024, 39(5): 457-466.
[2]	陈甜, 罗媛, 朱刘, 郭学益, 杨英. 有机-无机共添加增强柔性钙钛矿太阳能电池机械弯曲及环境稳定性能[J]. 无机材料学报, 2024, 39(5): 477-484.
[3]	于嫚, 高荣耀, 秦玉军, 艾希成. 上转换发光纳米材料对钙钛矿太阳能电池迟滞效应和离子迁移动力学的影响[J]. 无机材料学报, 2024, 39(4): 359-366.
[4]	刘锁兰, 栾福园, 吴子华, 寿春晖, 谢华清, 杨松旺. 原位生长钙钛矿太阳能电池共形氧化锡薄膜[J]. 无机材料学报, 2024, 39(12): 1397-1403.
[5]	周泽铸, 梁子辉, 李静, 吴聪聪. 基于挥发性溶剂制备MAPbI₃钙钛矿太阳能电池/模组[J]. 无机材料学报, 2024, 39(11): 1197-1204.
[6]	厉佥元, 李纪伟, 张钰涵, 刘焱康, 孟阳, 储余, 朱一佳, 徐诺言, 朱亮, 张传香, 陶海军. PbTiO₃修饰和极化处理提升钙钛矿太阳能电池性能[J]. 无机材料学报, 2024, 39(11): 1205-1211.
[7]	韩旭, 姚恒大, 吕梅, 陆红波, 朱俊. 单分子液晶添加剂在甲脒铅碘钙钛矿太阳能电池中的应用[J]. 无机材料学报, 2023, 38(9): 1097-1102.
[8]	方万丽, 沈黎丽, 李海艳, 陈薪羽, 陈宗琦, 寿春晖, 赵斌, 杨松旺. NiO_x介孔层的成膜过程对碳电极钙钛矿太阳能电池性能的影响[J]. 无机材料学报, 2023, 38(9): 1103-1109.
[9]	丁统顺, 丰平, 孙学文, 单沪生, 李琪, 宋健. Fmoc-FF-OH钝化钙钛矿薄膜及其太阳能电池性能研究[J]. 无机材料学报, 2023, 38(9): 1076-1082.
[10]	张伦, 吕梅, 朱俊. Cs₂AgBiBr₆钙钛矿太阳能电池研究进展[J]. 无机材料学报, 2023, 38(9): 1044-1054.
[11]	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.
[12]	张万文, 罗建强, 刘淑娟, 马建国, 张小平, 杨松旺. 氧化锆间隔层的低温喷涂制备及其三层结构钙钛矿太阳能电池应用性能[J]. 无机材料学报, 2023, 38(2): 213-218.
[13]	马婷婷, 汪志鹏, 张梅, 郭敏. 超长稳定的混合阳离子钙钛矿太阳能电池性能优化研究[J]. 无机材料学报, 2023, 38(12): 1387-1395.
[14]	王烨, 焦忆楠, 郭军霞, 刘欢, 李睿, 尚子璇, 张士东, 王永浩, 耿海川, 侯登录, 赵晋津. 钙钛矿太阳能电池界面工程优化研究[J]. 无机材料学报, 2023, 38(11): 1323-1330.
[15]	杨柱, 郭少波, 蔡恒辉, 董显林, 王根水. 高分子辅助沉积法制备LaNiO₃外延导电薄膜[J]. 无机材料学报, 2022, 37(5): 561-566.