Shanshan Chen, Zhiyong Bai, Xianyu Song, Tao Ouyang, Yanqiang Li, Qingran Ding, Han Wang, Wentong Chen, Junhua Luo, Sangen Zhao
{"title":"超宽带隙HTO型非线性光学氟磷酸盐","authors":"Shanshan Chen, Zhiyong Bai, Xianyu Song, Tao Ouyang, Yanqiang Li, Qingran Ding, Han Wang, Wentong Chen, Junhua Luo, Sangen Zhao","doi":"10.1002/smll.202408191","DOIUrl":null,"url":null,"abstract":"<p>Compounds having hexagonal tungsten oxides (HTO) topology are of intense research interests owing to their potential functional properties, such as nonlinear optical (NLO) performances. However, most of the reported HTO-type compounds exhibit narrow optical bandgaps because of the <i>d</i>–<i>d</i> electronic transition of compositional <i>d</i><sup>0</sup> transition metals and lone pair electrons effect of Se<sup>4+</sup>/Te<sup>4+</sup>, which hinder their applications in the high-energy field, such as deep-ultraviolet (deep-UV) region. In this work, a new fluorophosphate, (NH<sub>4</sub>)<sub>3</sub>[Sc<sub>3</sub>F<sub>5</sub>(PO<sub>4</sub>)](PO<sub>3</sub>F)<sub>2</sub> exhibiting HTO-topological structures is reported. Remarkably, the compound shows an ultrawide optical bandgap (<i>E</i><sub>g</sub>(exp.) > 6.2 eV, <i>E</i><sub>g</sub>(cal.) = 6.724 eV), surpassing those of reported HTO-type compounds. The fact is mainly ascribed to the collaborative effect of Sc<sup>3+</sup> without destructive <i>d</i>–<i>d</i> transition, the PO<sub>4</sub> and PO<sub>3</sub>F units having large LUMO-HOMO gaps. Furthermore, it exhibits a phase-matchable second-harmonic generation (SHG) response of ca. 0.65 × KDP, underscoring its potential use for NLO applications. This work provides new opportunities for discovering HTO-type NLO crystals with ultrawide bandgaps.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":"21 7","pages":""},"PeriodicalIF":12.1000,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A HTO-Type Nonlinear Optical Fluorophosphate with Ultrawide Bandgap\",\"authors\":\"Shanshan Chen, Zhiyong Bai, Xianyu Song, Tao Ouyang, Yanqiang Li, Qingran Ding, Han Wang, Wentong Chen, Junhua Luo, Sangen Zhao\",\"doi\":\"10.1002/smll.202408191\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Compounds having hexagonal tungsten oxides (HTO) topology are of intense research interests owing to their potential functional properties, such as nonlinear optical (NLO) performances. However, most of the reported HTO-type compounds exhibit narrow optical bandgaps because of the <i>d</i>–<i>d</i> electronic transition of compositional <i>d</i><sup>0</sup> transition metals and lone pair electrons effect of Se<sup>4+</sup>/Te<sup>4+</sup>, which hinder their applications in the high-energy field, such as deep-ultraviolet (deep-UV) region. In this work, a new fluorophosphate, (NH<sub>4</sub>)<sub>3</sub>[Sc<sub>3</sub>F<sub>5</sub>(PO<sub>4</sub>)](PO<sub>3</sub>F)<sub>2</sub> exhibiting HTO-topological structures is reported. Remarkably, the compound shows an ultrawide optical bandgap (<i>E</i><sub>g</sub>(exp.) > 6.2 eV, <i>E</i><sub>g</sub>(cal.) = 6.724 eV), surpassing those of reported HTO-type compounds. The fact is mainly ascribed to the collaborative effect of Sc<sup>3+</sup> without destructive <i>d</i>–<i>d</i> transition, the PO<sub>4</sub> and PO<sub>3</sub>F units having large LUMO-HOMO gaps. Furthermore, it exhibits a phase-matchable second-harmonic generation (SHG) response of ca. 0.65 × KDP, underscoring its potential use for NLO applications. This work provides new opportunities for discovering HTO-type NLO crystals with ultrawide bandgaps.</p>\",\"PeriodicalId\":228,\"journal\":{\"name\":\"Small\",\"volume\":\"21 7\",\"pages\":\"\"},\"PeriodicalIF\":12.1000,\"publicationDate\":\"2025-01-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Small\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/smll.202408191\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/smll.202408191","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
A HTO-Type Nonlinear Optical Fluorophosphate with Ultrawide Bandgap
Compounds having hexagonal tungsten oxides (HTO) topology are of intense research interests owing to their potential functional properties, such as nonlinear optical (NLO) performances. However, most of the reported HTO-type compounds exhibit narrow optical bandgaps because of the d–d electronic transition of compositional d0 transition metals and lone pair electrons effect of Se4+/Te4+, which hinder their applications in the high-energy field, such as deep-ultraviolet (deep-UV) region. In this work, a new fluorophosphate, (NH4)3[Sc3F5(PO4)](PO3F)2 exhibiting HTO-topological structures is reported. Remarkably, the compound shows an ultrawide optical bandgap (Eg(exp.) > 6.2 eV, Eg(cal.) = 6.724 eV), surpassing those of reported HTO-type compounds. The fact is mainly ascribed to the collaborative effect of Sc3+ without destructive d–d transition, the PO4 and PO3F units having large LUMO-HOMO gaps. Furthermore, it exhibits a phase-matchable second-harmonic generation (SHG) response of ca. 0.65 × KDP, underscoring its potential use for NLO applications. This work provides new opportunities for discovering HTO-type NLO crystals with ultrawide bandgaps.
期刊介绍：
Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments.
With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology.
Small's readership includes biochemists, biologists, biomedical scientists, chemists, engineers, information technologists, materials scientists, physicists, and theoreticians alike.
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