Structure and optoelectronic properties of organic-inorganic bismuth-based hybrid perovskites AaBibIc (A=CH3NH3+, (CH3)2NH2+ and (CH3)3NH+)

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2025-09-26 DOI:10.1016/j.molstruc.2025.144162

Yangchun Mo , Qiule Zhao , Jiaxing Qi , Xiaopeng Wei , Jilin Wang , Disheng Yao , Nan Tian , Fei Long

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Abstract

Lead-free metal halide perovskites have attracted considerable attention recently owing to their low toxicity, high stability, and tunable photoelectric properties. However, a performance gap still exists with lead-based perovskites, and A-site cation engineering has become a core strategy for enhancing material properties by modulating the lattice structure, electronic energy bands, and defect states. Using (CH₃NH₃)₃ Bi₂I₉ single crystals as a control, this study successfully synthesized two novel organic-inorganic hybrid bismuth-based perovskite single-crystal materials, [(CH₃)₂NH₂]BiI₄·I₂ and [(CH₃)₃NH]₃Bi₂I₉, via inverse temperature crystallization and solvent evaporation crystallization methods, and prepared perovskite photovoltaic devices based on these crystals. This study systematically investigates the influence of the number of methyl groups in the A-site cation on the crystal structure, optical properties, and device performance of bismuth-based perovskites. Experimentally, it has been shown that increasing the number of methyl groups on the A-site cation leads to a larger cation volume and intensified lattice distortion. Among them, (CH₃NH₃)₃Bi₂I₉ is a two-dimensional layered structure and [(CH₃)₂NH₂]BiI₄·I₂ have one-dimensional chain, while [(CH₃)₃NH]₃Bi₂I₉ adopts a zero-dimensional. Consequently, the band gaps and their types in the three crystals change as their structures alter. (CH₃NH₃)₃Bi₂I₉, [(CH₃)₂NH₂]BiI₄·I₂ and [(CH₃)₃NH]₃Bi₂I₉ exhibit high thermal stability, remaining stable below 300 °C, 305 °C, and 240 °C, respectively. Inverted structure devices (ITO/NiOx/Perovskite/C₆₀/BCP/Ag) with (CH₃NH₃)₃Bi₂I₉, [(CH₃)₂NH₂]BiI₄·I₂, and [(CH₃)₃NH]₃Bi₂I₉ as light-absorbing layers achieved power conversion efficiencies of 0.004 %, 0.088 %, and 0.043 %. This study provides valuable insights for the further optimization of the bandgap, stability, and optoelectronic properties of bismuth-based organic-inorganic hybrid perovskite materials.

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有机-无机铋基杂化钙钛矿AaBibIc (A=CH3NH3+, （CH3)2NH2+和（CH3） 3nhh +）的结构与光电性能

无铅金属卤化物钙钛矿因其低毒性、高稳定性和可调谐的光电特性而受到广泛关注。然而，铅基钙钛矿的性能差距仍然存在，a位阳离子工程已经成为通过调制晶格结构、电子能带和缺陷态来增强材料性能的核心策略。本研究以（CH3NH3）3 Bi2I9单晶为对照，通过反温结晶和溶剂蒸发结晶的方法，成功合成了两种新型的有机-无机杂化铋基钙钛矿单晶材料[(CH3)2NH2]BiI4·I2和[(CH3)3NH]3Bi2I9，并制备了基于这些晶体的钙钛矿光伏器件。本研究系统地探讨了a位阳离子中甲基数目对铋基钙钛矿晶体结构、光学性质和器件性能的影响。实验表明，增加a位阳离子上甲基的数量会导致阳离子体积增大和晶格畸变加剧。其中，（CH3NH3）3Bi2I9为二维层状结构，[(CH3)2NH2]BiI4·I2为一维链结构，[(CH3) 3nhh]3Bi2I9为零维结构。因此，三种晶体中的带隙及其类型随其结构的改变而改变。（CH3NH3）3Bi2I9、[(CH3)2NH2]BiI4·I2和[(CH3) 3nhh]3Bi2I9表现出较高的热稳定性，分别在300℃、305℃和240℃下保持稳定。以（CH3NH3）3Bi2I9、[(CH3)2NH2]BiI4·I2和[(CH3) 3nhh]3Bi2I9为吸光层的倒置结构器件（ITO/NiOx/钙钛矿/C60/BCP/Ag）的功率转换效率分别为0.004%、0.088%和0.043%。该研究为进一步优化铋基有机-无机杂化钙钛矿材料的带隙、稳定性和光电性能提供了有价值的见解。

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

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