A-site coordinating cation engineering in zero-dimensional antimony halide perovskites for strong self-trapped exciton emission

Low-dimensional hybrid halide perovskites represent a promising class of materials in optoelectronic applications because of strong broad self-trapped exciton (STE) emissions. However, there exists a limitation in designing the ideal A-site cation that makes the material satisfy the structure tolerance and exhibit STE emission raised by the appropriate electron-phonon coupling effect. To overcome this dilemma, we developed an inorganic metal-organic dimethyl sulfoxide (DMSO) coordinating strategy to synthesize a series of zero-dimensional (0D) Sb-based halide perovskites including Na3SbBr6 & BULL;DMSO6 (1), AlSbBr6 & BULL;DMSO6 (2), AlSbCl6 & BULL;DMSO6 (3), GaSbCl6 & BULL;DMSO6 (4), Mn2Sb2Br10 & BULL;DMSO13 (5) and MgSbBr5 & BULL;DMSO7 (6), in which the distinctive coordinating A-site cation [A(m)-DMSO6](n+) efficiently separate the [SbXz] polyhedrons. Advantageously, these materials all exhibit broadband-emissions with full widths at half maxima (FWHM) of 95-184 nm, and the highest photoluminescent quantum yield (PLQY) of 3 reaches 92%. Notably, compounds 2-4 are able to remain stable after storage of more than 120 d. First-principles calculations indicate that the origin of the efficient STE emission can be attributed to the localized distortion in [SbXz] polyhedron upon optical excitation. Experimental and calculational results demonstrate that the proposed coordinating strategy provides a way to efficiently expand the variety of novel high-performance STE emitters and continuously regulate their emission behaviors.

Automated summary

A series of zero-dimensional (0D) Sb-based halide perovskites were synthesized using an inorganic metal-organic dimethyl sulfoxide (DMSO) coordinating strategy, which exhibit broadband emissions and high photoluminescent quantum yields. These materials also remained stable after storage for more than 120 days. Experimental and calculational results demonstrate that the proposed coordinating strategy provides a way to efficiently expand the variety of novel high-performance self-trapped exciton (STE) emitters and continuously regulate their emission behaviors.