Optimizing Sublattice Correlation to Enhance Stability and Charge Carrier Lifetime in Mixed Halide Perovskites

IF 9.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Nano Letters Pub Date : 2025-01-02 DOI:10.1021/acs.nanolett.4c05701

Jiao Wang, Haoran Lu, Xuesong Tian, Run Long, Oleg V. Prezhdo

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Abstract

A-site cations in ABX₃ metal halide perovskites do not contribute to the frontier electronic states. They influence optoelectronic properties indirectly through interaction with the BX₃ sublattice. By systematically investigating correlated motions of Cs cations and the PbX₃ lattice (X = Cl, Br, I), we demonstrate that the interaction between the two subsystems depends on electronegativity and size of the X-site anion. The most electronegative Cl halide minimizes thermal atomic fluctuations, favoring optoelectronic performance. CsPbI₃ is improved by Cl-doping. Nonadiabatic molecular dynamics simulations demonstrate that charge carrier lifetime is extended by nearly an order of magnitude when atomic fluctuations are minimized, due to reduced electron–vibrational interactions, in agreement with experiments. The detailed atomistic examination of the significant impact of correlated motion of the A-site and BX₃ sublattices and its influence on perovskite stability and exciton lifetime offers theoretical guidelines for optimizing perovskite optoelectronic devices.

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优化亚晶格相关以提高混合卤化物钙钛矿的稳定性和载流子寿命

ABX3金属卤化物钙钛矿中的a位阳离子对前沿电子态没有贡献。它们通过与BX3亚晶格的相互作用间接影响光电性能。通过系统地研究Cs阳离子和PbX3晶格（X = Cl, Br， I）的相关运动，我们证明了两个子系统之间的相互作用取决于电负性和X位阴离子的大小。电负性最强的氯化卤化物使热原子波动最小化，有利于光电性能。通过掺杂cl对CsPbI3进行了改进。非绝热分子动力学模拟表明，当原子波动最小化时，由于电子-振动相互作用的减少，电荷载流子寿命延长了近一个数量级，与实验结果一致。详细的原子分析了a位和BX3亚晶格相关运动对钙钛矿稳定性和激子寿命的重要影响，为优化钙钛矿光电器件提供了理论指导。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Nano Letters 工程技术-材料科学：综合

CiteScore

16.80

自引率

2.80%

发文量

1182

审稿时长

1.4 months

期刊介绍： Nano Letters serves as a dynamic platform for promptly disseminating original results in fundamental, applied, and emerging research across all facets of nanoscience and nanotechnology. A pivotal criterion for inclusion within Nano Letters is the convergence of at least two different areas or disciplines, ensuring a rich interdisciplinary scope. The journal is dedicated to fostering exploration in diverse areas, including: - Experimental and theoretical findings on physical, chemical, and biological phenomena at the nanoscale - Synthesis, characterization, and processing of organic, inorganic, polymer, and hybrid nanomaterials through physical, chemical, and biological methodologies - Modeling and simulation of synthetic, assembly, and interaction processes - Realization of integrated nanostructures and nano-engineered devices exhibiting advanced performance - Applications of nanoscale materials in living and environmental systems Nano Letters is committed to advancing and showcasing groundbreaking research that intersects various domains, fostering innovation and collaboration in the ever-evolving field of nanoscience and nanotechnology.