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铕掺杂氮氧化镁磷酸盐BaSr[MgPN] : Eu(x = 0 - 3)的可调谐窄带蓝光发射

Tunable Narrow-Band Cyan-Emission of Eu-doped Nitridomagnesophosphates BaSr[MgPN] : Eu (x=0-3).

作者信息

Pritzl Reinhard M, Pointner Monika M, Witthaut Kristian, Strobel Philipp, Schmidt Peter J, Schnick Wolfgang

机构信息

Department of Chemistry, University of Munich (LMU), Butenandtstraße 5-13, 81377, Munich, Germany.

Lumileds Phosphor Center Aachen (LPCA), Lumileds (Germany) GmbH, Philipsstraße 8, 52068, Aachen, Germany.

出版信息

Angew Chem Int Ed Engl. 2024 Jun 3;63(23):e202403648. doi: 10.1002/anie.202403648. Epub 2024 May 2.

Abstract

Tetrahedron-based nitrides offer a wide range of properties and applications. Highly condensed nitridophosphates are examples of nitrides that exhibit fascinating luminescence properties when doped with Eu, making them appealing for industrial applications. Here, we present the first nitridomagnesophosphate solid solution series BaSr[MgPN] : Eu (x=0-3), synthesized by a high-pressure high-temperature approach using the multianvil technique (3 GPa, 1400 °C). Starting from the binary nitrides PN and MgN and the respective alkaline earth azides, we incorporate Mg into the P/N framework to increase the degree of condensation κ to 0.6, the highest observed value for alkaline earth nitridophosphates. The crystal structure was elucidated by single-crystal X-ray diffraction, powder X-ray diffraction, energy-dispersive X-ray spectroscopy (EDX), and solid-state NMR. DFT calculations were performed on the title compounds and other related highly condensed nitridophosphates to investigate the influence of Mg in the P/N network. Eu-doped samples of the solid solution series show a tunable narrow-band emission from cyan to green (492-515 nm), which is attributed to the preferred doping of a single crystallographic site. Experimental confirmation of this assumption was provided by overdoping experiments and STEM-HAADF studies on the series as well on the stoichiometric compound BaEu[MgPN] with additional atomic resolution energy-dispersive X-ray spectroscopy (EDX) mapping.

摘要

基于四面体的氮化物具有广泛的性质和应用。高度缩合的氮代磷酸盐是氮化物的例子,当掺杂Eu时,它们表现出迷人的发光特性,这使得它们在工业应用中具有吸引力。在这里,我们展示了第一个氮代镁磷酸盐固溶体系列BaSr[MgPN] : Eu (x = 0 - 3),它是通过使用多砧技术(3 GPa,1400 °C)的高温高压方法合成的。从二元氮化物PN和MgN以及各自的碱土金属叠氮化物开始,我们将Mg掺入P/N框架中,以将缩合度κ提高到0.6,这是碱土金属氮代磷酸盐中观察到的最高值。通过单晶X射线衍射、粉末X射线衍射、能量色散X射线光谱(EDX)和固态NMR阐明了晶体结构。对标题化合物和其他相关的高度缩合氮代磷酸盐进行了DFT计算,以研究Mg在P/N网络中的影响。固溶体系列的Eu掺杂样品显示出从青色到绿色(492 - 515 nm)的可调谐窄带发射,这归因于单个晶体学位置的优先掺杂。通过对该系列以及化学计量化合物BaEu[MgPN]的过掺杂实验和STEM-HAADF研究以及额外的原子分辨率能量色散X射线光谱(EDX)映射,提供了这一假设的实验证实。

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