Efficient Solar Spectrum‐Like White‐Light Emission in Zinc‐Based Zero‐Dimensional Hybrid Metal Halides

Abstract

Organic–inorganic metal halides (OIMHs) with high‐efficiency solar spectrum‐like emission are attracting broad and current interest. Here, five 0D Zn‐based hybrid halides are synthesized based on aromatic organic cations with different carbon‐chain lengths: C6H5CH2NH3+ (PMA+) and C6H5(CH2)4NH3+ (PBA+). (PMA)2ZnCl4 exhibits the highest photoluminescence quantum yield of 37.2% of reported Zn‐based white‐emission OIMHs. The emission spectrum of (PBA)2ZnI4 indicates a color rendering index of 98, which is the highest among single‐component white‐light‐emitting phosphors. Spectral characterizations and density functional theory calculations demonstrate that the extremely broad emission of (PBA)2ZnI4 originates from the synergistic emission of organic cations and self‐trapped excitons. The optical properties of the obtained (PMA)2ZnBr4, (PMA)2ZnI4·H2O, and (PBA)2ZnCl4 are also characterized for comparison, and with the same organic cations, the PLQY decreases from chloride to bromide to iodide. This work demonstrates that the selection of appropriate organics and halogens can enable fine tuning of single‐component white‐light emission, satisfying varying needs for solid‐state lighting.

Fine-Tuning Optoelectronic Features in Organic–Inorganic Hybrid Metal Halides: A Focus on the Phenylbutanammonium Series

“…To demonstrate the luminescence of (PBA) 2 SnCl 6 (Table S11), we conducted fluorescence spectrum measurement of PBACl, and the fluorescence spectra were exactly the same (Figure S7), ,, confirming that its luminescence originates from the organic cations, which is consistent with our previous observations in (PBA) 2 ZnCl 4 and (PBA) 2 MnCl 4 . , The fluorescence spectrum of (PBA) 2 SnBr 4 exhibits weak intensity, with a peak resembling that of the previously reported (PEA) 2 SnBr 4 (Table S12). Furthermore, the sample was subjected to time-resolved fluorescence spectroscopy measurements, followed by analysis of the fluorescence decay curve data, indicating that this compound demonstrates a prolonged lifetime in the microsecond level ( τ = 0.5 μs), which is in line with the observed PL features of STEs (Figure S8), as weak exciton binding decreases the number of STEs, leading to a higher nonradiative recombination rate (Figure b).…”

“…This phenomenon is caused by the conversion from [MnBr 4 (H 2 O) 2 ] 2− to [MnBr 4 ] 2− , indicating that [MnBr 4 ] 2− is more stable at low temperatures (Figure 4b). 23,24 To demonstrate the luminescence of (PBA) 2 SnCl 6 (Table S11), we conducted fluorescence spectrum measurement of PBACl, and the fluorescence spectra were exactly the same (Figure S7), 7,8,25 confirming that its luminescence originates from the organic cations, which is consistent with our previous observations in (PBA) 2 ZnCl 4 and (PBA) 2 MnCl 4 . 7,8 The fluorescence spectrum of (PBA) 2 SnBr 4 exhibits weak intensity, with a peak resembling that of the previously reported (PEA) 2 SnBr 4 (Table S12).…”

“…10 (PBA) 2 ZnCl 4 displays a high photoluminescence quantum yield (PLQY) of 14.2%. 8 The emission spectrum of (PBA) 2 ZnI 4 combines the organic and STE emissions resulting in a color rendering index of 98, the highest among singlecomponent white-light-emitting phosphors. 8 This outstanding property expands potential applications in solid-state lighting.…”

“…Remarkably, (PBA) 4 BiI 7 ·H 2 O exhibits a second-harmonic-generation (SHG) response in the infrared region, approximately 1.3 times that of AgGaS 2 , making it a promising candidate for laser conversion . (PBA) 2 ZnCl 4 displays a high photoluminescence quantum yield (PLQY) of 14.2% . The emission spectrum of (PBA) 2 ZnI 4 combines the organic and STE emissions resulting in a color rendering index of 98, the highest among single-component white-light-emitting phosphors .…”

Synthesis, Structure, and Optical Properties of a 0D Hybrid Organic–Inorganic Metal Halide (C5N2H14Cl)GeCl3

“…Meanwhile, the abundant structural diversity and favorable arrangement of both the organic and inorganic parts make the OIMHs attractive candidates for NLO applications. , All of these properties are closely related to their microstructures. Notably, OIMHs possess flexible structures varying from three-dimensional framework and two-dimensional layer to one-dimensional chain or zero-dimensional (0D) clusters, each of which has its own advantage. − Furthermore, for the wide selectivity of organic molecules, central cations, and halogen elements in the OIMHs, element substitutions are proven to be an efficient strategy in tuning their photoelectronic properties, which made lots of researchers pay their attention to the exploration of new materials and the studies of relationships between structures and properties. , …”