Pressure-induced yttrium oxides with unconventional stoichiometries and novel properties
Pressure-induced yttrium oxides with unconventional stoichiometries and novel properties
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DOI：
10.1103/physrevmaterials.5.044802
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发表时间：
2021-04
影响因子：
3.4
通讯作者：
Qiuping Yang;Jianyan Lin;Fei Li;Jing Zhang;E. Zurek;Guochun Yang
中科院分区：
文献类型：
--
作者：
Qiuping Yang;Jianyan Lin;Fei Li;Jing Zhang;E. Zurek;Guochun Yang
化合物中存在的含氧基序（例如 ${\mathrm{O}}^{2--}$、${{\mathrm{O}}_{2}}^{2\text{--}}$ ${{\mathrm{O}}_{2}}^{2\text{--}}$ 和 ${{\mathrm{O}}_{2}}^{\text{--}}$）对其电子结构和行为产生重大影响。在此，第一原理群体智能晶体结构搜索揭示了Y和O在高压下的反应导致形成具有独特性质的新型化合物。几种富含 O 的 Y-O 化合物（例如 ${\mathrm{YO}}_{2}$、${\mathrm{Y}}_{2}{\mathrm{O}}_{5}$ 和 ${\mathrm{YO}}_{3}$）表现出稳定。结果表明，稳定物种中发现的含氧基序取决于氧含量和压力（例如，YO 中的 ${\mathrm{O}}^{2\text{--}}$ 和 ${\mathrm{Y}}_{2}{\mathrm{O}}_{3}$，${\mathrm{O}}^{2\text{--}}$ 和 ${\mathrm{O}}^{2\text{--}}$ 的共存${{\mathrm{O}}_{2}}^{2\text{--}}$ 位于 ${\mathrm{YO}}_{2}$ 和 ${\mathrm{Y}}_{2}{\mathrm{O}}_{5}$、${{\mathrm{O}}_{2}}^{2\text{--}}$ 位于 $Pm\text{\ensuremath{-}}3$ ${\mathrm{YO}}_{3}$ 和 Cmcm ${\mathrm{YO}}_{3}$ 中的 ${\mathrm{O}}^{2\text{--}}$)，并伴随着电子结构从超导到金属再到半导体的转变。值得注意的是，Cmcm 对称 ${\mathrm{YO}}_{3}$ 相由具有 15 个面的 13 重配位共面多面体组成，可归类为过渡金属 (TM) 超氧化物。长期以来备受追捧的块状一氧化钇 (YO) 在高压下变得稳定。 NaCl型YO在25 GPa下具有超导性，临界温度$({T}_{c})$为13.0 K，成为已知${T}_{c}$最高的TM一氧化物。我们的工作将激发未来研究探索高压下富氧TM氧化物的化学和性质。
The oxygenic motifs (e.g., ${\mathrm{O}}^{2--}$, ${{\mathrm{O}}_{2}}^{2\text{--}}$ ${{\mathrm{O}}_{2}}^{2\text{--}}$, and ${{\mathrm{O}}_{2}}^{\text{--}}$) that are present in compounds have a substantial effect on their electronic structure and behavior. Herein, first-principles swarm-intelligence crystal structural searches reveal that the reaction between Y and O under high pressure leads to the formation of novel compounds with unique properties. Several O-rich Y-O compounds (e.g., ${\mathrm{YO}}_{2}$, ${\mathrm{Y}}_{2}{\mathrm{O}}_{5}$, and ${\mathrm{YO}}_{3}$) emerge as being stable. It is shown that the oxygenic motifs found within the stable species depend upon the oxygen content and pressure (e.g., ${\mathrm{O}}^{2\text{--}}$ in YO and ${\mathrm{Y}}_{2}{\mathrm{O}}_{3}$, the coexistence of ${\mathrm{O}}^{2\text{--}}$ and ${{\mathrm{O}}_{2}}^{2\text{--}}$ in ${\mathrm{YO}}_{2}$ and ${\mathrm{Y}}_{2}{\mathrm{O}}_{5}$, ${{\mathrm{O}}_{2}}^{2\text{--}}$ in $Pm\text{\ensuremath{-}}3$ ${\mathrm{YO}}_{3}$, and ${\mathrm{O}}^{2\text{--}}$ in Cmcm ${\mathrm{YO}}_{3}$), and are accompanied by a transition in the electronic structure from superconducting to metallic to semiconducting. Notably, the Cmcm symmetry ${\mathrm{YO}}_{3}$ phase, consisting of a 13-fold coordinated face-sharing polyhedron with 15 faces, can be classified as a transition metal (TM) superoxide. The long sought-after bulk yttrium monoxide (YO) is shown to become stable at high pressure. NaCl-type YO is superconducting with a critical temperature $({T}_{c})$ of 13.0 K at 25 GPa, becoming the TM monoxide with the highest known ${T}_{c}$. Our work will inspire future studies exploring the chemistry and properties of O-rich TM oxides at high pressure.