6H型六方钙钛矿相BaGeO<sub>3</sub>的高温高压合成

谢亚飞; 姜昌国; 罗兴丽; 谭大勇; 肖万生

doi:10.11858/gywlxb.20210761

6H型六方钙钛矿相BaGeO₃的高温高压合成

doi: 10.11858/gywlxb.20210761

谢亚飞^{1, 2, 3, 4,},
姜昌国^{1, 2, 3, 4},
罗兴丽^{1, 2, 3, 4},
谭大勇^{1, 2, 3},
肖万生^{1, 2, 3,*, ,}

1.
中国科学院广州地球化学研究所矿物学与成矿学重点实验室，广东广州　510640
2.
广东省矿物物理与材料研究开发重点实验室，广东广州　510640
3.
中国科学院深地科学卓越创新中心，广东广州　510640
4.
中国科学院大学，北京　100049

基金项目: 国家自然科学基金（41572030，41372047）；中国科学院战略性先导科技专项（B类）（XDB18010403）

详细信息

作者简介:
谢亚飞（1996－），男，硕士研究生，主要从事高压矿物学研究. E-mail：xieyafei@gig.ac.cn

通讯作者:
肖万生（1968－），男，博士，研究员，主要从事高压矿物学研究. E-mail：wsxiao@gig.ac.cn

中图分类号: O521.2; P311.9
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出版历程
- 收稿日期: 2021-03-29
- 修回日期: 2021-04-14

Synthesis of 6H-Type Hexagonal Perovskite Phase of BaGeO₃ at High Temperature and High Pressure

XIE Yafei^{1, 2, 3, 4
,},
JIANG Changguo^{1, 2, 3, 4},
LUO Xingli^{1, 2, 3, 4},
TAN Dayong^{1, 2, 3},
XIAO Wansheng^{1, 2, 3,*
, ,}

1.
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
2.
Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640, Guangdong, China
3.
CAS Center for Excellence in Deep Earth Science, Guangzhou 510640, Guangdong, China
4.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 利用金刚石对顶砧高压装置，结合显微激光双面加热技术，对BaGeO₃开展了高温高压实验研究。常温常压下赝硅灰石相的BaGeO₃于12 GPa左右开始非晶化。进一步加压到22 GPa并对已完全非晶化的BaGeO₃样品进行(1800 ± 200) K的高温处理，拉曼光谱显示其转变成一种未见报道的高压新相。在0～17.4 GPa压力范围对BaGeO₃高压新相开展同步辐射X射线衍射测试，其衍射谱可以用6H型六方钙钛矿相进行指标化，并且卸压到常压时仍保持稳定。以6H型钙钛矿相为结构模型，分别对17.4 GPa和常压下的X射线衍射谱进行Rietveld结构精修，获得其结构参数。应用二阶Birch-Murnaghan状态方程拟合实验体积-压力数据，得到其体弹模量K₀ = 150(2) GPa和零压晶胞体积V₀ = 373.0(3) Å³。在实验研究的基础上，对6H型钙钛矿相BaGeO₃进行第一性原理理论计算，所得不同压力下的晶格常数和体积数据与实验结果符合得很好，状态方程参数K₀ = 153(1) GPa，V₀ = 374.2(1) Å³。20.0 GPa时计算的拉曼光谱也很好地描述了拉曼实验测量结果。研究结果补充了赝硅灰石相BaGeO₃在更高温压条件下的结构相转变。6H型钙钛矿相BaGeO₃的获得为进一步表征该相的物理化学性质奠定了基础，为开发高性能钙钛矿结构锗酸盐材料提供了可能性，同时对于理解硅酸盐钙钛矿结构的相变规律及稳定性、地球下地幔物理化学性质及其变化等具有重要的指示意义。
- BaGeO₃ /
- 6H型六方钙钛矿相 /
- Rietveld结构精修 /
- 拉曼光谱 /
- 高温高压
Abstract: Barium germanate (BaGeO₃) was studied using double-sided laser-heating diamond anvil cell (LHDAC). At ambient conditions, BaGeO₃ has a pseudowollastonite structure. At about 12 GPa, BaGeO₃ crystal begin to translate into an amorphous phase. The amorphous BaGeO₃ was further pressurized to about 22 GPa and then heated at (1800 ± 200) K conditions. Raman spectra shows the amorphous BaGeO₃ transforms into a new high pressure phase, which has not been reported so far. The new high pressure phase of BaGeO₃ was further measured with the synchrotron radiation X-ray diffraction in the pressure ranges of 0−17.4 GPa. The diffraction patterns can be indexed with a 6H-type hexagonal perovskite structure and this structure remained stable as the pressure unloading to ambient pressure. In order to obtain the structural parameters of the new high pressure phase of BaGeO₃, the X-ray diffraction patterns of 17.4 GPa and ambient pressure were refined with a model structure of 6H-type perovskite using the Rietveld method. The experimental pressure-volume data was fitted with the second-order Birch-Murnaghan equation of state, and obtained the volume bulk modulus and zero-pressure unit-cell volume are K₀ = 150(2) GPa and V₀ = 373.0(3) A³ respectively. On the basis of the experimental results in this study, we also carried out the first-principle theoretical calculation on the 6H-type perovskite BaGeO₃. The calculated lattice constants and volume with the corresponding pressures are good agreement with the experimental results. Furthermore, the calculated volume bulk modulus and zero-pressure unit-cell volume are K₀ = 153(1) GPa, V₀ = 374.2(1) A³ respectively. The calculated Raman spectra at 20.0 GPa is also well consistent with the experimental results. This study not only complements the structural phase transition of pseudowallastonite BaGeO₃ at high temperature and high pressure, but also builds a solid foundation for further characterizing the physical and chemical properties of pseudowallastonite BaGeO₃, and gives a chance to develop the perovskite structured germanate functional materials. In addition, this study has an important indicative significance for us to understand the phase transition rule and stability of silicate perovskite, the physical and chemical properties and changes of Earth's lower mantle.
- BaGeO₃ /
- 6H-type hexagonal perovskite phase /
- Rietveld structure refinement /
- Raman spectra /
- high temperature and high pressure

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图 1 赝硅灰石结构(a)和6H型六方钙钛矿结构(b)示意图（大绿球、中紫球、小红球分别代表Ba、Ge、O原子）

Figure 1. Schematic of pseudowollastonite structure (a) and hexagonal perovskite (6H-type) structure (b) (Ba, Ge, O atoms are shown as big green, medium purple, small red spheres, respectively.)

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图 2 BaGeO₃高压新相合成过程中代表性拉曼光谱与计算拉曼光谱

Figure 2. Representative Raman spectra and calculated Raman spectra in the synthesis process of new high pressure phase BaGeO₃

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图 3 6H型六方钙钛矿相BaGeO₃在卸压过程中的代表性XRD谱

Figure 3. Representative XRD patterns of hexagonal perovskite phase BaGeO₃ (6H-type) on decompression

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图 4 6H型六方钙钛矿相BaGeO₃在常压和17.4 GPa的Rietveld结构精修图

Figure 4. Rietveld refinement XRD patterns of hexagonal perovskite phase BaGeO₃ (6H-type) at ambient pressure and 17.4 GPa

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图 5 6H型六方钙钛矿相BaGeO₃的晶面间距和晶轴与压力的关系

Figure 5. Pressure dependence of d-spacing, a-axis and c-axis of hexagonal perovskite phase BaGeO₃ (6H-type)

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图 6 实验和计算得到的6H型六方钙钛矿相BaGeO₃的体积-压力关系

Figure 6. Experimental and calculated p-V relationship of hexagonal perovskite phase BaGeO₃ (6H-type)

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表 1 6H型六方钙钛矿相BaGeO₃在常压和17.4 GPa的结构参数

Table 1. Structural parameters of hexagonal perovskite phase BaGeO₃ (6H-type) at ambient pressure and 17.4 GPa

Structural parameters at 17.4 GPa					Structural parameters at 0.1 MPa
Atom	Site	x	y	z	Atom	Site	x	y	z
Ba1	2b	0	0	0.2500	Ba1	2b	0	0	0.2500
Ba2	4f	0.3333	0.6667	0.0896(5)	Ba2	4f	0.3333	0.6667	0.0930(5)
Ge1	2a	0	0	0	Ge1	2a	0	0	0
Ge2	4f	0.3333	0.6667	0.8392(5)	Ge2	4f	0.3333	0.6667	0.8427(5)
O1	6h	0.5178(27)	0.0360(5)	0.2500	O1	6h	0.4976(23)	−0.0050(5)	0.2500
O2	12k	0.8342(27)	0.6680(5)	0.0730(5)	O2	12k	0.8140(23)	0.6280	0.0765

Bond lengths at 17.4 GPa/Å					Bond lengths at 0.1 MPa/Å
Ge1―O2	Ge2―O2		Ge2―O1		Ge1―O2	Ge2―O2		Ge2―O1
1.837(19) × 6	1.961(16) × 3		1.835(17) × 3		2.088(17) × 6	1.808(14) × 3		2.075(15) × 3
Note: Numbers in parentheses indicate standard deviation.

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表 2 计算得到的6H型六方钙钛矿相BaGeO₃在20.0 GPa下的拉曼振动模

Table 2. Calculated Raman vibrational modes of hexagonal perovskite phase BaGeO₃ (6H-type) at 20.0 GPa cm⁻¹

E_2g	E_1g	A_1g	E_2g	E_1g	E_2g	E_2g	E_1g	A_1g	E_1g
88	131	142	158	202	213	242	264	381	395

E_2g	E_2g	E_1g	A_1g	E_2g	E_2g	E_1g	A_1g	A_1g
399	429	431	444	529	576	578	698	840

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