Zero-Dimensional Lead-Free Halide with Indirect Optical Gap and Enhanced Photoluminescence by Sb Doping

Three new lead-free organic-inorganic metal halides (OIMHs) (C₇H₈N₃)₃InX₆·H₂O (X = Cl, Br) and (C₇H₈N₃)₂SbBr₅ were synthesized. First-principles calculations indicate that the highest occupied molecular orbitals (HOMOs) of the two In-based OIMHs are constituted of π orbitals from [C₇H₈N₃]⁺ spacers. (C₇H₈N₃)₃InX₆·H₂O (X = Cl, Br) shows an indirect optical gap, which may result from this organic-contributed band edge. Despite the indirect-gap nature with extra phonon process during absorption, the photoluminescence of (C₇H₈N₃)₃InBr₆·H₂O can still be significantly enhanced through Sb doping, with the internal photoluminescence quantum yields (PLQY) increased 10-fold from 5% to 52%. A white light-emitting diode (WLED) was fabricated based on (C₇H₈N₃)₃InBr₆·H₂O:Sb³⁺, exhibiting a high color-rendering index of 90. Our work provides new systems to deeply understand the principles for organic spacer choice to obtain the 0D metal OIMHs with specific band structure and also the significant enhancement of luminescence performance by chemical doping.