Jae Won Seol , Jong-Sook Lee , Maxim Avdeev , Young-Il Kim
{"title":"氧化氮化物包晶 ACa0.2M0.8O2.6N0.4（A= Sr、Ba；M= Nb、Ta）的结构、光学和介电特性表征","authors":"Jae Won Seol , Jong-Sook Lee , Maxim Avdeev , Young-Il Kim","doi":"10.1016/j.progsolidstchem.2024.100439","DOIUrl":null,"url":null,"abstract":"<div><p><span>Perovskite-type oxynitrides ACa</span><sub>0.2</sub>M<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> (A = Sr, Ba; M = Nb, Ta) were synthesized <em>via</em> the ammonolytic reaction between A<sub>5</sub>M<sub>4</sub>O<sub>15</sub> and CaCl<sub>2</sub>, where the Ca<sup>2+</sup> insertion and O<sup>2−</sup>/N<sup>3−</sup> substitution occurred cooperatively. In terms of the average structure, SrCa<sub>0.2</sub>Nb<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> and SrCa<sub>0.2</sub>Ta<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> belong to the orthorhombic <em>Pnma</em> space group, and BaCa<sub>0.2</sub>Nb<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> and BaCa<sub>0.2</sub>Ta<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub>, the primitive cubic <em>Pm</em> <span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span> <em>m</em> group. The comparison between the experimental lattice volume and the summed ionic volume suggested that ACa<sub>0.2</sub>M<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> have higher degrees of ionicity than AM'<sub>0.2</sub>M<sub>0.8</sub>O<sub>3−<em>x</em></sub>N<sub><em>x</em></sub> (M′ = Li, Mg, Mn), but are more covalent than ANa<sub>0.2</sub>M<sub>0.8</sub>O<sub>2.8</sub>N<sub>0.2</sub>. Despite the significant mismatches of size and charge between Ca<sup>2+</sup> and Nb<sup>5+</sup> (or Ta<sup>5+</sup>), no cation ordering was detected on the octahedral site. On the other hand, the O/N distribution appeared to depend on the bonding geometry around the anion sites in a way N favors the straighter bonding connectivity of M−N−M. The band gap energies of ACa<sub>0.2</sub>M<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> were estimated to be 1.9–2.25 eV depending on A and M. The band gaps and color properties of AMO<sub>2</sub>N and AM'<sub>0.2</sub>M<sub>0.8</sub>O<sub>3−<em>x</em></sub>N<sub><em>x</em></sub><span><span> (A = Sr, Ba; M = Nb, Ta; M′ = Li, Na, Mg, Ca, Mn) are compared. Thermogravimetry and </span>differential scanning calorimetry<span> were conducted in the air to assess the oxynitride stability. The electrical behaviors were studied by the equivalent circuit analysis of the impedance spectrum using compacted polycrystalline specimens, where BaCa</span></span><sub>0.2</sub>Ta<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub><span> was found to possess a bulk dielectric constant of 4550 along with an electrical conductivity of ≈10</span><sup>−6</sup> S/cm at 27 °C. It remains, however, necessary to assess the extrinsic effects arising from the non-ideal sintering to interpret thoroughly the electrical property of BaCa<sub>0.2</sub>Ta<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub>.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"73 ","pages":"Article 100439"},"PeriodicalIF":9.1000,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Characterizations of structural, optical, and dielectric properties of oxynitride perovskites ACa0.2M0.8O2.6N0.4 (A= Sr, Ba; M = Nb, Ta)\",\"authors\":\"Jae Won Seol , Jong-Sook Lee , Maxim Avdeev , Young-Il Kim\",\"doi\":\"10.1016/j.progsolidstchem.2024.100439\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><span>Perovskite-type oxynitrides ACa</span><sub>0.2</sub>M<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> (A = Sr, Ba; M = Nb, Ta) were synthesized <em>via</em> the ammonolytic reaction between A<sub>5</sub>M<sub>4</sub>O<sub>15</sub> and CaCl<sub>2</sub>, where the Ca<sup>2+</sup> insertion and O<sup>2−</sup>/N<sup>3−</sup> substitution occurred cooperatively. In terms of the average structure, SrCa<sub>0.2</sub>Nb<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> and SrCa<sub>0.2</sub>Ta<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> belong to the orthorhombic <em>Pnma</em> space group, and BaCa<sub>0.2</sub>Nb<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> and BaCa<sub>0.2</sub>Ta<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub>, the primitive cubic <em>Pm</em> <span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span> <em>m</em> group. The comparison between the experimental lattice volume and the summed ionic volume suggested that ACa<sub>0.2</sub>M<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> have higher degrees of ionicity than AM'<sub>0.2</sub>M<sub>0.8</sub>O<sub>3−<em>x</em></sub>N<sub><em>x</em></sub> (M′ = Li, Mg, Mn), but are more covalent than ANa<sub>0.2</sub>M<sub>0.8</sub>O<sub>2.8</sub>N<sub>0.2</sub>. Despite the significant mismatches of size and charge between Ca<sup>2+</sup> and Nb<sup>5+</sup> (or Ta<sup>5+</sup>), no cation ordering was detected on the octahedral site. On the other hand, the O/N distribution appeared to depend on the bonding geometry around the anion sites in a way N favors the straighter bonding connectivity of M−N−M. The band gap energies of ACa<sub>0.2</sub>M<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub> were estimated to be 1.9–2.25 eV depending on A and M. The band gaps and color properties of AMO<sub>2</sub>N and AM'<sub>0.2</sub>M<sub>0.8</sub>O<sub>3−<em>x</em></sub>N<sub><em>x</em></sub><span><span> (A = Sr, Ba; M = Nb, Ta; M′ = Li, Na, Mg, Ca, Mn) are compared. Thermogravimetry and </span>differential scanning calorimetry<span> were conducted in the air to assess the oxynitride stability. The electrical behaviors were studied by the equivalent circuit analysis of the impedance spectrum using compacted polycrystalline specimens, where BaCa</span></span><sub>0.2</sub>Ta<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub><span> was found to possess a bulk dielectric constant of 4550 along with an electrical conductivity of ≈10</span><sup>−6</sup> S/cm at 27 °C. It remains, however, necessary to assess the extrinsic effects arising from the non-ideal sintering to interpret thoroughly the electrical property of BaCa<sub>0.2</sub>Ta<sub>0.8</sub>O<sub>2.6</sub>N<sub>0.4</sub>.</p></div>\",\"PeriodicalId\":415,\"journal\":{\"name\":\"Progress in Solid State Chemistry\",\"volume\":\"73 \",\"pages\":\"Article 100439\"},\"PeriodicalIF\":9.1000,\"publicationDate\":\"2024-03-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Progress in Solid State Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0079678624000025\",\"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":"Progress in Solid State Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0079678624000025","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Characterizations of structural, optical, and dielectric properties of oxynitride perovskites ACa0.2M0.8O2.6N0.4 (A= Sr, Ba; M = Nb, Ta)
Perovskite-type oxynitrides ACa0.2M0.8O2.6N0.4 (A = Sr, Ba; M = Nb, Ta) were synthesized via the ammonolytic reaction between A5M4O15 and CaCl2, where the Ca2+ insertion and O2−/N3− substitution occurred cooperatively. In terms of the average structure, SrCa0.2Nb0.8O2.6N0.4 and SrCa0.2Ta0.8O2.6N0.4 belong to the orthorhombic Pnma space group, and BaCa0.2Nb0.8O2.6N0.4 and BaCa0.2Ta0.8O2.6N0.4, the primitive cubic Pmm group. The comparison between the experimental lattice volume and the summed ionic volume suggested that ACa0.2M0.8O2.6N0.4 have higher degrees of ionicity than AM'0.2M0.8O3−xNx (M′ = Li, Mg, Mn), but are more covalent than ANa0.2M0.8O2.8N0.2. Despite the significant mismatches of size and charge between Ca2+ and Nb5+ (or Ta5+), no cation ordering was detected on the octahedral site. On the other hand, the O/N distribution appeared to depend on the bonding geometry around the anion sites in a way N favors the straighter bonding connectivity of M−N−M. The band gap energies of ACa0.2M0.8O2.6N0.4 were estimated to be 1.9–2.25 eV depending on A and M. The band gaps and color properties of AMO2N and AM'0.2M0.8O3−xNx (A = Sr, Ba; M = Nb, Ta; M′ = Li, Na, Mg, Ca, Mn) are compared. Thermogravimetry and differential scanning calorimetry were conducted in the air to assess the oxynitride stability. The electrical behaviors were studied by the equivalent circuit analysis of the impedance spectrum using compacted polycrystalline specimens, where BaCa0.2Ta0.8O2.6N0.4 was found to possess a bulk dielectric constant of 4550 along with an electrical conductivity of ≈10−6 S/cm at 27 °C. It remains, however, necessary to assess the extrinsic effects arising from the non-ideal sintering to interpret thoroughly the electrical property of BaCa0.2Ta0.8O2.6N0.4.
期刊介绍：
Progress in Solid State Chemistry offers critical reviews and specialized articles written by leading experts in the field, providing a comprehensive view of solid-state chemistry. It addresses the challenge of dispersed literature by offering up-to-date assessments of research progress and recent developments. Emphasis is placed on the relationship between physical properties and structural chemistry, particularly imperfections like vacancies and dislocations. The reviews published in Progress in Solid State Chemistry emphasize critical evaluation of the field, along with indications of current problems and future directions. Papers are not intended to be bibliographic in nature but rather to inform a broad range of readers in an inherently multidisciplinary field by providing expert treatises oriented both towards specialists in different areas of the solid state and towards nonspecialists. The authorship is international, and the subject matter will be of interest to chemists, materials scientists, physicists, metallurgists, crystallographers, ceramists, and engineers interested in the solid state.
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