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无稀有金属的超宽带近红外磷光体

Rare-Metal-Free Ultrabroadband Near-Infrared Phosphors.

作者信息

Zheng Guojun, Lou Chenjie, Yuan Zeyue, Xiao Wenge, Shang Longbing, Zhong Jiyou, Tang Mingxue, Qiu Jianrong

机构信息

Institute of Light+X Science and Technology, College of Information Science and Engineering, Ningbo University, Ningbo, 315211, China.

College of Optical Science and Engineering, Zhejiang University, Hangzhou, 310027, China.

出版信息

Adv Mater. 2025 Jan;37(4):e2415791. doi: 10.1002/adma.202415791. Epub 2024 Dec 1.

Abstract

Trivalent chromium (Cr) is an attractive near-infrared (NIR) emitter, but its ultrabroadband NIR emission is limited to host crystals containing large amounts of rare-metal elements and usually suffers from low internal quantum efficiency (IQE) and poor thermal stability. Here, a class of high-performance, rare-metal-free ultrabroadband NIR phosphors, are reported by revealing that weak-field Cr centers featuring broadband NIR emission with near-unity IQEs are intrinsic, though in trace quantities, to Cr doped MgAlO spinel (MAS) and its derivatives well-known for their narrowband far-red emission. It is shown that such weak-field Cr centers stem from cation inversion ubiquitous in spinel compounds, and their quantity can be increased simply by superstoichiometric AlO/GaO. Then SiO is introduced into AlO-excess MAS to break the inversion symmetry of Cr centers for greatly improving the probabilities of their otherwise parity-forbidden 3d-3d transitions. The as-fabricated phosphor-converted light-emitting diodes are capable of emitting ultrabroadband NIR light with high photoelectric efficiency (16.0%) and optical power (180.8 mW), and excellent spectral stability, which apparently outperforms existing state-of-the-art devices.

摘要

三价铬(Cr)是一种引人注目的近红外(NIR)发射体,但其超宽带近红外发射仅限于含有大量稀有金属元素的基质晶体,并且通常存在内部量子效率(IQE)低和热稳定性差的问题。在此,通过揭示具有近单位IQE的宽带近红外发射的弱场Cr中心虽然数量稀少,但对于以窄带远红发射而闻名的Cr掺杂MgAlO尖晶石(MAS)及其衍生物而言是固有的,报道了一类高性能、无稀有金属的超宽带近红外荧光粉。结果表明,这种弱场Cr中心源于尖晶石化合物中普遍存在的阳离子反转,并且其数量可以通过超化学计量的AlO/GaO简单地增加。然后将SiO引入过量AlO的MAS中,以打破Cr中心的反转对称性,从而大大提高其原本禁戒的3d-3d跃迁的概率。所制备的荧光粉转换发光二极管能够发射具有高光电效率(16.0%)和光功率(180.8 mW)以及优异光谱稳定性的超宽带近红外光,这明显优于现有的最先进器件。

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