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用于甲脒基钙钛矿薄膜愈合后的氨。

Ammonia for post-healing of formamidinium-based Perovskite films.

作者信息

Li Zhipeng, Wang Xiao, Wang Zaiwei, Shao Zhipeng, Hao Lianzheng, Rao Yi, Chen Chen, Liu Dachang, Zhao Qiangqiang, Sun Xiuhong, Gao Caiyun, Zhang Bingqian, Wang Xianzhao, Wang Li, Cui Guanglei, Pang Shuping

机构信息

Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266101, P. R. China.

Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.

出版信息

Nat Commun. 2022 Jul 29;13(1):4417. doi: 10.1038/s41467-022-32047-z.

Abstract

Solvents employed for perovskite film fabrication not only play important roles in dissolving the precursors but also participate in crystallization process. High boiling point aprotic solvents with O-donor ligands have been extensively studied, but the formation of a highly uniform halide perovskite film still requires the participation of additives or an additional step to accelerate the nucleation rate. The volatile aliphatic methylamine with both coordinating ligands and hydrogen protons as solvent or post-healing gas facilitates the process of methylamine-based perovskite films with high crystallinity, few defects, and easy large-scale fabrication as well. However, the attempt in formamidinium-containing perovskites is challenged heretofore. Here, we reveal that the degradation of formamidinium-containing perovskites in aliphatic amines environment results from the transimination reaction of formamidinium cation and aliphatic amines along with the formation of ammonia. Based on this mechanism, ammonia is selected as a post-healing gas for a highly uniform, compact formamidinium-based perovskite films. In particular, low temperature is proved to be crucial to enable formamidinium-based perovskite materials to absorb enough ammonia molecules and form a liquid intermediate state which is the key to eliminating voids in raw films. As a result, the champion perovskite solar cell based on ammonia post-healing achieves a power conversion efficiency of 23.21% with excellent reproducibility. Especially the module power conversion efficiency with 14 cm active area is over 20%. This ammonia post-healing treatment potentially makes it easier to upscale fabrication of highly efficient formamidinium-based devices.

摘要

用于制备钙钛矿薄膜的溶剂不仅在溶解前驱体方面发挥重要作用,还参与结晶过程。含O供体配体的高沸点非质子溶剂已得到广泛研究,但形成高度均匀的卤化物钙钛矿薄膜仍需要添加剂的参与或额外步骤来加速成核速率。具有配位配体和氢质子的挥发性脂肪族甲胺作为溶剂或后处理气体,有助于制备具有高结晶度、缺陷少且易于大规模制备的甲胺基钙钛矿薄膜。然而,迄今为止,在含甲脒的钙钛矿方面的尝试面临挑战。在此,我们揭示了含甲脒的钙钛矿在脂肪族胺环境中的降解是由甲脒阳离子与脂肪族胺的转亚胺化反应以及氨的形成导致的。基于这一机理,氨被选为后处理气体用于制备高度均匀、致密的甲脒基钙钛矿薄膜。特别地,低温被证明对于使甲脒基钙钛矿材料吸收足够的氨分子并形成液体中间态至关重要,而这种液体中间态是消除原始薄膜中孔隙的关键。结果,基于氨后处理的冠军钙钛矿太阳能电池实现了23.21%的功率转换效率,且具有出色的可重复性。尤其是活性面积为14平方厘米的组件功率转换效率超过20%。这种氨后处理方法可能使高效甲脒基器件的大规模制备变得更容易。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9bbb/9338283/cee72117e64a/41467_2022_32047_Fig1_HTML.jpg

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