Dongdong Chu, Kewang Zhang, Congwei Xie*, Keith T. Butler, Zhihua Yang and Shilie Pan*,
{"title":"在深紫外透明的 d0 过渡金属氧氟化物中，双阴离子策略诱导超短相匹配波长的双重增强作用","authors":"Dongdong Chu, Kewang Zhang, Congwei Xie*, Keith T. Butler, Zhihua Yang and Shilie Pan*, ","doi":"10.1021/acsmaterialslett.4c00197","DOIUrl":null,"url":null,"abstract":"<p >The d<sup>0</sup> transition metal oxides are the most commonly used nonlinear optical (NLO) materials in the visible light region; however, their limited band gaps seriously hinder their application in ultraviolet (UV) and deep-ultraviolet (DUV) regions. Achieving the double enhancement of band gap and birefringence by regulating anionic units helps to push their phase-matching (PM) wavelength into UV/DUV regions. Herein, starting from the famous NLO material LiNbO<sub>3</sub>, a “dual-anion strategy” is proposed to regulate the [NbO<sub>6–<i>x</i></sub>F<sub><i>x</i></sub>] octahedra, and the predicted Li<sub>2</sub>Nb<sub>2</sub>O<sub>6–<i>x</i></sub>F<sub>2<i>x</i></sub>·(LiF)<sub><i>y</i></sub> (<i>x</i> = 1, 2, 4; <i>y</i> = 0, 2) materials exhibit the dual-property magnification of wide band gaps (3.82–6.26 eV, 1–3 eV larger than LiNbO<sub>3</sub>) and extraordinary birefringence (0.100–0.322, 1–4 times that of LiNbO<sub>3</sub>), along with a strong second harmonic generation (SHG) response of 2.6–6.2 × KDP. Remarkably, Li<sub>2</sub>NbOF<sub>5</sub>-I and LiNbOF<sub>4</sub>-II have extremely short PM wavelength (λ<sub>PM</sub> = 209 nm) ever reported for d<sup>0</sup> transition metal oxyfluorides. Further analysis uncovers that the fluorinated modification of band edges and the increase of octahedral anisotropy in [NbO<sub>6−x</sub>F<sub>x</sub>] anionic groups are the main reasons for the enhanced PM ability.</p>","PeriodicalId":19,"journal":{"name":"ACS Materials Letters","volume":"6 4","pages":"1094–1102"},"PeriodicalIF":9.6000,"publicationDate":"2024-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Dual-Anion Strategy Induces Dual Enhancement Toward Ultrashort Phase-Matching Wavelength in Deep-UV Transparent d0 Transition Metal Oxyfluorides\",\"authors\":\"Dongdong Chu, Kewang Zhang, Congwei Xie*, Keith T. Butler, Zhihua Yang and Shilie Pan*, \",\"doi\":\"10.1021/acsmaterialslett.4c00197\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The d<sup>0</sup> transition metal oxides are the most commonly used nonlinear optical (NLO) materials in the visible light region; however, their limited band gaps seriously hinder their application in ultraviolet (UV) and deep-ultraviolet (DUV) regions. Achieving the double enhancement of band gap and birefringence by regulating anionic units helps to push their phase-matching (PM) wavelength into UV/DUV regions. Herein, starting from the famous NLO material LiNbO<sub>3</sub>, a “dual-anion strategy” is proposed to regulate the [NbO<sub>6–<i>x</i></sub>F<sub><i>x</i></sub>] octahedra, and the predicted Li<sub>2</sub>Nb<sub>2</sub>O<sub>6–<i>x</i></sub>F<sub>2<i>x</i></sub>·(LiF)<sub><i>y</i></sub> (<i>x</i> = 1, 2, 4; <i>y</i> = 0, 2) materials exhibit the dual-property magnification of wide band gaps (3.82–6.26 eV, 1–3 eV larger than LiNbO<sub>3</sub>) and extraordinary birefringence (0.100–0.322, 1–4 times that of LiNbO<sub>3</sub>), along with a strong second harmonic generation (SHG) response of 2.6–6.2 × KDP. Remarkably, Li<sub>2</sub>NbOF<sub>5</sub>-I and LiNbOF<sub>4</sub>-II have extremely short PM wavelength (λ<sub>PM</sub> = 209 nm) ever reported for d<sup>0</sup> transition metal oxyfluorides. Further analysis uncovers that the fluorinated modification of band edges and the increase of octahedral anisotropy in [NbO<sub>6−x</sub>F<sub>x</sub>] anionic groups are the main reasons for the enhanced PM ability.</p>\",\"PeriodicalId\":19,\"journal\":{\"name\":\"ACS Materials Letters\",\"volume\":\"6 4\",\"pages\":\"1094–1102\"},\"PeriodicalIF\":9.6000,\"publicationDate\":\"2024-02-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Materials Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsmaterialslett.4c00197\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Materials Letters","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsmaterialslett.4c00197","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Dual-Anion Strategy Induces Dual Enhancement Toward Ultrashort Phase-Matching Wavelength in Deep-UV Transparent d0 Transition Metal Oxyfluorides
The d0 transition metal oxides are the most commonly used nonlinear optical (NLO) materials in the visible light region; however, their limited band gaps seriously hinder their application in ultraviolet (UV) and deep-ultraviolet (DUV) regions. Achieving the double enhancement of band gap and birefringence by regulating anionic units helps to push their phase-matching (PM) wavelength into UV/DUV regions. Herein, starting from the famous NLO material LiNbO3, a “dual-anion strategy” is proposed to regulate the [NbO6–xFx] octahedra, and the predicted Li2Nb2O6–xF2x·(LiF)y (x = 1, 2, 4; y = 0, 2) materials exhibit the dual-property magnification of wide band gaps (3.82–6.26 eV, 1–3 eV larger than LiNbO3) and extraordinary birefringence (0.100–0.322, 1–4 times that of LiNbO3), along with a strong second harmonic generation (SHG) response of 2.6–6.2 × KDP. Remarkably, Li2NbOF5-I and LiNbOF4-II have extremely short PM wavelength (λPM = 209 nm) ever reported for d0 transition metal oxyfluorides. Further analysis uncovers that the fluorinated modification of band edges and the increase of octahedral anisotropy in [NbO6−xFx] anionic groups are the main reasons for the enhanced PM ability.
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ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.
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