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掺杂钙钛矿薄膜的气体修复技术及电池器件研究
常悦
Thesis Advisor逄淑平
2017-05
Degree Grantor中国科学院大学;中科院青岛生物能源与过程研究所
Place of Conferral青岛
Degree Discipline材料学
Keyword钙钛矿 太阳能电池 甲胺气体 溴掺杂 铯掺杂
Abstract有机无机杂化钙钛矿材料凭借其合适的带隙宽度、较大的载流子扩散长度、大的吸收系数、低廉的成本、可溶液法制备等优势,吸引了科研工作者的广泛关注。有机无机杂化钙钛矿太阳能电池自2009年诞生以来,电池效率从开始的3.8%,上升为目前的22.1%,展现出巨大的发展潜力和商业前景。钙钛矿太阳能电池效率的飞速提升,与钙钛矿的成膜工艺不断改善密切相关。抗溶剂法和两步法等是制备小面积钙钛矿膜的常用方法,但制备高质量大面积的钙钛矿太阳能电池仍面临一定的困难。另一方面有机无机杂化材料本身由于其离子活化能较低,造成其对水,热,光等的稳定性较差,限制着其进一步发展。因此,钙钛矿薄膜的大面积制备技术及其器件稳定性是目前钙钛矿太阳能电池发展所面临的两大核心问题。我们课题组前期开发的甲胺气体后修复技术与商业化涂布技术兼容度较高,基本满足了大面积制备钙钛矿薄膜的要求,本文将重点研究该技术在掺杂钙钛矿太阳能电池方面的应用。 本文首先研究了卤素掺杂钙钛矿薄膜的制备技术及其稳定性问题。通过甲胺气体修复技术得到了高度均匀的甲胺类钙钛矿(MAPbI3,MAPbBr3,MAPb(I1-xBrx)3 ) 薄膜并系统研究了Br掺杂钙钛矿太阳能电池分别作为硅叠层器件顶部电池和单节电池的应用。在单节太阳能电池研究中发现适量的卤素掺杂可以稍微提高电池器件的开路电压,但由于掺杂带来吸收范围变窄,总体效果不佳。更为严重的是我们发现卤素Br的引入,不仅没有限制卤素离子的扩散,还加速了Ag电极的腐蚀速率,造成器件性能的衰减。原因可能是其Br的离子半径更小,更容易在钙钛矿层、空穴传输层中扩散,对器件持续光照稳定性方面尤为不利。 我们继而选择无机阳离子掺杂方案,选用较甲胺离子电负性更强的铯(Cs+)离子,因为其与I-更强的作用力,从而提高了材料中碘离子的活化能。我们发现铯掺杂的钙钛矿材料同样适用于甲胺气体修复工艺,原因是CsI和MA气体同样可以生成可流动的CsI•xCH3NH2中间相。这种方法制备的Cs掺杂钙钛矿太阳能电池的光电效率达到17%,更为明显的是其稳定性比纯相MAPbI3钙钛矿电池得到较大改善。这是由于Cs离子更高电负性和非极化结构,其掺杂后钙钛矿材料中PbI6八面体的对称性得到了显著提高,10%的Cs掺杂后材料的降解速率降低了2倍。从而获得了更加稳定的钙钛矿材料及电池器件。 本文的研究针对于钙钛矿太阳能电池商业化发展的瓶颈问题,相关实验结果和基础理论的分析对进一步优化钙钛矿薄膜的制备工艺、材料体系以及器件结构等具有一定借鉴意义。
Other AbstractIn the past few years, organo-lead halide perovskites (such as CH3NH3PbI3, MAPbI3 and NH2CH=NH2PbI3, FAPbI3) have drawn the attention of many scientists due to their attractive optical and electrical properties, together with their moderate cost and low temperature solution-process ability. These merits make them one of the most promising candidates for the industrial development of next-generation optoelectronic devices. The first reported solar cell of CH3NH3PbI3 achieved an efficiency of 3.81% in 2009, and now, the certified record for power conversion efficiency (PCE) of PSCs has been 22.1%. The increase of efficiency of PSC can be contributed to the improvement of perovskite film fabrication technology. The fabrication technologies, such as two-step solution method, antisolvent method and so on, show the advantage in the small-area perovskite film fabrication. But there are also some hard challenges for the large-area perovskite solar cells fabrication. Besides, perovskite solar cell is not stable to water, heat, light and so on. In this case, A technology suitable for large scale fabrication of perovskite films and the stability of devices are the two core problems of perovskite solar cells. The technology of methylamine gas healing which is reported by our research group previously is highly compatible with the commercial coating technology. It can basically meet the requirements for a large scale fabrication of perovskite thin film. In the article. based on the technology of MA gas healing,the doped perovskite solar cells has been researched systematically. In this article, The fabrication process and the stability of Br doped perovskite film are studied firstly. A highly uniform methylamine perovskite (MAPbI3, MAPbBr3 and MAPb(I1-xBrx)3) thin film have been gained by methylamine gas healing process and the applications of Br doped perovskite in tandom and single solar cells are researched systematically. In the research of Br doped single solar cell, it is found that the open circuit voltage can be improved a little, and the absorption range of material is narrowed due to Br doping, as a result of very little improvement of PCE for the Br doped perovskite solar cells. What is more important is that the corrosion of Ag electrode is accelerated after the introduction of Br, due to the more smaller Br ion radius smaller, which is more easily to migrate in the perovskite layer and the hole transport layer. In order to solve this problem, a Cs doped perovskite solar cell is studied. In theory, There is a stronger electronegativity for Cs+ compared to MA+ ,which can provide a stronger force with iodin ion, as a result of an increased activation energy in the material. We found that the MA gas healing process is also suitable for the Cs doping perovskite material due to a fatasy reaction between CsI and MA gas with a liquid CsI.xCH3NH2 as mesophase. The Cs doped perovskite solar cell prepared by this method has a PCE of 17%, and its stability is greatly improved,compared to that of pure MAPbI3 perovskite cell. Besides, through structure calculation, it is found that due to the introduction of smaller Cs ion, the symmetry of PbI6 has been significantly improved, which result in more stable perovskite materials. This study is focused on bottleneck problems of perovskite solar cell business development. we believe the relevant experimental results and theoretical analysis in this article will have an important effect on the further optimization of perovskite solar cells.
Department仿生能源与储能系统团队
Subject Area材料学
Date Available2017-07-01
Subtype硕士 ; 学位论文
Language中文
Document Type学位论文
Identifierhttp://ir.qibebt.ac.cn/handle/337004/9970
Collection仿生能源与储能系统团队
Affiliation中国科学院大学;中科院青岛生物能源与过程研究所
Recommended Citation
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常悦. 掺杂钙钛矿薄膜的气体修复技术及电池器件研究[D]. 青岛. 中国科学院大学;中科院青岛生物能源与过程研究所,2017.
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