铜基稀土过渡金属钙钛矿La1–xNdxCuO3（0≤x≤1）的高压合成

孙浩; 叶鹏达; 刘雨微; 金美玲; 李翔

doi:10.11858/gywlxb.20230784

铜基稀土过渡金属钙钛矿La_1–xNd_xCuO₃（0≤x≤1）的高压合成

doi: 10.11858/gywlxb.20230784

孙浩^1,,
叶鹏达²,
刘雨微¹,
金美玲^1,*, ,,
李翔^1,*, ,

1.
北京理工大学物理学院，先进光电量子结构设计与测量教育部重点实验室, 北京　100081
2.
北京理工大学机电学院，精工书院, 北京　100081

基金项目: 国家自然科学基金（12174025，11904020）

详细信息

作者简介:
孙　浩（1995－），男，博士研究生，主要从事极端高压条件下凝聚态物理研究. E-mail：haosun@bit.edu.cn

通讯作者:
金美玲 (1988－)，女，博士，主要从事极端高压条件下凝聚态物理研究. E-mail：jinml@bit.edu.cn

李　翔（1985－），男，博士，教授，主要从事极端高压条件下凝聚态物理研究. E-mail：xiangli@bit.edu.cn

中图分类号: O521.2
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出版历程
- 收稿日期: 2023-11-08
- 修回日期: 2023-12-30
- 录用日期: 2024-01-02
- 刊出日期: 2024-02-05

High-Pressure Synthesis of Copper-Based Rare-Earth Perovskite La_1–xNd_xCuO₃ (0≤x≤1)

SUN Hao^1
,,
YE Pengda²,
LIU Yuwei¹,
JIN Meiling^{1,*
, ,},
LI Xiang^{1,*
, ,}

1.
Key Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement, School of Physics, Beijing Institute of Technology, Beijing 100081, China
2.
Jing Gong College, School of Mechatronical Engineering, Beijing Institute of Technology, Beijing 100081, China

摘要

摘要: 在高温高压条件下，利用自主设计加工的Walker型高压组件合成新型铜基稀土过渡金属钙钛矿La_1–xNd_xCuO₃（0≤x≤1）。结构精修结果表明：La_1–xNd_xCuO₃（0≤x≤0.4）具有菱方结构，空间群为$R\overline 3 c $；当0.5≤x≤0.7时，该体系表现出$R\overline 3 c $菱方结构与Pnma正交结构共存的混合相；进一步增加Nd的掺杂比例，当0.8≤x≤1时样品具有单一的Pnma正交结构。获得了La_1–xNd_xCuO₃（0≤x≤1）的完整结构相图，为深入研究稀土-3d过渡金属氧化物的磁性、金属-绝缘体相变等物性演化规律提供了新的材料选项。
- 高压合成 /
- 铜基稀土-3d过渡金属氧化物 /
- 金属绝缘体相变
Abstract: The copper-based rare-earth perovskites La_1–xNd_xCuO₃(0≤x≤1) have been synthesized in the two-stage Walker-type high-pressure apparatus. The refined crystal structure results revealed that La_1–xNd_xCuO₃ (0≤x≤0.4) adopts a rhombohedral structure with the space group $R\overline 3 c $. When 0.5≤x≤0.7, a mixed phase with both $R\overline 3 c $ rhombohedral and Pnma orthorhombic structures was observed in the system. With a further increase in Nd³⁺ doping, the system exhibits a single Pnma orthorhombic phase when x=0.8, 0.9 and 1. A comprehensive structural phase diagram of La_1–xNd_xCuO₃ (0≤x≤1) was established in this study, providing a new material platform for investigating the magnetic properties, metal-insulator transitions, and other physical property evolutions in rare-earth 3d transition metal oxides.
- high-pressure synthesis /
- copper-based rare-earth 3d transition metal oxides /
- metal-insulator transitions

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图 1 (a) 高压合成组件侧面图；(b) 高压合成组件剖面图；(c)高压合成组件的校压曲线；(d) 高压合成组件在14 GPa下的标温曲线

Figure 1. (a) Side view of the high-pressure assembly; (b) sectional drawing of the high-pressure assembly; (c) pressure calibration of high-pressure assembly; (d) temperature calibration of high-pressure assembly under 14 GPa

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图 2 (a) LaCuO₃、(b) La_0.5Nd_0.5CuO₃、(c) La_0.2Nd_0.8CuO₃和(d) NdCuO₃ 的PXRD Rietveld 精修谱图

Figure 2. Rietveld refinement of PXRD patterns of (a) LaCuO₃, (b) La_0.5Nd_0.5CuO₃, (c) La_0.2Nd_0.8CuO₃ and (d) NdCuO₃

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图 3 La_1–xNd_xCuO₃（0≤x≤1）的结构相图

Figure 3. Structural phase diagram of La_1–xNd_xCuO₃ (0≤x≤1)

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表 1 La_1–xNd_xCuO₃ （0≤x≤1）样品合成的压力和温度优化条件

Table 1. Pressure and temperature conditions of synthesizing La_1–xNd_xCuO₃ (0≤x≤1)

Sample	Pressure/GPa	Temperature/℃	Time/min
LaCuO₃	6	1000	30
La_0.9Nd_0.1CuO₃	6	1000	30
La_0.8Nd_0.2CuO₃	6	1000	30
La_0.7Nd_0.3CuO₃	10	1000	30
La_0.6Nd_0.4CuO₃	10	1000	30
La_0.5Nd_0.5CuO₃	10	1000	30
La_0.4Nd_0.6CuO₃	10	1000	30
La_0.3Nd_0.7CuO₃	14	1000	30
La_0.2Nd_0.8CuO₃	14	1000	30
La_0.1Nd_0.9CuO₃	14	1000	30
NdCuO₃	14	1000	30

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表 2 La_1–xNd_xCuO₃（0≤x≤1）的晶格参数

Table 2. Structural parameters of La_1–xNd_xCuO₃ (0≤x≤1)

Sample	Space group	Lattice parameters/Å	R_P/%	R_WP/%	Chi2
LaCuO₃	$R\overline 3 c $	a=b=5.4976(6), c=13.2062(9)	3.05	5.59	7.01
La_0.9Nd_0.1CuO₃	$R\overline 3 c $	a=b=5.4976(9), c=13.1917(5)	1.45	1.92	1.10
La_0.8Nd_0.2CuO₃	$R\overline 3 c $	a=b=5.4988(9), c=13.1732(7)	1.25	1.68	0.79
La_0.7Nd_0.3CuO₃	$R\overline 3 c $	a=b=5.4961(1), c=13.1625(7)	1.91	2.73	2.48
La_0.6Nd_0.4CuO₃	$R\overline 3 c $	a=5.4933(9), c=13.1326(6)	2.41	4.14	7.09
La_0.5Nd_0.5CuO₃	Phase 1: $R\overline 3 c $ (36.43%)	a=b=5.4627(1), c=13.2988(9)	4.23	5.85	2.42
La_0.5Nd_0.5CuO₃	Phase 2: Pnma (63.57%)	a=6.1821(1), b=7.3597(8), c=5.4318(7)	4.23	5.85	2.42
La_0.4Nd_0.6CuO₃	Phase 1: $R\overline 3 c $ (43.49%)	a=b=5.4571(7), c=13.2982(1)	1.25	1.68	0.79
La_0.4Nd_0.6CuO₃	Phase 2: Pnma (56.51%)	a=6.5015(2), b=7.6552(6), c=5.3354(4)	1.25	1.68	0.79
La_0.3Nd_0.7CuO₃	Phase 1: $R\overline 3 c $ (44.42%)	a=b=5.4542(6), c=13.3191(9)	3.76	4.81	1.43
La_0.3Nd_0.7CuO₃	Phase 2: Pnma (55.58%)	a=6.3189(6), b=7.2736(7), c=5.3706(8)	3.76	4.81	1.43
La_0.2Nd_0.8CuO₃	Pnma	a=6.3197(8), b=7.2408(1), c=5.3561(1)	7.75	9.92	2.20
La_0.1Nd_0.9CuO₃	Pnma	a=6.3045(3), b=7.2421(7), c=5.3462(9)	1.54	2.24	1.66
NdCuO₃	Pnma	a=6.3039(2), b=7.2176(2), c=5.3334(5)	1.72	2.48	1.42

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