Unveiling the role of surface iodine vacancies in CsPbI3 perovskite: carrier recombination dynamics and defect passivation mechanisms†

IF 6.1 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Jing Wang and Xiang-Mei Duan
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Abstract

Lead–iodine perovskites are emerging as promising candidates for next-generation solar cells, yet a divergence persists between the theoretical and experimental realms regarding the impact of surface iodine vacancies (VI) on device performance. To elevate cell efficiency, a profound understanding and delicate control of VI and their passivation mechanisms are crucial. In this work, we studied various VI defects near the surface of all-inorganic CsPbI3 perovskite using ab initio non-adiabatic molecular dynamics. The results show that the electron–hole (e–h) recombination lifetime highly depends on the defect positions and configurations, as well as the efficacy of Lewis base additives in passivating defects. Despite the outermost layer VI creating no defect state within the band gap, the carrier recombination rate accelerates significantly by a factor of 2 compared to that with the defect-free surface, owing to strong electron–phonon coupling. Subsurface defects create a localized hole trapping state, enabling swift capture of valence band holes, which subsequently accelerate recombination with the conduction band electrons by a factor of 6.5. Remarkably for Pb-dimers, this rate escalates 13-fold. Incorporating the Lewis base molecule HCOO forms the stable Pb–O bonds with lead ions, preventing surface VI reconstruction (iodine migration), Pb-dimer formation, and an in-band defect state. These effectively reduce the electron–phonon coupling, achieving performance comparable to that of the defect-free surface. This work reconciles contradictory of surface VI on perovskite performance, and enriches our understanding of surface defect properties and their effects on carrier dynamics and device efficiency.

Abstract Image

揭示CsPbI3钙钛矿中表面碘空位的作用:载流子重组动力学和缺陷钝化机制
铅碘钙钛矿被认为是下一代太阳能电池的有希望的候选者,但关于表面缺陷碘空位(VI)对器件性能的影响,理论和实验领域仍然存在分歧。为了提高细胞效率,深入了解和精细控制VI及其钝化机制至关重要。本文采用从头算非绝热分子动力学方法研究了无机CsPbI3钙钛矿表面的各种VI缺陷。结果表明,电子-空穴复合寿命高度依赖于缺陷的位置和结构,以及路易斯碱添加剂钝化缺陷的效果。尽管最外层VI在带隙内没有产生缺陷状态,但由于强电子-声子耦合,与无缺陷表面相比,载流子复合速率显著提高了2倍。亚表面缺陷产生局部空穴捕获状态,使价带空穴能够快速捕获,从而加速与导带电子的复合,速度为6.5倍。值得注意的是,对于铅二聚体,这个速率上升了13倍。加入Lewis碱分子HCOO¯与铅离子形成稳定的Pb-O键,防止了表面VI重构(碘迁移)、pb二聚体形成和带内缺陷态。这些有效地减少了电子-声子耦合,实现了与无缺陷表面相当的性能。这项工作调和了表面VI对钙钛矿性能的矛盾,丰富了我们对表面缺陷性质及其对载流子动力学和器件效率的影响的理解。
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来源期刊
Inorganic Chemistry Frontiers
Inorganic Chemistry Frontiers CHEMISTRY, INORGANIC & NUCLEAR-
CiteScore
10.40
自引率
7.10%
发文量
587
审稿时长
1.2 months
期刊介绍: The international, high quality journal for interdisciplinary research between inorganic chemistry and related subjects
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