{"title":"用于β-PbF2:Eu3+/K+氟化氧玻璃陶瓷中多个晶格位点的橘红色发光和荧光探针的 5D0/7F4 转变异常强发射†。","authors":"Kejie Xu, Lijuan Zhao, Yuao Guo and Yuting Fu","doi":"10.1039/D4NJ01481B","DOIUrl":null,"url":null,"abstract":"<p >Herein, β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small>/K<small><sup>+</sup></small> glass ceramics (GCs) were synthesized and characterized by X-ray diffraction (XRD), photoluminescence (PL) and decay curves. Based on the XRD analysis, it was inferred that Eu<small><sup>3+</sup></small> and K<small><sup>+</sup></small> ions were doped in the β-PbF<small><sub>2</sub></small> lattice by substituting Pb<small><sup>2+</sup></small> ions. Compared with the interstitial fluorine (F<small><sub><em>i</em></sub></small><small><sup>−</sup></small>) (Eu<small><sup>3+</sup></small> + F<small><sub><em>i</em></sub></small><small><sup>−</sup></small> = Pb<small><sup>2+</sup></small>), K<small><sup>+</sup></small> substitutional doping (Eu<small><sup>3+</sup></small> + K<small><sup>+</sup></small> = 2Pb<small><sup>2+</sup></small>) was the preferential charge-compensating mechanism with the introduction of K<small><sup>+</sup></small> ions in the β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs. Consequently, this is the first report on the anomalous emission of the <small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>4</sub></small> transition in β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs. Based on this anomalous <small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>4</sub></small> transition, a new lattice site with <em>D</em><small><sub>4d</sub></small> symmetry occupied by Eu<small><sup>3+</sup></small> ions was proposed for the first time in β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs. Moreover, according to the intensity ratio of <em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>0</sub></small>)/<em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>2</sub></small>) (<em>I</em><small><sub>00</sub></small>/<em>I</em><small><sub>02</sub></small>), <em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>2</sub></small>)/<em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>1</sub></small>) (<em>I</em><small><sub>02</sub></small>/<em>I</em><small><sub>01</sub></small>) and <em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>4</sub></small>)/<em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>1</sub></small>) (<em>I</em><small><sub>04</sub></small>/<em>I</em><small><sub>01</sub></small>), the breaking of the local lattice symmetry around the Eu<small><sup>3+</sup></small> ions induced by K<small><sup>+</sup></small> ions was demonstrated in detail. With the introduction of K<small><sup>+</sup></small> ions in β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs, the local lattice symmetry around the Eu<small><sup>3+</sup></small> ions continued to decrease from <em>O</em><small><sub>h</sub></small> to <em>D</em><small><sub>4d</sub></small>, <em>C</em><small><sub>4v</sub></small>, <em>C</em><small><sub>3v</sub></small>, <em>C</em><small><sub>2v</sub></small>, and <em>C</em><small><sub>1</sub></small>. Due to the effective charge-compensation of the K<small><sup>+</sup></small> ions, we successfully realized the adjustment and enhancement of the reddish-orange emission from β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs. Simultaneously, an example of Er<small><sup>3+</sup></small>-doped β-PbF<small><sub>2</sub></small> GC was employed to demonstrate the spectral broadening effect of trivalent lanthanide ions (Ln<small><sup>3+</sup></small>) caused by lattice distortion and charge compensation. All these results provide insights to investigate the lattice structures of compounds and also guide researchers to design new emitting devices.</p>","PeriodicalId":95,"journal":{"name":"New Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Anomalous intense emission of the 5D0/7F4 transition for reddish-orange light-emitting and fluorescent probe for multiple lattice sites in β-PbF2:Eu3+/K+ oxyfluoride glass ceramics†\",\"authors\":\"Kejie Xu, Lijuan Zhao, Yuao Guo and Yuting Fu\",\"doi\":\"10.1039/D4NJ01481B\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Herein, β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small>/K<small><sup>+</sup></small> glass ceramics (GCs) were synthesized and characterized by X-ray diffraction (XRD), photoluminescence (PL) and decay curves. Based on the XRD analysis, it was inferred that Eu<small><sup>3+</sup></small> and K<small><sup>+</sup></small> ions were doped in the β-PbF<small><sub>2</sub></small> lattice by substituting Pb<small><sup>2+</sup></small> ions. Compared with the interstitial fluorine (F<small><sub><em>i</em></sub></small><small><sup>−</sup></small>) (Eu<small><sup>3+</sup></small> + F<small><sub><em>i</em></sub></small><small><sup>−</sup></small> = Pb<small><sup>2+</sup></small>), K<small><sup>+</sup></small> substitutional doping (Eu<small><sup>3+</sup></small> + K<small><sup>+</sup></small> = 2Pb<small><sup>2+</sup></small>) was the preferential charge-compensating mechanism with the introduction of K<small><sup>+</sup></small> ions in the β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs. Consequently, this is the first report on the anomalous emission of the <small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>4</sub></small> transition in β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs. Based on this anomalous <small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>4</sub></small> transition, a new lattice site with <em>D</em><small><sub>4d</sub></small> symmetry occupied by Eu<small><sup>3+</sup></small> ions was proposed for the first time in β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs. Moreover, according to the intensity ratio of <em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>0</sub></small>)/<em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>2</sub></small>) (<em>I</em><small><sub>00</sub></small>/<em>I</em><small><sub>02</sub></small>), <em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>2</sub></small>)/<em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>1</sub></small>) (<em>I</em><small><sub>02</sub></small>/<em>I</em><small><sub>01</sub></small>) and <em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>4</sub></small>)/<em>I</em>(<small><sup>5</sup></small>D<small><sub>0</sub></small>/<small><sup>7</sup></small>F<small><sub>1</sub></small>) (<em>I</em><small><sub>04</sub></small>/<em>I</em><small><sub>01</sub></small>), the breaking of the local lattice symmetry around the Eu<small><sup>3+</sup></small> ions induced by K<small><sup>+</sup></small> ions was demonstrated in detail. With the introduction of K<small><sup>+</sup></small> ions in β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs, the local lattice symmetry around the Eu<small><sup>3+</sup></small> ions continued to decrease from <em>O</em><small><sub>h</sub></small> to <em>D</em><small><sub>4d</sub></small>, <em>C</em><small><sub>4v</sub></small>, <em>C</em><small><sub>3v</sub></small>, <em>C</em><small><sub>2v</sub></small>, and <em>C</em><small><sub>1</sub></small>. Due to the effective charge-compensation of the K<small><sup>+</sup></small> ions, we successfully realized the adjustment and enhancement of the reddish-orange emission from β-PbF<small><sub>2</sub></small>:Eu<small><sup>3+</sup></small> GCs. Simultaneously, an example of Er<small><sup>3+</sup></small>-doped β-PbF<small><sub>2</sub></small> GC was employed to demonstrate the spectral broadening effect of trivalent lanthanide ions (Ln<small><sup>3+</sup></small>) caused by lattice distortion and charge compensation. All these results provide insights to investigate the lattice structures of compounds and also guide researchers to design new emitting devices.</p>\",\"PeriodicalId\":95,\"journal\":{\"name\":\"New Journal of Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-06-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"New Journal of Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/nj/d4nj01481b\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"New Journal of Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/nj/d4nj01481b","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Anomalous intense emission of the 5D0/7F4 transition for reddish-orange light-emitting and fluorescent probe for multiple lattice sites in β-PbF2:Eu3+/K+ oxyfluoride glass ceramics†
Herein, β-PbF2:Eu3+/K+ glass ceramics (GCs) were synthesized and characterized by X-ray diffraction (XRD), photoluminescence (PL) and decay curves. Based on the XRD analysis, it was inferred that Eu3+ and K+ ions were doped in the β-PbF2 lattice by substituting Pb2+ ions. Compared with the interstitial fluorine (Fi−) (Eu3+ + Fi− = Pb2+), K+ substitutional doping (Eu3+ + K+ = 2Pb2+) was the preferential charge-compensating mechanism with the introduction of K+ ions in the β-PbF2:Eu3+ GCs. Consequently, this is the first report on the anomalous emission of the 5D0/7F4 transition in β-PbF2:Eu3+ GCs. Based on this anomalous 5D0/7F4 transition, a new lattice site with D4d symmetry occupied by Eu3+ ions was proposed for the first time in β-PbF2:Eu3+ GCs. Moreover, according to the intensity ratio of I(5D0/7F0)/I(5D0/7F2) (I00/I02), I(5D0/7F2)/I(5D0/7F1) (I02/I01) and I(5D0/7F4)/I(5D0/7F1) (I04/I01), the breaking of the local lattice symmetry around the Eu3+ ions induced by K+ ions was demonstrated in detail. With the introduction of K+ ions in β-PbF2:Eu3+ GCs, the local lattice symmetry around the Eu3+ ions continued to decrease from Oh to D4d, C4v, C3v, C2v, and C1. Due to the effective charge-compensation of the K+ ions, we successfully realized the adjustment and enhancement of the reddish-orange emission from β-PbF2:Eu3+ GCs. Simultaneously, an example of Er3+-doped β-PbF2 GC was employed to demonstrate the spectral broadening effect of trivalent lanthanide ions (Ln3+) caused by lattice distortion and charge compensation. All these results provide insights to investigate the lattice structures of compounds and also guide researchers to design new emitting devices.