Guo Zhu, Lin Jiawei, Mao Lingling
Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, Guangdong, China.
SUSTech Energy Institute for Carbon Neutrality, Southern University of Science and Technology, Shenzhen, 518055, Guangdong, China.
Chem Soc Rev. 2025 Sep 1. doi: 10.1039/d5cs00475f.
Metal halide perovskites (MHPs) are rapidly developing as a class of versatile materials combining the exceptional optoelectronic characteristics with tunable ferroelectricity and nonlinear optical responses. Spanning across the three-dimensional, two-dimensional, and one-dimensional architectures, these materials have demonstrated exceptional structural diversity, providing immense opportunities for tailored property design. We start by referencing the classic oxide perovskites, sharing differences and similarities of these material systems. The fundamental mechanisms driving ferroelectricity in MHPs range from displacive distortions and lone-pair stereoactivity to organic cation ordering. The ability to control these mechanisms through precise organic cation site (A-site) and metal site (B-site) engineering, dimensionality tuning, and external stimuli opens new avenues for designing high-performance ferroelectric and second-harmonic generation (SHG)-active materials. This review highlights the rich structural diversity in halide perovskites, with a focus on the critical structure-property relationships that govern their ferroelectric and nonlinear optical behaviors. We discuss key design strategies that exploit asymmetric coordination, excitonic channels, and resonance effects to enhance SHG responses and polarization switching. Furthermore, we analyze how these materials might be included into useful devices such as ferroelectric photovoltaics and photodetectors, as well as how they could be used in multipurpose optoelectronic applications. Finally, we discuss the stability and scalability issues that MHP ferroelectrics are having in the commercialization process and provide insights for future research avenues that may help realize these materials' full potential.
金属卤化物钙钛矿（MHPs）作为一类多功能材料正在迅速发展，它兼具卓越的光电特性、可调节的铁电性和非线性光学响应。这些材料涵盖三维、二维和一维结构，展现出非凡的结构多样性，为定制性能设计提供了巨大机遇。我们首先参考经典的氧化物钙钛矿，阐述这些材料体系的异同。在MHPs中驱动铁电性的基本机制包括位移畸变、孤对电子立体活性以及有机阳离子有序排列。通过精确的有机阳离子位点（A位）和金属位点（B位）工程、维度调控以及外部刺激来控制这些机制的能力，为设计高性能铁电和二次谐波产生（SHG）活性材料开辟了新途径。本综述着重介绍卤化物钙钛矿丰富的结构多样性，重点关注决定其铁电和非线性光学行为的关键结构 - 性能关系。我们讨论了利用不对称配位、激子通道和共振效应来增强SHG响应和极化切换的关键设计策略。此外，我们分析了如何将这些材料应用于诸如铁电光电器件和光电探测器等有用器件，以及它们如何用于多功能光电应用。最后，我们讨论了MHP铁电体在商业化过程中面临的稳定性和可扩展性问题，并为未来的研究方向提供见解，这可能有助于实现这些材料的全部潜力。
