Enhanced red emission in germanate glass-ceramics via controlled crystallization of Mn⁴⁺:K2Ge4O9 crystals with isolated [GeO6] octahedra

IF 6.2 2区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of The European Ceramic Society Pub Date : 2025-08-27 DOI:10.1016/j.jeurceramsoc.2025.117778

Kai Chang , Jingyuan Liao , Zhaodong Zhang , Lingwei Zeng , Hong He , Guannan Li , Chunmei Li , Hua Lin , Jing Liu , Jianfeng Tang

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引用次数: 0

Abstract

Mn⁴⁺-activated luminescent materials are highly valued for their intense red emission. This study explores Mn⁴⁺-activated germanate glass-ceramics (GCs) made by in situ crystallization of a germanate parent glass. Controlled heat treatment enabled the sequential precipitation of two crystalline phases: Mn⁴⁺:K₄Ge₉O₂₀ (K4) and Mn⁴⁺:K₂Ge₄O₉ (K2). Mn⁴⁺ ions favor six-fold coordinated Ge⁴⁺ sites in these phases. The isolated trigonal-distorted [GeO₆] octahedra in K2 enhance the ²E → ⁴A₂ emission intensity ten-fold compared to K4. Theoretical calculations indicate that Mn⁴⁺ ions incorporation strengthens metal-ligand interaction and introduce new d-electron-related defect states within the forbidden band. The Mn⁴⁺:K2-embedded GC sample with 0.1 mol% Mn⁴⁺ nominal concentration achieves optimal luminescence performance. It exhibits superior thermal stability compared to the Mn⁴⁺:K2 phosphor synthesized by solid-state reaction. These findings demonstrate the potential of Mn⁴⁺:K2-embedded germanate GC as an excellent red-emitting component for white LEDs, which can enhance indoor lighting quality by improving color rendering performance.

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通过具有分离的[GeO6]八面体的Mn⁴+:K2Ge4O9晶体的控制结晶，增强了锗酸盐玻璃陶瓷中的红色发射

Mn4+激活的发光材料因其强烈的红光发射而受到重视。本研究通过原位结晶法制备了Mn4+活化的锗酸盐微晶玻璃（GCs）。控制热处理使两种晶相Mn4+:K4Ge9O20 （K4）和Mn4+:K2Ge4O9 （K2）有序析出。在这些相中，Mn4+离子有利于六倍配位的Ge4+位点。与K4相比，K2中孤立的三角畸变[GeO6]八面体的2E→4A2发射强度增强了10倍。理论计算表明，Mn4+离子的掺入增强了金属与配体的相互作用，并在禁带内引入了新的与d电子相关的缺陷态。以0.1 mol% Mn4+标称浓度为Mn4+: k2包埋的GC样品具有最佳的发光性能。与固相反应合成的Mn4+:K2荧光粉相比，它具有更好的热稳定性。这些发现证明了Mn4+: k2嵌入锗酸盐GC作为白光led的优秀红发组件的潜力，它可以通过改善显色性能来提高室内照明质量。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of The European Ceramic Society 工程技术-材料科学：硅酸盐

CiteScore

10.70

自引率

12.30%

发文量

863

审稿时长

35 days

期刊介绍： The Journal of the European Ceramic Society publishes the results of original research and reviews relating to ceramic materials. Papers of either an experimental or theoretical character will be welcomed on a fully international basis. The emphasis is on novel generic science concerning the relationships between processing, microstructure and properties of polycrystalline ceramics consolidated at high temperature. Papers may relate to any of the conventional categories of ceramic: structural, functional, traditional or composite. The central objective is to sustain a high standard of research quality by means of appropriate reviewing procedures.