Mekhrdod S. Kurboniyon, Alok M. Srivastava, Bibo Lou, Dilshod D. Nematov, Amondulloi Burhonzoda, Tomoyuki Yamamoto, Chong-Geng Ma, Mikhail G. Brik
{"title":"Na2SiF6、NaKSiF6 和 K2SiF6 荧光中 Mn4+ 的热淬机制:第一原理分析的启示","authors":"Mekhrdod S. Kurboniyon, Alok M. Srivastava, Bibo Lou, Dilshod D. Nematov, Amondulloi Burhonzoda, Tomoyuki Yamamoto, Chong-Geng Ma, Mikhail G. Brik","doi":"10.1021/acs.inorgchem.4c03589","DOIUrl":null,"url":null,"abstract":"This study aims to identify the key factors governing the thermal quenching of Mn<sup>4+</sup> ion luminescence in fluoride-based phosphor materials used as red emitters in modern-day phosphor-converted LED devices. Here, we employ first-principles calculations for Mn<sup>4+</sup>-doped Na<sub>2</sub>SiF<sub>6</sub>, NaKSiF<sub>6</sub>, and K<sub>2</sub>SiF<sub>6</sub> hosts to explore how host properties and local coordination environments influence thermal quenching behavior. The ΔSCF method was used to model the geometric structures of the Mn<sup>4+4</sup>A<sub>2</sub> (ground) and <sup>2</sup>E, <sup>4</sup>T<sub>2</sub> (excited) states and the energies of the optical transitions between these states. Our results reveal that thermal quenching in Na<sub>2</sub>SiF<sub>6</sub> and K<sub>2</sub>SiF<sub>6</sub> phosphors occurs through thermally activated <sup>2</sup>E → <sup>4</sup>T<sub>2</sub> → <sup>4</sup>A<sub>2</sub> crossover. In contrast, thermal quenching in NaKSiF<sub>6</sub> is due to other nonradiative decay pathways. Investigations of the mechanical stability of these fluorides show that NaKSiF<sub>6</sub> is mechanically unstable. We suggest that this property of the host limits the luminescence efficiency of the embedded Mn<sup>4+</sup> ions. We also determined the reason for the difference in the intensity of the <sup>2</sup>E → <sup>4</sup>A<sub>2</sub> emission transition (ZPL) in the systems. These findings advance our fundamental understanding of the thermal quenching mechanism of Mn<sup>4+</sup> ion luminescence in fluorides, and the results can aid future discoveries of technologically useful phosphors through high-throughput design methodologies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3000,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Thermal Quenching Mechanism of Mn4+ in Na2SiF6, NaKSiF6, and K2SiF6 Phosphors: Insights from the First-Principles Analysis\",\"authors\":\"Mekhrdod S. Kurboniyon, Alok M. Srivastava, Bibo Lou, Dilshod D. Nematov, Amondulloi Burhonzoda, Tomoyuki Yamamoto, Chong-Geng Ma, Mikhail G. Brik\",\"doi\":\"10.1021/acs.inorgchem.4c03589\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"This study aims to identify the key factors governing the thermal quenching of Mn<sup>4+</sup> ion luminescence in fluoride-based phosphor materials used as red emitters in modern-day phosphor-converted LED devices. Here, we employ first-principles calculations for Mn<sup>4+</sup>-doped Na<sub>2</sub>SiF<sub>6</sub>, NaKSiF<sub>6</sub>, and K<sub>2</sub>SiF<sub>6</sub> hosts to explore how host properties and local coordination environments influence thermal quenching behavior. The ΔSCF method was used to model the geometric structures of the Mn<sup>4+4</sup>A<sub>2</sub> (ground) and <sup>2</sup>E, <sup>4</sup>T<sub>2</sub> (excited) states and the energies of the optical transitions between these states. Our results reveal that thermal quenching in Na<sub>2</sub>SiF<sub>6</sub> and K<sub>2</sub>SiF<sub>6</sub> phosphors occurs through thermally activated <sup>2</sup>E → <sup>4</sup>T<sub>2</sub> → <sup>4</sup>A<sub>2</sub> crossover. In contrast, thermal quenching in NaKSiF<sub>6</sub> is due to other nonradiative decay pathways. Investigations of the mechanical stability of these fluorides show that NaKSiF<sub>6</sub> is mechanically unstable. We suggest that this property of the host limits the luminescence efficiency of the embedded Mn<sup>4+</sup> ions. We also determined the reason for the difference in the intensity of the <sup>2</sup>E → <sup>4</sup>A<sub>2</sub> emission transition (ZPL) in the systems. These findings advance our fundamental understanding of the thermal quenching mechanism of Mn<sup>4+</sup> ion luminescence in fluorides, and the results can aid future discoveries of technologically useful phosphors through high-throughput design methodologies.\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-10-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.inorgchem.4c03589\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.4c03589","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Thermal Quenching Mechanism of Mn4+ in Na2SiF6, NaKSiF6, and K2SiF6 Phosphors: Insights from the First-Principles Analysis
This study aims to identify the key factors governing the thermal quenching of Mn4+ ion luminescence in fluoride-based phosphor materials used as red emitters in modern-day phosphor-converted LED devices. Here, we employ first-principles calculations for Mn4+-doped Na2SiF6, NaKSiF6, and K2SiF6 hosts to explore how host properties and local coordination environments influence thermal quenching behavior. The ΔSCF method was used to model the geometric structures of the Mn4+4A2 (ground) and 2E, 4T2 (excited) states and the energies of the optical transitions between these states. Our results reveal that thermal quenching in Na2SiF6 and K2SiF6 phosphors occurs through thermally activated 2E → 4T2 → 4A2 crossover. In contrast, thermal quenching in NaKSiF6 is due to other nonradiative decay pathways. Investigations of the mechanical stability of these fluorides show that NaKSiF6 is mechanically unstable. We suggest that this property of the host limits the luminescence efficiency of the embedded Mn4+ ions. We also determined the reason for the difference in the intensity of the 2E → 4A2 emission transition (ZPL) in the systems. These findings advance our fundamental understanding of the thermal quenching mechanism of Mn4+ ion luminescence in fluorides, and the results can aid future discoveries of technologically useful phosphors through high-throughput design methodologies.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.