A novel photoluminescence theory and design rule based on solution entropy for rare earth ion doped alkaline metal silicates

IF 1.9 3区材料科学 Q4 CHEMISTRY, PHYSICAL

Calphad-computer Coupling of Phase Diagrams and Thermochemistry Pub Date : 2024-09-10 DOI:10.1016/j.calphad.2024.102740

Ping Wu , Ashutosh Agarwal , Hasanthi L. Senevirathna , Shunnian Wu , Cheng-Fu Yang

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引用次数: 0

Abstract

This paper introduces an innovative theory for customizing photoluminescence (PL) emission wavelengths in rare earth ion (Eu²⁺⁾ doped alkaline earth metals (Ca, Mg) silicates, rooted in the entropy of fusion and configurational entropy of congruent and incongruent silicates, respectively, aiming to reveal dynamic deformation of the tetrahedral SiO₄ ligand within these materials. Using FactSage, we computationally calculate the fusion entropy of congruent silicates in the CaO-MgO-SiO₂ system. Synthesized ternary silicates confirm our theory by highlighting correlations between lower/higher fusion entropy (for congruent) and configurational entropy (for incongruent) silicates, leading to red/blue shifts in PL emission wavelengths. In binary silicate systems, we observe an inverse correlation between PL emission wavelengths and fusion entropy of congruent silicates or pseudo-congruent silicates like MgSiO₃, whose solid-liquid decomposition temperature is close to its melting point. Furthermore, the non-ideal liquid phase entropy of incongruent silicates positioned between congruent CaMgSi₂O₆ (Pyroxene) and congruent Ca₂MgSi₂O₇ (Akermanite) in the MgO-CaO-SiO₂ ternary phase diagram comprehensively explains diverse PL emission wavelengths. Beyond its scholarly impact, this work expands perspectives in lighting and photonic research, opening an exciting frontier in entropy-lighting research and enabling predictions of host chemical composition and tunable PL emission wavelengths, particularly relevant to LED technologies.

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基于稀土离子掺杂碱金属硅酸盐溶液熵的新型光致发光理论和设计规则

本文介绍了一种用于定制稀土离子（Eu2+）掺杂碱土金属（钙、镁）硅酸盐光致发光（PL）发射波长的创新理论，该理论分别植根于同位硅酸盐和非同位硅酸盐的融合熵和构型熵，旨在揭示这些材料中四面体 SiO4 配体的动态变形。我们利用 FactSage 计算了 CaO-MgO-SiO2 体系中同位硅酸盐的熔融熵。合成的三元硅酸盐证实了我们的理论，突出了较低/较高熔融熵（同相）和构型熵（不相容）之间的相关性，从而导致聚光辐射波长的红/蓝偏移。在二元硅酸盐体系中，我们观察到聚光辐射波长与同熔硅酸盐或假同熔硅酸盐（如 MgSiO3）的熔融熵之间存在反相关关系，后者的固液分解温度接近其熔点。此外，在 MgO-CaO-SiO2 三元相图中，位于全等 CaMgSi2O6（辉石）和全等 Ca2MgSi2O7（赤铁矿）之间的非全等硅酸盐的非理想液相熵全面解释了不同的聚光辐射波长。除了学术影响之外，这项工作还拓展了照明和光子研究的视野，为熵照明研究开辟了令人兴奋的前沿领域，并实现了对宿主化学成分和可调聚光辐射波长的预测，特别是与 LED 技术相关的预测。

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

Calphad-computer Coupling of Phase Diagrams and Thermochemistry 化学-热力学

CiteScore

4.00

自引率

16.70%

发文量

审稿时长

2.5 months

期刊介绍： The design of industrial processes requires reliable thermodynamic data. CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) aims to promote computational thermodynamics through development of models to represent thermodynamic properties for various phases which permit prediction of properties of multicomponent systems from those of binary and ternary subsystems, critical assessment of data and their incorporation into self-consistent databases, development of software to optimize and derive thermodynamic parameters and the development and use of databanks for calculations to improve understanding of various industrial and technological processes. This work is disseminated through the CALPHAD journal and its annual conference.