Bulk synthesis of Zn$_3$WN$_4$ via solid-state metathesis
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arXiv
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| Format: | Preprint |
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2024
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| author | Rom, Christopher L. O'Donnell, Shaun Huang, Kayla Klein, Ryan A. Kramer, Morgan J. Smaha, Rebecca W. Zakutayev, Andriy |
| author_facet | Rom, Christopher L. O'Donnell, Shaun Huang, Kayla Klein, Ryan A. Kramer, Morgan J. Smaha, Rebecca W. Zakutayev, Andriy |
| contents | Ternary nitrides are of growing technological importance, with applications as semiconductors, catalysts, and magnetic materials; however, new synthetic tools are needed to advance materials discovery efforts. Here, we show that Zn$_3$WN$_4$ can be synthesized via metathesis reactions between Li$_6$WN$_4$ and Zn$X_2$ ($X$ = Br, Cl, F). In situ synchrotron powder X-ray diffraction and differential scanning calorimetry show that the reaction onset is correlated with the Zn$X_2$ melting point and that product purity is inversely correlated with the reaction's exothermicity. High resolution synchrotron powder X-ray diffraction measurements show that this bulk synthesis produces a structure with substantial cation ordering, as opposed to the disordered structure initially discovered via thin film sputtering. Diffuse reflectance spectroscopy reveals that Zn$_3$WN$_4$ powders exhibit two optical absorption onsets at 2.5 eV and 4.0 eV, indicating wide-bandgap semiconducting behavior and suggesting a small amount of structural disorder. We hypothesize that this synthesis strategy is generalizable because many potential Li-$M$-N precursors (where $M$ is a metal) are available for synthesizing new ternary nitride materials. This work introduces a promising synthesis strategy that will accelerate the discovery of novel functional ternary nitrides and other currently inaccessible materials. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2401_01964 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Bulk synthesis of Zn$_3$WN$_4$ via solid-state metathesis Rom, Christopher L. O'Donnell, Shaun Huang, Kayla Klein, Ryan A. Kramer, Morgan J. Smaha, Rebecca W. Zakutayev, Andriy Materials Science Ternary nitrides are of growing technological importance, with applications as semiconductors, catalysts, and magnetic materials; however, new synthetic tools are needed to advance materials discovery efforts. Here, we show that Zn$_3$WN$_4$ can be synthesized via metathesis reactions between Li$_6$WN$_4$ and Zn$X_2$ ($X$ = Br, Cl, F). In situ synchrotron powder X-ray diffraction and differential scanning calorimetry show that the reaction onset is correlated with the Zn$X_2$ melting point and that product purity is inversely correlated with the reaction's exothermicity. High resolution synchrotron powder X-ray diffraction measurements show that this bulk synthesis produces a structure with substantial cation ordering, as opposed to the disordered structure initially discovered via thin film sputtering. Diffuse reflectance spectroscopy reveals that Zn$_3$WN$_4$ powders exhibit two optical absorption onsets at 2.5 eV and 4.0 eV, indicating wide-bandgap semiconducting behavior and suggesting a small amount of structural disorder. We hypothesize that this synthesis strategy is generalizable because many potential Li-$M$-N precursors (where $M$ is a metal) are available for synthesizing new ternary nitride materials. This work introduces a promising synthesis strategy that will accelerate the discovery of novel functional ternary nitrides and other currently inaccessible materials. |
| title | Bulk synthesis of Zn$_3$WN$_4$ via solid-state metathesis |
| topic | Materials Science |
| url | https://arxiv.org/abs/2401.01964 |