零维TTF铋基卤化物钙钛矿电子结构和光学性质的第一性原理研究

张坚; 李萍

doi:10.19976/j.cnki.43-1448/TF.2025085

粉末冶金材料科学与工程 >

2026 , Vol. 31 >Issue 2: 125 - 135

DOI: https://doi.org/10.19976/j.cnki.43-1448/TF.2025085

理论研究

零维TTF铋基卤化物钙钛矿电子结构和光学性质的第一性原理研究

张坚 ,
李萍

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山西师范大学化学与化工学院,太原 030031

收稿日期: 2025-12-17

修回日期: 2026-02-02

网络出版日期: 2026-05-07

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First principles study on electronic structures and optical properties of 0D TTF bismuth-based halide perovskites

ZHANG Jian ,
LI Ping

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School of Chemistry and Chemical Engineering, Shanxi Normal University, Taiyuan 030031, China

Received date: 2025-12-17

Revised date: 2026-02-02

Online published: 2026-05-07

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摘要

针对铋基卤化物钙钛矿在空气中易水解、实验表征受限的问题,本研究通过第一性原理计算,系统探究了3种不同价态(+2、+1及混合价态)零维四硫富瓦烯(tetrathiafulvalene, TTF)铋基卤化物钙钛矿[TMT-TTF]BiCl₅、[TMT-TTF]Bi₃Cl₁₁和[TMT-TTF]Bi₄Cl₁₆的电子结构、光学性质及弱相互作用机制。结果表明：3种零维TTF铋基卤化物钙钛矿材料的能带结构均表现为直接带隙,导带底和价带顶均集中于X|Y高对称点;均呈现弱光学各向异性,并展示出特征性光学响应;TTF阳离子与铋基卤化物骨架之间的相互作用以范德华力为主导,材料内部则以化学键作用为主。本研究可为开发高稳定性、高效率低维钙钛矿提供关键理论支撑。

关键词： 四硫富瓦烯; 零维铋基卤化物钙钛矿; 电子结构; 光学性质; 相互作用分析

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张坚 , 李萍 . 零维TTF铋基卤化物钙钛矿电子结构和光学性质的第一性原理研究[J]. 粉末冶金材料科学与工程, 2026 , 31(2) : 125 -135 . DOI: 10.19976/j.cnki.43-1448/TF.2025085

Abstract

Addressing the susceptibility of bismuth-based halide perovskites to hydrolysis in air and the consequent limitations on experimental characterization, this study employs first principles calculations to systematically investigate the electronic structures, optical properties, and weak interaction mechanisms of three kinds of 0D tetrathiafulvalene (TTF) bismuth-based halide perovskites [TMT-TTF]BiCl₅, [TMT-TTF]Bi₃Cl₁₁, and [TMT-TTF]Bi₄Cl₁₆ with distinct valence states (+2, +1, and mixed valence state). The results demonstrate that all three kinds of 0D TTF bismuth-based halide perovskite materials exhibit direct bandgap structures, with both the conduction band minimum and valence band maximum concentrating at the X|Y high-symmetry points. These materials display weak optical anisotropy and distinctive optical responses. The interaction between TTF cations and the bismuth-based halide frameworks is dominated by van der Waals forces, while the interior of the materials is primarily governed by chemical bonding interactions. This study provides crucial theoretical support for developing high-stability and high-efficiency low-dimensional perovskites.

Key words： tetrathiafulvalene; 0D bismuth-based halide perovskite; electronic structure; optical property; interaction analysis

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