Barium Titanium Oxynitride from Ammonia-Free Nitridation of Reduced BaTiO<sub>3</sub>
We investigated the nitridation of reduced BaTiO<sub>3</sub>, BaTiO<sub>2.60</sub>H<sub>0.08</sub>, corresponding to an oxyhydride with a large concentration of O defects (>10%). The material is readily nitrided under flowing N<sub>2</sub> gas at te...
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MDPI AG
2021-08-01
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| author | Hua Guo Aleksander Jaworski Zheng Chen Can Lu Adam Slabon Ulrich Häussermann |
| author_facet | Hua Guo Aleksander Jaworski Zheng Chen Can Lu Adam Slabon Ulrich Häussermann |
| author_sort | Hua Guo |
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| description | We investigated the nitridation of reduced BaTiO<sub>3</sub>, BaTiO<sub>2.60</sub>H<sub>0.08</sub>, corresponding to an oxyhydride with a large concentration of O defects (>10%). The material is readily nitrided under flowing N<sub>2</sub> gas at temperatures between 400 and 450 °C to yield oxynitrides BaTiO<sub>2.6</sub>N<i><sub>x</sub></i> (<i>x</i> = 0.2−0.22) with a slightly tetragonally distorted perovskite structure, <i>a</i> ≈ 4.01 and <i>c</i> ≈ 4.02 Å, and Ti partially remaining in the oxidation state III. The tetragonal structure was confirmed from Raman spectroscopy. <sup>14</sup>N MAS NMR spectroscopy shows a single resonance at 270 ppm, which is typical for perovskite transition metal oxynitrides. However, largely different signal intensity for materials with very similar N content suggests N/O/vacancy ordering when prolonging nitridation times to hours. Diffuse reflectance UV-VIS spectroscopy shows a reduction of the intrinsic band gap to 2.4–2.45 eV compared to BaTiO<sub>3</sub> (~3.2 eV). Mott-Schottky measurements confirm n-type conductivity and reveal a slight negative shift of the conduction band edge from –0.59 V (BaTiO<sub>3</sub>) to ~–0.65 eV. |
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| last_indexed | 2024-03-10T08:43:16Z |
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| spelling | doaj.art-c1d919c873514d7cb8f998de0a78034a2023-11-22T08:06:36ZengMDPI AGInorganics2304-67402021-08-01986210.3390/inorganics9080062Barium Titanium Oxynitride from Ammonia-Free Nitridation of Reduced BaTiO<sub>3</sub>Hua Guo0Aleksander Jaworski1Zheng Chen2Can Lu3Adam Slabon4Ulrich Häussermann5Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, SwedenDepartment of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, SwedenInstitute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, DE-52074 Aachen, GermanyInstitute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, DE-52074 Aachen, GermanyDepartment of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, SwedenDepartment of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, SwedenWe investigated the nitridation of reduced BaTiO<sub>3</sub>, BaTiO<sub>2.60</sub>H<sub>0.08</sub>, corresponding to an oxyhydride with a large concentration of O defects (>10%). The material is readily nitrided under flowing N<sub>2</sub> gas at temperatures between 400 and 450 °C to yield oxynitrides BaTiO<sub>2.6</sub>N<i><sub>x</sub></i> (<i>x</i> = 0.2−0.22) with a slightly tetragonally distorted perovskite structure, <i>a</i> ≈ 4.01 and <i>c</i> ≈ 4.02 Å, and Ti partially remaining in the oxidation state III. The tetragonal structure was confirmed from Raman spectroscopy. <sup>14</sup>N MAS NMR spectroscopy shows a single resonance at 270 ppm, which is typical for perovskite transition metal oxynitrides. However, largely different signal intensity for materials with very similar N content suggests N/O/vacancy ordering when prolonging nitridation times to hours. Diffuse reflectance UV-VIS spectroscopy shows a reduction of the intrinsic band gap to 2.4–2.45 eV compared to BaTiO<sub>3</sub> (~3.2 eV). Mott-Schottky measurements confirm n-type conductivity and reveal a slight negative shift of the conduction band edge from –0.59 V (BaTiO<sub>3</sub>) to ~–0.65 eV.https://www.mdpi.com/2304-6740/9/8/62solid-state chemistrymixed-anion compoundsbarium titanateoxyhydrideoxynitridesolid-state NMR |
| spellingShingle | Hua Guo Aleksander Jaworski Zheng Chen Can Lu Adam Slabon Ulrich Häussermann Barium Titanium Oxynitride from Ammonia-Free Nitridation of Reduced BaTiO<sub>3</sub> Inorganics solid-state chemistry mixed-anion compounds barium titanate oxyhydride oxynitride solid-state NMR |
| title | Barium Titanium Oxynitride from Ammonia-Free Nitridation of Reduced BaTiO<sub>3</sub> |
| title_full | Barium Titanium Oxynitride from Ammonia-Free Nitridation of Reduced BaTiO<sub>3</sub> |
| title_fullStr | Barium Titanium Oxynitride from Ammonia-Free Nitridation of Reduced BaTiO<sub>3</sub> |
| title_full_unstemmed | Barium Titanium Oxynitride from Ammonia-Free Nitridation of Reduced BaTiO<sub>3</sub> |
| title_short | Barium Titanium Oxynitride from Ammonia-Free Nitridation of Reduced BaTiO<sub>3</sub> |
| title_sort | barium titanium oxynitride from ammonia free nitridation of reduced batio sub 3 sub |
| topic | solid-state chemistry mixed-anion compounds barium titanate oxyhydride oxynitride solid-state NMR |
| url | https://www.mdpi.com/2304-6740/9/8/62 |
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