{"title":"Na6(SO4)2SiF6：具有宽深紫外透明窗和强二次谐波响应的稳定的硫酸盐氟硅酸盐","authors":"Zi-Long Geng, , , Zuju Ma, , , Rui-Biao Fu*, , and , Xin-Tao Wu, ","doi":"10.1021/acs.chemmater.5c02009","DOIUrl":null,"url":null,"abstract":"<p >During the development of deep-ultraviolet (DUV) nonlinear optical (NLO) crystals, how to better balance a wide DUV transparency window and strong second-harmonic generation (SHG) response has always been a challenge because they are usually contradictory in one NLO crystal. Herein, we report the design and synthesis of the first DUV transparent sulfate fluosilicate NLO crystal, Na<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub>. The introduction of the perfluorinated [SiF<sub>6</sub>] group with a large HOMO–LUMO gap and the weakening of the <i>d</i>–<i>p</i> π-bond in the [SO<sub>4</sub>] group by alkali metal cations widen the DUV transparency window. Meanwhile, the oriented arrangement of [SO<sub>4</sub>] groups gives rise to the optimal superposition of their microscopic second-order susceptibilities to strengthen the SHG response. Remarkably, Na<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub> features the strongest SHG response (1.45 × KH<sub>2</sub>PO<sub>4</sub>) among DUV transparent fluosilicate NLO crystals and a short DUV cutoff edge below 190 nm. Moreover, Na<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub> exhibits a wide transparency window of 0.19–8.45 μm, a large laser-induced damage threshold of 315 MW/cm<sup>2</sup>, high thermal stability up to 400 °C under an air atmosphere, and feasible growth of centimeter-sized single crystals. This research indicates that Na<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub> has great application potential and provides a method to pave the way for the exploration of next-generation DUV NLO crystals.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 19","pages":"8059–8067"},"PeriodicalIF":7.0000,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Na6(SO4)2SiF6: A Stable Sulfate Fluosilicate with Wide Deep-Ultraviolet Transparency Window and Strong Second-Harmonic Generation Response\",\"authors\":\"Zi-Long Geng, , , Zuju Ma, , , Rui-Biao Fu*, , and , Xin-Tao Wu, \",\"doi\":\"10.1021/acs.chemmater.5c02009\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >During the development of deep-ultraviolet (DUV) nonlinear optical (NLO) crystals, how to better balance a wide DUV transparency window and strong second-harmonic generation (SHG) response has always been a challenge because they are usually contradictory in one NLO crystal. Herein, we report the design and synthesis of the first DUV transparent sulfate fluosilicate NLO crystal, Na<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub>. The introduction of the perfluorinated [SiF<sub>6</sub>] group with a large HOMO–LUMO gap and the weakening of the <i>d</i>–<i>p</i> π-bond in the [SO<sub>4</sub>] group by alkali metal cations widen the DUV transparency window. Meanwhile, the oriented arrangement of [SO<sub>4</sub>] groups gives rise to the optimal superposition of their microscopic second-order susceptibilities to strengthen the SHG response. Remarkably, Na<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub> features the strongest SHG response (1.45 × KH<sub>2</sub>PO<sub>4</sub>) among DUV transparent fluosilicate NLO crystals and a short DUV cutoff edge below 190 nm. Moreover, Na<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub> exhibits a wide transparency window of 0.19–8.45 μm, a large laser-induced damage threshold of 315 MW/cm<sup>2</sup>, high thermal stability up to 400 °C under an air atmosphere, and feasible growth of centimeter-sized single crystals. This research indicates that Na<sub>6</sub>(SO<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub> has great application potential and provides a method to pave the way for the exploration of next-generation DUV NLO crystals.</p>\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":\"37 19\",\"pages\":\"8059–8067\"},\"PeriodicalIF\":7.0000,\"publicationDate\":\"2025-10-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.chemmater.5c02009\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.5c02009","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Na6(SO4)2SiF6: A Stable Sulfate Fluosilicate with Wide Deep-Ultraviolet Transparency Window and Strong Second-Harmonic Generation Response
During the development of deep-ultraviolet (DUV) nonlinear optical (NLO) crystals, how to better balance a wide DUV transparency window and strong second-harmonic generation (SHG) response has always been a challenge because they are usually contradictory in one NLO crystal. Herein, we report the design and synthesis of the first DUV transparent sulfate fluosilicate NLO crystal, Na6(SO4)2SiF6. The introduction of the perfluorinated [SiF6] group with a large HOMO–LUMO gap and the weakening of the d–p π-bond in the [SO4] group by alkali metal cations widen the DUV transparency window. Meanwhile, the oriented arrangement of [SO4] groups gives rise to the optimal superposition of their microscopic second-order susceptibilities to strengthen the SHG response. Remarkably, Na6(SO4)2SiF6 features the strongest SHG response (1.45 × KH2PO4) among DUV transparent fluosilicate NLO crystals and a short DUV cutoff edge below 190 nm. Moreover, Na6(SO4)2SiF6 exhibits a wide transparency window of 0.19–8.45 μm, a large laser-induced damage threshold of 315 MW/cm2, high thermal stability up to 400 °C under an air atmosphere, and feasible growth of centimeter-sized single crystals. This research indicates that Na6(SO4)2SiF6 has great application potential and provides a method to pave the way for the exploration of next-generation DUV NLO crystals.
期刊介绍：
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.
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