Ping Wu , Ashutosh Agarwal , Hasanthi L. Senevirathna , Shunnian Wu , Cheng-Fu Yang
{"title":"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","authors":"Ping Wu , Ashutosh Agarwal , Hasanthi L. Senevirathna , Shunnian Wu , Cheng-Fu Yang","doi":"10.1016/j.calphad.2024.102740","DOIUrl":null,"url":null,"abstract":"<div><p>This paper introduces an innovative theory for customizing photoluminescence (PL) emission wavelengths in rare earth ion (Eu<sup>2+)</sup> 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 SiO<sub>4</sub> ligand within these materials. Using FactSage, we computationally calculate the fusion entropy of congruent silicates in the CaO-MgO-SiO<sub>2</sub> 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 MgSiO<sub>3</sub>, whose solid-liquid decomposition temperature is close to its melting point. Furthermore, the non-ideal liquid phase entropy of incongruent silicates positioned between congruent CaMgSi<sub>2</sub>O<sub>6</sub> (Pyroxene) and congruent Ca<sub>2</sub>MgSi<sub>2</sub>O<sub>7</sub> (Akermanite) in the MgO-CaO-SiO<sub>2</sub> 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.</p></div>","PeriodicalId":9436,"journal":{"name":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A novel photoluminescence theory and design rule based on solution entropy for rare earth ion doped alkaline metal silicates\",\"authors\":\"Ping Wu , Ashutosh Agarwal , Hasanthi L. Senevirathna , Shunnian Wu , Cheng-Fu Yang\",\"doi\":\"10.1016/j.calphad.2024.102740\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>This paper introduces an innovative theory for customizing photoluminescence (PL) emission wavelengths in rare earth ion (Eu<sup>2+)</sup> 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 SiO<sub>4</sub> ligand within these materials. Using FactSage, we computationally calculate the fusion entropy of congruent silicates in the CaO-MgO-SiO<sub>2</sub> 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 MgSiO<sub>3</sub>, whose solid-liquid decomposition temperature is close to its melting point. Furthermore, the non-ideal liquid phase entropy of incongruent silicates positioned between congruent CaMgSi<sub>2</sub>O<sub>6</sub> (Pyroxene) and congruent Ca<sub>2</sub>MgSi<sub>2</sub>O<sub>7</sub> (Akermanite) in the MgO-CaO-SiO<sub>2</sub> 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.</p></div>\",\"PeriodicalId\":9436,\"journal\":{\"name\":\"Calphad-computer Coupling of Phase Diagrams and Thermochemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2024-09-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Calphad-computer Coupling of Phase Diagrams and Thermochemistry\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0364591624000828\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Calphad-computer Coupling of Phase Diagrams and Thermochemistry","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0364591624000828","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
A novel photoluminescence theory and design rule based on solution entropy for rare earth ion doped alkaline metal silicates
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.
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.