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

Abstract

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·DMSO₆ (1), AlSbBr₆·DMSO₆ (2), AlSbCl₆·DMSO₆ (3), GaSbCl₆·DMSO₆ (4), Mn₂Sb₂Br₁₀·DMSO₁₃ (5) and MgSbBr₅·DMSO₇ (6), in which the distinctive coordinating A-site cation [A_m-DMSO₆]ⁿ⁺ efficiently separate the [SbX_z] 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 [SbX_z] 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.

Keywords

A-site cation / antimony-based perovskites / metal-DMSO coordination / self-trapped excitons

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