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清华大学学报(自然科学版)  2024, Vol. 64 Issue (5): 879-888    DOI: 10.16511/j.cnki.qhdxxb.2024.22.001
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氯化铷添加剂对钙钛矿太阳能电池性能的影响
高宇, 张衍国, 周会, 李清海
清华大学 能源与动力工程系, 热科学与动力工程教育部重点实验室, 北京 100084
Effects of RbCl additive on performance of perovskite solar cells
GAO Yu, ZHANG Yanguo, ZHOU Hui, LI Qinghai
Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Energy and Power Engineering, Beijing 100084, China
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摘要 在钙钛矿前驱体溶液中加入添加剂, 是改善钙钛矿薄膜质量、提高钙钛矿太阳能电池性能的重要手段。该研究采用氯化铷(RbCl)作为添加剂, 通过扫描电子显微图像、X射线衍射图谱、光致发光光谱等表征手段, 研究了不同比例添加RbCl对钙钛矿薄膜形貌与结构的影响, 并通过外量子效率测试等方法, 比较了不同比例RbCl添加后的钙钛矿太阳能电池器件性能。结果表明:RbCl的添加有利于引导钙钛矿晶粒生长, 增大晶粒尺度, 形成致密薄膜, 从而抑制界面处载流子复合。适量添加RbCl后, 钙钛矿太阳能电池的光电转化效率从18.88 %提升到20.06 %, 开路电压、短路电流密度和填充因子等参数均显著提高, 钙钛矿太阳能电池性能得到明显改善。
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关键词 钙钛矿太阳能电池氯化铷添加剂钙钛矿薄膜晶粒尺寸    
Abstract:[Objective] Perovskite solar cells have drawn considerable attention in recent years. The addition of additives to perovskite precursor solutions is an important method to improve the quality of perovskite films for enhancing the performance of perovskite solar cells. In the past, alkali metal ions were extensively used as additives. Rubidium ions (Rb+) were generally added into perovskite films alongside other kinds of cations, following which the photovoltaic performance of the solar cells was clearly improved. However, few researchers studied the effects of only adding various proportions of Rb+ on perovskite films. In this study, rubidium chloride (RbCl) was used as an additive in perovskite precursor solutions and the morphology and structure of perovskite films were analyzed. Perovskite films were fabricated using a two-step method. RbCl was used as an additive into lead (II) iodide (PbI2) precursor solutions with the RbCl proportions 2 %, 4 %, 6 %, 8 %, 10 %, and 12 % versus PbI2, and a PbI2 precursor solution with no RbCl added was used as the control. Scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD) analysis were employed to analyze the difference in surface morphology and structure of the perovskite films. Steady-state photoluminescence (SSPL) and time-resolved photoluminescence (TRPL) spectra were recorded using devices of fluorine-doped tin oxide (FTO)/SnO2/perovskite films to study the carrier-transporting properties. The photovoltaic performances of the perovskite solar cells were studied through a solar simulator and external quantum efficiency testing. UV-visible (UV-vis) absorption spectra were recorded to explore the change in light absorption. The crystalline grain size is clearly enhanced upon adding 4 % RbCl. The grain size is 1.61 μm in the control and 2.14 μm upon adding 4 % RbCl. However, a high addition proportion (>8 %) damages and distorts the crystal structure, decreasing the film quality. Adding RbCl at a low proportion is beneficial for guiding the growth of perovskite grains, increasing grain size, and forming a dense film with fewer holes. The XRD patterns reveal that the peak at 12.6° corresponding to PbI2 is suppressed upon adding RbCl, whereas a new peak appears at 11.3°. The suppression of the PbI2 peak and the appearance of the new peak can be attributed to the formation of the RbCl complex and excessive PbI2, and the complex can be observed in the SEM images, which is confirmed by EDS results. The TRPL results reveal that adding RbCl at a low proportion enhances the transport and extraction of charge carriers, which is consistent with the SSPL results. Furthermore, the photovoltaic performance results reveal that with RbCl as an additive, the photoelectric conversion efficiency of the perovskite solar cells increases from 18.88 % to 20.06 %, and photoelectric properties such as open-circuit voltage, short-circuit current density, and filling factor are considerably improved. However, the UV-vis absorption spectra show that the absorption is not improved upon adding RbCl and even decreases with a high addition proportion, which is due to the increasing roughness of the perovskite films with increasing RbCl proportion. The enhancement of the photoelectric properties is due to the increase in transport and extraction of charge carriers caused by the improvement in film quality. This research demonstrates that adding RbCl at low proportions can enhance the grain size and transport of the carriers, improving the photovoltaic performance. The optimal RbCl addition proportion is ~4 %. This study has considerable potential for improving the performance of perovskite solar cells.
Key wordsperovskite solar cells    rubidium chloride    additives    perovskite thin film    grain size
收稿日期: 2023-06-18      出版日期: 2024-04-22
基金资助:国家自然科学基金项目(52070116);清华大学山西清洁能源研究院种子基金项目
通讯作者: 李清海,副研究员,E-mail:liqh@tsinghua.edu.cn     E-mail: liqh@tsinghua.edu.cn
引用本文:   
高宇, 张衍国, 周会, 李清海. 氯化铷添加剂对钙钛矿太阳能电池性能的影响[J]. 清华大学学报(自然科学版), 2024, 64(5): 879-888.
GAO Yu, ZHANG Yanguo, ZHOU Hui, LI Qinghai. Effects of RbCl additive on performance of perovskite solar cells. Journal of Tsinghua University(Science and Technology), 2024, 64(5): 879-888.
链接本文:  
http://jst.tsinghuajournals.com/CN/10.16511/j.cnki.qhdxxb.2024.22.001  或          http://jst.tsinghuajournals.com/CN/Y2024/V64/I5/879
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