A位有序四重钙钛矿氧化物：结构、物性和展望

王潇; 刘哲宏; 卢达标; 皮茂材; 潘昭; 龙有文

doi:10.11858/gywlxb.20230785

A位有序四重钙钛矿氧化物：结构、物性和展望

doi: 10.11858/gywlxb.20230785

王潇^1,,
刘哲宏¹,
卢达标^{1, 2},
皮茂材^{1, 2},
潘昭¹,
龙有文^{1, 2, 3,*, ,}

1.
中国科学院物理研究所, 北京凝聚态物理国家研究中心, 北京　100190
2.
中国科学院大学物理科学学院, 北京　100049
3.
松山湖材料实验室, 广东东莞　523808

基金项目: 国家重点研发计划（2021YFA1400300）；国家自然科学基金（11934017，12261131499，11921004，12304159, 12204516）；北京市自然科学基金（Z200007）；中国科学院先导B项目（XDB33000000）

详细信息

作者简介:
王　潇（1991－），男，博士，博士后，主要从事高压极端条件材料制备与物性研究. E-mail：wangxiao@iphy.ac.cn

通讯作者:
龙有文（1979－），男，博士，研究员，主要从事新型高压磁电量子功能材料研究. E-mail：ywlong@iphy.ac.cn

中图分类号: O469; O521.2
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出版历程
- 收稿日期: 2023-11-08
- 修回日期: 2023-12-15
- 网络出版日期: 2024-02-04
- 刊出日期: 2024-02-05

A-Site Ordered Quadruple Perovskite Oxides: Structures, Properties and Prospects

WANG Xiao^1
,,
LIU Zhehong¹,
LU Dabiao^{1, 2},
PI Maocai^{1, 2},
PAN Zhao¹,
LONG Youwen^{1, 2, 3,*
, ,}

1.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
2.
School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
3.
Songshan Lake Materials Laboratory, Dongguan 523808, Guangdong, China

摘要

摘要: A位有序四重钙钛矿氧化物$\rm AA'_3 B^{\;}_4 O^{\;}_{12} $具有丰富的物理性质和优异的材料性能，是当今凝聚态物理和材料科学的重要研究对象。相较于简单的ABO₃型钙钛矿，在A位有序四重钙钛矿氧化物中，3/4的A位离子被过渡金属离子A′所取代，形成了1∶3的A/A′有序结构。因此，A位有序四重钙钛矿氧化物中的磁-电相互作用不再局限于B位子晶格内部，新颖的A′-A′、A′-B等磁-电相互作用也随之产生，从而展现出许多新现象和新物理机制，并为未来的实际应用提供了材料基础。围绕几种具有代表性的A位有序四重钙钛矿氧化物，回顾其研究脉络，对其晶体结构、物理性质和内在机理进行简单介绍，并对这类材料体系的研究方向和应用前景做出一些展望。
- 高压制备 /
- 钙钛矿氧化物 /
- 介电性 /
- 电荷有序 /
- 多铁性 /
- 半金属
Abstract: A-site ordered quadruple perovskite oxides with a formula as $\rm AA'_3 B^{\;}_4 O^{\;}_{12}$ exhibit multiple physical properties and superior performances, thus act as important subjects of current condensed matter physics and material science. Compared to the simple ABO₃ perovskite, in the A-site ordered quadruple perovskite three quarters of the A atoms are replaced by transition metal Aʹ, forming ordered A/Aʹ occupancy with a 1∶3 ratio. As a result, the electric and magnetic interactions such as Aʹ-Aʹ and Aʹ-B can occur, leading to novel phenomena and new physics. Here we focus on several representative A-site ordered quadruple perovskites, recall their researches, briefly introduce their structures, physical properties and inner mechanisms, and discuss the opportunities for both fundamental studies and potential applications.
- high-pressure synthesis /
- perovskite oxide /
- dielectricity /
- charge order /
- multiferroics /
- half metal

HTML全文

图 1 (a) $\rm ABO^{\;}_3 $型钙钛矿、(b) A位有序四重钙钛矿$\rm AA'_3 B^{\;}_4 O^{\;}_{12} $和(c) A位有序四重钙钛矿$\rm AA'_3 B^{\;}_2 B'_2 O^{\;}_{12} $的结构示意图

Figure 1. Schematic crystal structures of (a) $\rm ABO^{\;}_3 $ perovskite, A-site ordered perovskites (b) $\rm AA'_3 B^{\;}_4 O^{\;}_{12} $ and (c) $\rm AA'_3 B^{\;}_2 B'_2 O^{\;}_{12} $

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图 2 (a) Aʹ的氧配位示意图（黄色表示Aʹ离子，红色表示O离子，颜色由深至浅表示Aʹ―O键长由短至长），(b) AʹO₄平面四边形晶体场示意图（10Dq为d轨道（t_2g、e_g）的劈裂，Δt_2g、Δe_g分别为t_2g（xy、xz、yz）和e_g（x²–y²、z²–r²）轨道的劈裂），(c) BO₆八面体的倾斜（蓝色表示B离子，红色表示O离子）

Figure 2. (a) Coordination of the Aʹ site, the Aʹ ion is displayed in yellow, the O anions are displayed in red, and the different colors of O indicate the different Aʹ―O bond lengths; (b) crystal field of AʹO₄ square planar, the 10Dq represents the split of the d orbit (t_2g, e_g), the Δt_2g and Δe_g represent the split of the t_2g (xy, xz, yz) and e_g (x²–y², z²–r²) orbits, respectively; (c) tilt of the BO₆ octahedra, the B ions are displayed in blue, and the O anions are displayed in red

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图 3 (a) CaCu₃Ti₄O₁₂的εʹ和tan δ随温度的变化关系（2条曲线分别为2个样品的测试数据）^[27]；(b) 不同频率下εʹ、tan δ和ω₀随温度的变化关系^[27]；(c) εʹ随频率的变化关系；(d) 弛豫时间（τ）随温度的变化关系（10 K的τ为预测值）^[29]

Figure 3. (a) Temperature-dependent εʹ and tan δ of two CaCu₃Ti₄O₁₂ samples^[27]; (b) temperature-dependent εʹ, tan δ and ω₀ at selected frequencies^[27]; (c) frequency-dependent εʹ of CaCu₃Ti₄O₁₂ and (d) the relaxation time (τ) as a function of 1/T, the legend also gives the estimated τ at 10 K^[29]

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图 4 (a) 本征与非本征因素构成的等效电路示意图，(b) 该等效电路的εʹ和εʹʹ随频率的变化曲线^[33]

Figure 4. (a) Equivalent circuit that describes the main features of the dielectric response; (b) frequency-dependent dielectric response^[33]

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图 5 (a) CaCu₃Ti₄O₁₂多晶表面形貌，(b) 晶粒内和晶粒间的I-V曲线^[42]

Figure 5. (a) Surface morphology with patterned gold electrodes of CaCu₃Ti₄O₁₂; (b) I-V characteristics within single grains and across individual grain boundaries^[42]

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图 6 LaCu₃Fe₄O₁₂在T_N=393 K的多种转变：(a) Cu―O键、Fe―O键的键长随温度的变化关系；(b) 体积随温度的变化关系；(c) 穆斯堡尔（Mössbauer）谱的光吸收随运动速度的变化关系；(d) 磁化率（χ）和电阻率（ρ）随温度的变化曲线（插图为磁矩M随温度的变化曲线）^[7]

Figure 6. Multiple transitions of LaCu₃Fe₄O₁₂ at T_N=393 K: (a) temperature-dependent Cu―O and Fe―O bond lengths; (b) temperature-dependent negative thermal expansion; (c) Mössbauer spectra, the velocity-dependent absorption; (d) temperature-dependent magnetic susceptibility (χ) and resistivity (ρ), the inset displays the temperature-dependent magnetization (M)^[7]

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图 7 (a) LnCu₃Fe₄O₁₂的电荷有序形式总览；(b) LnCu₃Fe₄O₁₂在相变温度附近的体积随温度的变化曲线；(c) Ln和Fe的键合状态（d为价键求和（bond valence sum，BVS）计算得到的价态与自由离子价态之差，d < 0表示欠键合，d > 0表示过键合）^[61]

Figure 7. (a) An overview of charge order of LnCu₃Fe₄O₁₂; (b) temperature-dependent volume of LnCu₃Fe₄O₁₂; (c) correlation between d_Ln and d_Fe (d is the difference between bond valence sum (BVS) and ionic valence state. d < 0 indicates underbonding and d > 0 indicates overbonding.)^[61]

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图 8 (a) ACu₃Fe₄O₁₂体系电荷有序能级示意图^[62]；(b) 当体积为原体积的102%、100%、96%、90%、88%、80%、78%时的电荷分布（不同颜色表示不同位置电荷相对密度差异Δn(r)）^[63]

Figure 8. (a) Schematic diagram of charge order in the ACu₃Fe₄O₁₂ compounds^[62]; (b) computed charge densities for volumes of 102%, 100%, 96%, 90%, 88%, 80% and 78%, the colors represent the charge density differences Δn(r)^[63]

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图 9 (a) PbCoO₃^[66]、(b) Mn₂O₃^[67]以及(c) Fe₂O₃^[68]的相图

Figure 9. Phase diagrams of (a) PbCoO₃^[66], (b) Mn₂O₃^[67], and (c) Fe₂O₃^[68]

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图 10 磁电耦合多铁性材料中磁场对电极化的调控以及电场对磁化的调控示意图^[75]

Figure 10. Controlling of polarization/magnetization by magnetic/electric field in magnetoelectric multiferroics^[75]

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图 11 LaMn₃Cr₄O₁₂的晶格结构、NPD图谱和磁结构^[9]

Figure 11. Crystal structure, NPD pattern and magnetic structure of LaMn₃Cr₄O₁₂^[9]

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图 12 LaMn₃Cr₄O₁₂在不同磁场下的热释电电流、电极化和介电常数随温度的变化关系^[9]

Figure 12. Pyroelectric current, electric polarization and dielectric constant of LaMn₃Cr₄O₁₂ under selected magnetic fields^[9]

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图 13 BiMn₃Cr₄O₁₂通过不同的极化过程实现的 4 种极化态^[86]

Figure 13. Four states of BiMn₃Cr₄O₁₂ from different poling procedures^[86]

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图 14 5 K时SmMn₃Cr₄O₁₂在不同磁场和电场配置下的电极化随磁场大小的变化关系^[88]

Figure 14. Magnetic field dependent polarization of SmMn₃Cr₄O₁₂ at 5 K measured at H//E and H⊥E configurations^[88]

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图 15 电极化在罗马面上的转动路径和实验测量结果（ψ为外加磁场H与极化电场E的夹角）^[92]

Figure 15. Induced fundamental polarization trajectories on Roman surface and related experiment results, ψ represents the angle between H and E^[92]

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图 16 (a) La_0.7Sr_0.3MnO₃的能带示意图，(b) 自旋分辨光电子能谱测量结果^[97]

Figure 16. (a) Schematic band structure and (b) spin-resolved photoemission spectra of La_0.7Sr_0.3MnO₃^[97]

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图 17 Sr₂FeMoO₆的电阻率和磁化强度随磁场的变化关系^[99]

Figure 17. Field-dependent electrical resistivity and magnetization of Sr₂FeMoO₆^[99]

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图 18 CaCu₃Fe₂Re₂O₁₂的 (a) 磁化率χ随温度的变化曲线、(b) 电阻率和磁化强度随磁场的变化曲线以及 (c) 能带计算结果^[11]

Figure 18. (a) Temperature-dependent magnetic susceptibility, (b) field-dependent magnetization and magnetoresistance, and (c) calculated band structure from first principles of CaCu₃Fe₂Re₂O₁₂^[11]

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图 19 LaCu₃Fe₂Re₂O₁₂的 (a) 磁化率随温度的变化曲线、(b) 磁化强度随磁场的变化曲线、(c) 能带计算结果以及 (d) 半金属综合性能指标η与其他半金属氧化物的比较^[101]

Figure 19. (a) Temperature-dependent magnetic susceptibility, (b) field-dependent magnetization, (c) calculated band structure from first principles and (d) overall performance factor η of LaCu₃Fe₂Re₂O₁₂ (The η values of some selected half-metallic oxides are displayed for comparison.)^[101]

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图 20 ACu₃Fe₂Os₂O₁₂体系不同 A 位离子对费米面的调控^[108]

Figure 20. Regulation of the Fermi surface by the nonmagnetic A-site ions in the ACu₃Fe₂Os₂O₁₂ system^[108]

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图 21 全过渡金属A位有序四重钙钛矿氧化物$\rm AA'_3 B^{\;}_2 B'_2 O^{\;}_{12} $丰富的磁-电相互作用（红色代表氧离子）

Figure 21. Multiple magnetic and electric interactions in the transition-metal-only A-site ordered quadruple perovskite oxide, the oxygen ions are shown in red

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