控制碘化铅形貌两步连续刮涂法大面积制备甲脒基钙钛矿薄膜

doi:10.3866/PKU.WHXB202203048

物理化学学报 >> 2023, Vol. 39 >> Issue (2): 2203048.doi: 10.3866/PKU.WHXB202203048

控制碘化铅形貌两步连续刮涂法大面积制备甲脒基钙钛矿薄膜

文永涛¹^,², 李静¹, 高晓峰³, 田聪聪¹, 朱昊³, 余国木¹, 张晓俐⁴, Park Hyesung⁵^,*(), 黄福志¹^,²^,*()

¹ 武汉理工大学材料复合新技术国家重点实验室, 武汉 430070
² 先进能源科学与技术广东省实验室佛山分中心佛山仙湖实验室, 广东佛山 528216
³ 武汉理工大学材料科学与工程国际化示范学院, 武汉 430070
⁴ 郑州大学材料科学与工程学院, 郑州 450001
⁵ Department of Materials Science and Engineering, Graduate School of Semiconductor Materials and Devices Engineering, Perovtronics Research Center, Low Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of Korea

收稿日期:2022-03-28 录用日期:2022-04-25 发布日期:2022-04-29
通讯作者: Park Hyesung,黄福志 E-mail:hspark@unist.ac.kr;fuzhi.huang@whut.edu.cn
基金资助:
科技部重点研发计划(2019YFE0107200);科技部重点研发计划(2017YFE0131900);国家自然科学基金(21875178);国家自然科学基金(52172230);国家自然科学基金(91963209);中央高校基本科研业务费专项资金(202443004);先进能源科学与技术广东省实验室佛山分中心佛山仙湖实验室开放基金(XDT2020-001);先进能源科学与技术广东省实验室佛山分中心佛山仙湖实验室开放基金(XHT2020-005)

Two-Step Sequential Blade-Coating Large-Area FA-Based Perovskite Thin Film via a Controlled PbI₂ Microstructure

Yongtao Wen¹^,², Jing Li¹, Xiaofeng Gao³, Congcong Tian¹, Hao Zhu³, Guomu Yu¹, Xiaoli Zhang⁴, Hyesung Park⁵^,*(), Fuzhi Huang¹^,²^,*()

¹ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
² Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Foshan 528216, Guangdong Province, China
³ International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
⁴ School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China
⁵ Department of Materials Science and Engineering, Graduate School of Semiconductor Materials and Devices Engineering, Perovtronics Research Center, Low Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology, Ulsan 44919, Republic of Korea

Received:2022-03-28 Accepted:2022-04-25 Published:2022-04-29
Contact: Hyesung Park,Fuzhi Huang E-mail:hspark@unist.ac.kr;fuzhi.huang@whut.edu.cn
About author:Email: fuzhi.huang@whut.edu.cn (F.H.)
Email: hspark@unist.ac.kr (H.P.)
Supported by:
the National Key Research and Development Plan(2019YFE0107200);the National Key Research and Development Plan(2017YFE0131900);the National Natural Science Foundation of China(21875178);the National Natural Science Foundation of China(52172230);the National Natural Science Foundation of China(91963209);the Fundamental Research Funds for the Central Universities(202443004);Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(XDT2020-001);Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(XHT2020-005)

1. 附件.pdf(1010KB)

摘要/Abstract

摘要：

钙钛矿太阳能电池在实现高性能光伏器件方面展现出巨大的商业化应用前景，但面临着一个最主要的挑战是开发工业化规模生产的大面积高质量钙钛矿薄膜制备工艺。在本研究中，为解决大面积印刷难题，通过两步连续刮涂法制备甲脒基钙钛矿吸光层。两步法中第一步沉积的PbI₂很容易形成致密的薄膜，这将导致后续沉积的有机胺盐无法和PbI₂充分完全反应，在钙钛矿薄膜中残留PbI₂，这会严重影响载流子的传输。为了实现理想的多孔PbI₂薄膜结构，我们通过在PbI₂前驱体溶液中引入四亚甲基亚砜(THTO)。通过形成PbI₂·THTO络合物，PbI₂的结晶过程被有效控制，易形成片状的PbI₂晶粒并沿着垂直基底方向上排列，得到了理想的纳米通道。这为后续的有机胺盐渗入提供了理想的纳米通道。最终5 cm × 5 cm模组实现了18.65%的功率转化效率，并具有出色的存储和热稳定性。这一结果展现了两步连续刮涂法策略在制备大面积钙钛矿太阳能电池方面具备一定的优势。

关键词: 钙钛矿太阳能电池, 两步法, 刮涂, 印刷, 模组

Abstract:

Solar cells, which are excellent alternatives to traditional fossil fuels, can efficiently convert sunlight into electricity. The intensive development of high-performance photovoltaic materials plays an important role in environmental protection and the utilization of renewable energy. Organic–inorganic hybrid perovskite materials, with a formula of ABX₃ (A = methylammonium (MA) or formamidinium (FA); B = Pb or Sn; X = Cl, I, or Br), have exhibited remarkable commercial prospects in high-performance photovoltaic devices owing to their long carrier diffusion length, excellent light absorption properties, high charge carrier mobility, and weak exciton binding energy. Recently, perovskite solar cells, fabricated using halide perovskite materials as light-absorbing layers, have achieved remarkable results; their certified power conversion efficiency has continuously improved and reached 25.7%. However, high-performance devices are usually fabricated using spin-coating methods with active areas below 0.1 cm². Hence, long-term research goals include achieving a large-scale uniform preparation of high-quality photoactive layers. The current one-step preparation of perovskite films involves the nucleation-crystalline growth process of perovskite. Auxiliary processes, such as using an anti-solvent, are often required to increase the nucleation rate and density of the film, which is not suitable for industrial large-area preparation. Additionally, the large-area preparation of perovskite films by spin-coating will result in different film thicknesses in the center and edge regions of the film due to an uneven centrifugal force. This will cause intense carrier recombination in the thicker area of the film and weak light absorption in the thinner area, which will reduce the performance of the device. To address these problems, the development of a large-area fabrication method for high-performance perovskite light-absorbing layers is essential. In this study, a two-step sequential blade-coating strategy was developed to prepare the FA-based perovskite layer. In general, PbI₂ easily forms a dense film; therefore, formamidinium iodide (FAI) cannot deeply penetrate to completely react with PbI₂. The PbI₂ residue is therefore detrimental to charge transportation. To fabricate the desired porous PbI₂ film, tetrahydrothiophene 1-oxide (THTO) was introduced into the PbI₂ precursor solution. By forming PbI₂·THTO complexes, PbI₂ crystallization is controlled, resulting in the formation of vertically packed PbI₂ flaky crystals. These crystals provide nanochannels for easy FAI penetration. The 5 cm × 5 cm modules fabricated through this strategy achieved a high efficiency of 18.65% with excellent stability. This indicates that the two-step sequential blade-coating strategy has considerable potential for scaling up the production of perovskite solar cells.

Key words: Perovskite solar cell, Two-step, Blade-coating, Printing, Module

文永涛, 李静, 高晓峰, 田聪聪, 朱昊, 余国木, 张晓俐, Park Hyesung, 黄福志. 控制碘化铅形貌两步连续刮涂法大面积制备甲脒基钙钛矿薄膜[J]. 物理化学学报, 2023, 39(2), 2203048. doi: 10.3866/PKU.WHXB202203048

Yongtao Wen, Jing Li, Xiaofeng Gao, Congcong Tian, Hao Zhu, Guomu Yu, Xiaoli Zhang, Hyesung Park, Fuzhi Huang. Two-Step Sequential Blade-Coating Large-Area FA-Based Perovskite Thin Film via a Controlled PbI₂ Microstructure[J]. Acta Phys. -Chim. Sin. 2023, 39(2), 2203048. doi: 10.3866/PKU.WHXB202203048

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202203048

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I2/2203048

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控制碘化铅形貌两步连续刮涂法大面积制备甲脒基钙钛矿薄膜

Two-Step Sequential Blade-Coating Large-Area FA-Based Perovskite Thin Film via a Controlled PbI₂ Microstructure

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控制碘化铅形貌两步连续刮涂法大面积制备甲脒基钙钛矿薄膜

Two-Step Sequential Blade-Coating Large-Area FA-Based Perovskite Thin Film via a Controlled PbI2 Microstructure

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Two-Step Sequential Blade-Coating Large-Area FA-Based Perovskite Thin Film via a Controlled PbI₂ Microstructure