LAUSR

Efficient white-light emitting single-material sources are ideal for sustainable lighting applications. Though layered hybrid lead-halide perovskite materials have demonstrated attractive broadband white-light emission properties, they pose a serious long-term environmental and health risk as they contain lead (Pb2+) and are readily soluble in water. Recently, lead-free halide double perovskite (HDP) materials with a generic formula A(I)2B'(III)B''(I)X6 (where A and B are cations and X is a halide ion) have demonstrated white-light emission with improved photolumi-nescence quantum yields (PLQYs). Here, we present a series of Bi3+/In3+ mixed-cationic Cs2Bi1-xInxAgCl6 HDP solid solutions that span the indirect to direct bandgap modification which exhibit tailorable optical properties. Density function theory (DFT) calculations indicate an indirect-direct bandgap crossover composition when x > 0.50. These HDP materials emit over the entire visible light spectrum, centered at 600 ± 30 nm with full-width at half maxima ca. 200 nm upon ultraviolet light excitation and a maximum PLQY of 34 ± 4% for Cs2Bi0.085In0.915AgCl6. Short-range structural insight for these materials is crucial to unravel the unique atomic-level structural properties which are difficult to distinguish by diffraction-based techniques. Hence, we demonstrate the advantage of using solid-state nuclear magnetic resonance (NMR) spectroscopy to deconvolute the local structural environments of these mixed-cationic HDPs. Using ultrahigh field (21.14 T) NMR spectroscopy of quadrupolar nuclei (115In, 133Cs, and 209Bi), we show that there is a high degree of atomic-level B'(III)/B''(I) site ordering (i.e., no evidence of antisite defects). Furthermore, a combination of XRD, NMR and DFT calculations were used to unravel the complete atomic-level random Bi3+/In3+ cationic mixing in Cs2Bi1-xInxAgCl6 HDPs. Briefly, this work provides an advance in understanding the photophysical properties that correlate long- to short-range structural elucidation of these newly developed solid-state white-light emitting HDP materials.