Herein, a new family of hybrid metal halides, (DMAP)2MBr4(M = Cu, Zn), featuring zero‐dimensional (0D), pseudo‐layered crystal structures containing isolated molecular 4‐dimethylaminopyridinium (DMAP, C7H11N2+) cations and MBr42−tetrahedral anions are reported. (DMAP)2MBr4show remarkable long‐term stability, with no signs of degradation after one year of ambient air exposure. The reported solution synthesis affords large crystals measuring up to 1 cm, which showed significant response to soft 8 keV X‐ray photons when implemented into X‐ray detectors. Furthermore, (DMAP)2ZnBr4demonstrates tunable color light emission properties, which is attributed to the organic molecular units based on our combined experimental and computational results. The measured photoluminescence quantum yield (PLQY) for (DMAP)2ZnBr4is 7.35 %, a remarkable enhancement of emission efficiency as compared to a weak emission from the organic precursor. The inexpensive and earth‐abundant chemical compositions and ease of preparation of the new hybrid metal halides make them promising candidates for optical and electronic applications.
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Abstract Copper(I) halides are emerging as attractive alternatives to lead halide perovskites for optical and electronic applications. However, blue‐emitting all‐inorganic copper(I) halides suffer from poor stability and lack of tunability of their photoluminescence (PL) properties. Here, the preparation of silver(I) halides A2AgX3(A = Rb, Cs; X = Cl, Br, I) through solid‐state synthesis is reported. In contrast to the Cu(I) analogs, A2AgX3are broad‐band emitters sensitive to A and X site substitutions. First‐principle calculations show that defect‐bound excitons are responsible for the observed main PL peaks in Rb2AgX3and that self‐trapped excitons (STEs) contribute to a minor PL peak in Rb2AgBr3. This is in sharp contrast to Rb2CuX3, in which the PL is dominated by the emission by STEs. Moreover, the replacement of Cu(I) with Ag(I) in A2AgX3significantly improves photostability and stability in the air under ambient conditions, which enables their consideration for practical applications. Thus, luminescent inks based on A2AgX3are prepared and successfully used in anti‐counterfeiting applications. The excellent light emission properties, significantly improved stability, simple preparation method, and tunable light emission properties demonstrated by A2AgX3suggest that silver(I) halides may be attractive alternatives to toxic lead halide perovskites and unstable copper(I) halides for optical applications.
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All‐inorganic copper(I) halides have recently emerged as attractive alternatives to lead‐based halide perovskites and rare‐earth‐doped inorganics for light emission applications. Most of the newly discovered all‐inorganic Cu(I) halides demonstrate high‐efficiency blue emission albeit with unusually poor tunability of photoluminescence (PL) properties. This work reports the facile preparation of three new copper(I) halides based on the guanidinium cation: (CN3H6)3CuCl4, (CN3H6)7Cu3Br10·3(C3H7NO), and (CN3H6)7Cu3I10·3(C3H7NO). A comprehensive characterization of PL is presented for these novel materials, which have highly tunable, dual blue–yellow emission responsive to both excitation wavelength and vacuum annealing. These have remarkable photoluminescence quantum yield (PLQY) values of up to 34.6% and color‐rendering indices (CRI) up to 97% for tunable, single‐phase white light emission with correlated color temperatures (CCT) ranging from 4851 to 18 921 K, demonstrating the excellent potential of Cu(I) halides for light emission applications.