Crystal Structure and Physica Properties of Perovskite Oxide BaMO3 (M Being Transition Metal)
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摘要: 钙钛矿氧化物BaMO3（M为过渡族金属）具有复杂的晶体结构和物理性质，本文系统地总结了BaMO3的研究进展，重点关注在 M 元素变化过程中晶体结构和物理性质的演化，以及高压调控下的结构相变、电输运性质和磁学性质的变化，讨论了M离子半径及合成压力对六方钙钛矿到钙钛矿演化过程的影响，同时对该领域中一些问题做了展望，探讨了这一体系可能出现的新的原子组合和结构，相应材料可能具有的新特性和科学意义。Abstract: The perovskite oxide BaMO3 (M being transition metal) has a complex crystal structure and physical properties. This article systematically summarizes the research progress, focusing on the evolution of crystal structure and physical properties during the M element change process, as well as the structural phase transition, electrical transport properties, and magnetic properties regulation under high-pressure. The influence of M ion radius and synthesis pressure on the evolution process from hexagonal perovskite to perovskite is discussed, and some issues in this field are also discussed. The possible new atomic combinations and structures in this system, as well as the new characteristics and scientific significance of these corresponding materials, are discussed.
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图 1 (a) 立方和(b) 正交钙钛矿的晶体结构示意图
Figure 1. Schematic views of the crystallographic forms of (a) cubic and (b) orthorhombic perovskite
图 2 BX6八面体(a)共顶点连接和(b)共面连接时A-X配位示意图
Figure 2. Schematic views of A-X coordinations while BX6 octahedrons are connected by (a) vertex and (b) plane
图 4 (a) 5H-BaMO3和(b) 14H-BaMO3的晶体结构示意图
Figure 4. Schematic views of crystal structure of (a) 5H-BaMO3 and (b) 14H-BaMO3
图 8 (a) 4H-BaMO3、(b) 12R-BaMO3和(c) 27R-BaMO3的晶体结构示意图
Figure 8. Schematic diagram of crystal structure of (a) 4H-BaMO3, (b) 12R-BaMO3, and (c) 27R-BaMO3
图 11 (a) 2H-BaMO3、(b) 9R-BaMO3、(c) 6H'-BaMO3、(d) 8H-BaMO3、(e) 10H-BaMO3、(f) 15R-BaMO3和(g) 21R-BaMO3的晶体结构示意图
Figure 11. Schematic diagrams of crystal structures of (a) 2H-BaMO3, (b) 9R-BaMO3, (c) 6H'-BaMO3, (d) 8H-BaMO3, (e) 10H-BaMO3, (f) 15R-BaMO3, and (g) 21R-BaMO3
图 13 (a) “12R”-BaMO3和(b) 12M-BaMO3的晶体结构示意图
Figure 13. Schematic diagram of crystal structure of(a) “12R”-BaMO3 and (b) 12M-BaMO3
图 16 (a) 2H'-BaMO3、(b) 12H-BaMO3和(c) 3C'-BaMO3的晶体结构示意图
Figure 16. Schematic diagram of crystal structure of (a) 2H'-BaMO3, (b) 12H-BaMO3, and (c) 3C'-BaMO3
图 21 (a) 9M-BaMO3、(b) 5M-BaMO3、(c) 6M-BaMO3和(d) 四方钙钛矿BaMO3的晶体结构示意图
Figure 21. Schematic views of the crystal structure of (a) 9M-BaMO3, (b) 5M-BaMO3,(c) 6M-BaMO3, and (d) tetragonal perovskite BaMO3
图 26 BaMO3（M为过渡金属离子）的多层堆积变体
Figure 26. Multi-layer stacked variants of BaMO3 (M is a transition metal)
图 27 BaMO3（M = V, Cr, Mn, Ru, Os, Rh, Ir）在不同合成压力范围内的多层堆积变体
Figure 27. Multi-layer stacked variants of BaMO3 (M = V, Cr, Mn, Ru, Os, Rh, Ir) in different synthetic pressures
图 28 BaMO3中MO6八面体连接情况随合成压力的演化
Figure 28. Evolution of MO6 octahedron’s connectivity in BaMO3 with synthetic pressure
图 29 BaMO3的(a) 每个化学式的晶胞体积V/Z、(b) 近邻多聚体之间的M-M距离dM-M、(c) 轴比率(c/a)/N、(d) 多聚体内M-M之间的距离
${d'_{{\text{M-M}}}} $ ，(e) Ba-O之间的平均距离${\bar d_{{\text{Ba-O}}}}$ 和(f) M-O之间的平均距离${\bar d_{{\text{M-O}}}}$ 随M离子半径的变化关系Figure 29. Relations of (a) volume per chemical formula V/Z, (b) M-M distance between neighbour polymers dM-M,(c) axis ratio (c/a)/N, (d) M-M distance in one polymer
${d'_{{\text{M-M}}}} $ ; (e) average distance of Ba-O${\bar d_{{\text{Ba-O}}}}$ ; (f) average distance of M-O${\bar d_{{\text{M-O}}}}$ versus M ion radius of BaMO3
图 30 BaMO3的“容忍因子”t'随M离子半径的变化关系
Figure 30. Relationship of “tolerance factor” t' versus M ion radius of BaMO3
图 31 BaMO3的(a) 剩余电阻率ρ0和(b) 剩余电阻比率rRRR
Figure 31. (a) Residual resistivity ρ0 and (b) residual resistivity ratio rRRR of BaMO3
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