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小斯托克斯位移诱导的高效且热稳定的宽带近红外锑酸盐双钙钛矿发光体用于光谱学应用

Small Stokes Shift Induced Highly Efficient and Thermally Stable Broadband Near-Infrared Antimonite Double Perovskite Emitters for Spectroscopy Applications.

作者信息

Zhou Zhihao, Jiang Hongjun, Yin Bozhao, Ji Guocheng, Song Enhai, Qiu Jianrong, Yang Zhongmin, Dong Guoping

机构信息

State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques, School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, China.

School of Optoelectronic Engineering, Guangdong Polytechnic Normal University, Guangzhou, 510665, China.

出版信息

Adv Sci (Weinh). 2025 Jul 12:e09583. doi: 10.1002/advs.202509583.

Abstract

The exploration of efficient broadband portable near-infrared (NIR) light sources is crucial for next-generation NIR spectroscopy-based technologies. However, developing thermally stable and highly efficient NIR photonic materials exceeding 830 nm is met with limited success. Here, a series of broadband NIR phosphors with long-wavelength emission (λ > 830 nm) is designed by incorporating activator Cr ions into ALaMgSbO (A = Ca, Sr) double perovskite matrices. Specifically, a cation site substitution strategy is proposed to reduce the Stokes shift of ALaMgSbO:Cr (A = Ca, Sr), rendering these as-prepared NIR phosphors possess excellent thermal resistance performance (89.80%@423 K) and high quantum efficiency (82.5%) simultaneously. Structural analyses, DFT calculations, and spectroscopy measurements revealed that Cr ions can occupy both [SbO] and [MgO] polyhedral sites but prefer to replace Sb ions in ALaMgSbO (A = Ca, Sr). The luminescence efficiency and thermal stability of the samples are further improved through a flux strategy, and the emission spectra are effectively broadened by the introduction of Yb as an extra NIR emitter. Furthermore, the designed phosphors exhibit a full visible-spectrum conversion ability from 400 to 800 nm, showing great promise for versatile NIR spectroscopy applications in solar energy harvesting, night vision, non-destructive visualization, and dental analysis.

摘要

探索高效宽带便携式近红外(NIR)光源对于基于下一代近红外光谱的技术至关重要。然而,开发热稳定且高效的波长超过830 nm的近红外光子材料取得的成功有限。在此,通过将激活剂Cr离子掺入ALaMgSbO(A = Ca,Sr)双钙钛矿基质中,设计了一系列具有长波长发射(λ> 830 nm)的宽带近红外磷光体。具体而言,提出了一种阳离子位点取代策略以降低ALaMgSbO:Cr(A = Ca,Sr)的斯托克斯位移,使这些制备的近红外磷光体同时具有优异的耐热性能(423 K时为89.80%)和高量子效率(82.5%)。结构分析、密度泛函理论计算和光谱测量表明,Cr离子可以占据[ SbO ]和[ MgO ]多面体位点,但更倾向于取代ALaMgSbO(A = Ca,Sr)中的Sb离子。通过助熔剂策略进一步提高了样品的发光效率和热稳定性,并且通过引入Yb作为额外的近红外发射体有效地拓宽了发射光谱。此外,所设计的磷光体在400至800 nm范围内表现出全可见光谱转换能力,在太阳能收集、夜视、无损可视化和牙科分析等多功能近红外光谱应用中显示出巨大潜力。

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