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有机–无机杂化Cu基卤化物由独立的有机阳离子和金属卤化物阴离子组成，具有多样的结构和丰富的发光性质。Cu具有多种配位构型，可以组成形式各样的阴离子，与不同种类的有机离子结合形成多种多样的结构和丰富可调的发光性质。有机–无机杂化Cu基卤化物具有丰富的发光机理，如自陷态发射、团簇发射、金属或卤素到有机配体的电荷转移、卤素到金属的电荷转移、金属中心(MC)的d~9s1→d10跃迁等。其发射具有宽带发射、大stokes位移、长寿命等特点，发光颜色可覆盖从蓝光到近红外发光。有机–无机杂化Cu基卤化物合成方法简单、环保、性能优异、可应用在高效白光发光二极管(LED)和高性能X射线成像等方面。文章首先讨论了有机–无机杂化Cu基卤化物的合成方法、不同类型的结构；其次，分别讨论了不同发光机理的特点，不同阴离子结构、不同取向、溶剂响应等对发光性质的影响；之后研究了有机–无机杂化Cu基卤化物在白光LED、X射线成像、近红外夜视成像、防伪等方面的应用。最后对有机–无机杂化Cu基卤化物未来研究进行了展望，提出了目前亟待解决的问题和未来可进一步研究的方向。
Abstract：As an emerging luminescent material, organic-inorganic hybrid metal halides have some advantages such as simple preparation methods, good solution processability, and tunable structures. They exhibit excellent optoelectronic properties and show a promising potential in cutting-edge applications such as solid-state lighting, anti-counterfeiting, scintillators, and detectors. Conventional high-efficiency organic-inorganic hybrid metal halides are mainly lead-based, but they have limited performance in terms of humidity and thermal stability, and the high toxicity of lead seriously restricts practical applications, necessitating a search for alternative metals. Metals that can replace Pb include those with a ns2 configuration(i.e., mainly Ge2+, Sn2+, Sb3+, Bi3+, and Te4+, etc.) transition metals(i.e., Cu+, Zn2+, Ag+, etc.) and rare-earth metals. Among them, organic-inorganic hybrid Cu-based halides have some advantages such as low cost, simple synthesis methods, rich structures and luminescent properties, and high stability, making them effective materials to replace conventional high-efficiency organic–inorganic Pb-based halides, gradually attracting much attention.This review summarizes the different synthesis methods, structures, optical properties, and practical applications of organic-inorganic hybrid copper-based halides in fields such as white LED lighting, X-ray imaging, near-infrared night vision imaging, and anti-counterfeiting. Organic-inorganic hybrid Cu-based halides are simple to be synthesized by some methods such as solvent evaporation, hydrothermal synthesis, cooling crystallization, anti-solvent diffusion, as well as more convenient methods like grinding and ultrasonication. Different structures can be obtained via simply changing the reaction conditions during synthesis, giving organic–inorganic hybrid Cu-based halides a significant advantage in synthesis. Organic–inorganic hybrid Cu-based halides are composed of independent organic cations and metal halide anions, with Cu exhibiting multiple coordination configurations and capable of forming various anionic structures with halide ions(i.e., Cl~-, Br~-, and I~-). Common low-dimensional(0D, 1D, and 2D)organic–inorganic hybrid Cu-based halides feature Cu in the inorganic part coordinated with halide ions in two-, three-, or four-coordination numbers. After halide coordination, various units are formed, such as linear(CuX2)~-, triangular(CuX3)2-, and tetrahedral(CuX4)3-units. These units are further connected via sharing vertices, edges, or faces, and are periodically embedded into the organic matrix. They can combine with different types of organic cations to form diverse structures, resulting in richer and more tunable luminescent properties.Organic–inorganic hybrid Cu-based halides possess a variety of luminescence mechanisms, such as self-trapped state emission,cluster emission, metal or halogen to organic ligand charge transfer, halogen to metal charge transfer, and d~9s1→d10 transitions of the metal center(MC). The complex luminescence mechanisms endow organic-inorganic hybrid Cu-based halides with fascinating optical properties, characterized by broad-band emission, large Stokes shifts, long lifetimes, and emission colors ranging from blue light to near-infrared. This review discusses the characteristics of different luminescence mechanisms and provides a detailed analysis of the effects of dimensional structures, types and sizes of organic cations, types of inorganic anions, types of halogens, crystal orientations, and solvent responses on the luminescent properties of organic-inorganic hybrid Cu-based halide single crystals.Subsequently, the applications of organic–inorganic hybrid Cu-based halides are studied. Organic-inorganic hybrid Cu-based halides can be applied in numerous fields like WLEDs, X-ray imaging, near-infrared night vision imaging, and anti-counterfeiting due to their low-cost synthesis, processability via solution methods, diverse structures, and tunable optical properties.Summary and prospects Although a significant progress is made in the research on material design and luminescent properties of organic–inorganic hybrid Cu-based halides, there are still some issues with organic–inorganic hybrid Cu-based halides that need to be addressed. This review proposes some directions for future in-depth research. First, in future explorations of organic–inorganic hybrid Cu-based halides, it is recommended for high-performance and widely applicable organic-inorganic hybrid Cu-based halides to design structures and synthesize the related materials with specific performance targets. Second, a deeper exploration of the luminescence mechanisms of organic-inorganic hybrid Cu-based halides is needed. Currently, the luminescence mechanisms of organic-inorganic hybrid Cu-based halides are complex and diverse. Previous reports have not clearly clarified the mechanisms of metal-to-organic ligand charge transfer and halogen-to-organic ligand charge transfer luminescence. Future studies can conduct more in-depth discussions in this area. Then, a research on organic–inorganic hybrid Cu-based halide glasses should be increased. These glasses have rich luminescent properties, but the existing research is limited. A future work can enrich studies in the field of organic–inorganic hybrid Cu-based halide glasses. In addition, conventional films of organic–inorganic hybrid Cu-based halides used for X-ray imaging face some problems such as particle aggregation and low transparency, restricting their practical application to some extent. Glass materials with high optical transparency and processability can be made into transparent scintillator materials,which are crucial for achieving high-resolution X-ray imaging. Finally, the applications of organic–inorganic hybrid Cu-based halides should be expanded. Their practical applications should be enriched in fields such as WLEDs, X-ray imaging, near-infrared night vision imaging, and anti-counterfeiting. For white WLEDs and X-ray imaging, exploring the value of practical applications requires the development of novel systems. For near-infrared night vision imaging, there are currently few reports of organic-inorganic hybrid Cu-based halides with near-infrared luminescence. In the future, more near-infrared luminescent materials can be explored to obtain near-infrared night vision imaging materials with the excellent performance.
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基本信息:
DOI：10.14062/j.issn.0454-5648.20250955
中图分类号:TQ422
引用信息:
[1]李微,魏忆,廖寒蕊,等.有机-无机杂化Cu基卤化物发光材料的结构、发光和应用研究进展[J].硅酸盐学报,2026,54(09):3108-3122.DOI:10.14062/j.issn.0454-5648.20250955.
基金信息:
国家自然科学基金（12374386,52402207,U25A20235）; 中国博士后科学基金（2024M753024,GZC20241594）; 湖北省博士后项目（2024HBBHJD098）; 湖北省国际科技合作项目（2025EHA058）; 深圳市科学技术创新委员会（JCYJ20240813114017022,JCYJ20250604183427037）
2026-08-18
2026-08-18
2026-08-18