压力诱导下CsGeBr<sub>3</sub>的结构相变

曲佳; 王弈铭; 王欣; 杨文革

doi:10.11858/gywlxb.20230769

压力诱导下CsGeBr₃的结构相变

doi: 10.11858/gywlxb.20230769

曲佳^{1, 2,},
王弈铭²,
王欣^1,*, ,,
杨文革^2,*, ,

1.
吉林大学物理学院，超硬材料国家重点实验室, 吉林长春　130012
2.
北京高压科学研究中心, 上海　201203

详细信息

作者简介:
曲　佳（1995－），女，博士研究生，主要从事卤化物钙钛矿的高压物性研究.E-mail：qujia19@mails.jlu.edu.cn

通讯作者:
王　欣（1973－），男，博士，教授，主要从事极端条件下材料的物性研究. E-mail：xin_wang@jlu.edu.cn

杨文革（1968－），男，博士，教授，主要从事高压材料的结构和物性研究. E-mail：yangwg@hpstar.ac.cn

中图分类号: O521.2
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- 文章访问数: 20
- HTML全文浏览量: 5
- PDF下载量: 9
出版历程
- 收稿日期: 2023-10-25
- 修回日期: 2023-12-15
- 录用日期: 2023-12-25
- 网络出版日期: 2024-07-19

Pressure-Induced Structural Phase Transition in Halide Perovskite CsGeBr₃

QU Jia^{1, 2
,},
WANG Yiming²,
WANG Xin^{1,*
, ,},
YANG Wenge^{2,*
, ,}

1.
State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012, Jilin, China
2.
Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, China

摘要

摘要: 近年来，压力下卤化物钙钛矿成为新的研究热点，呈现出许多优异的电学和光学等特性。高压下钙钛矿结构演变研究是所有物性研究的基石和重点。利用金刚石对顶砧压机，结合原位高压同步辐射X射线衍射、原位高压拉曼光谱、紫外-可见-近红外分光光度计测量技术和第一性原理计算，对全无机卤化物钙钛矿CsGeBr₃在高压下的结构演变进行了系统研究。结果表明：CsGeBr₃在常压下是菱方$ R3m $结构；在1 GPa时，CsGeBr₃发生菱方$ R3m $到立方$ Pm\overline{3}m $的结构相变；在更高的压力下保持立方结构；菱方$ R3m $到立方$ Pm\overline{3}m $的相变是可逆的。研究结果为进一步探索卤化物钙钛矿在压力下的性质、拓展其应用前景提供了重要的科学依据。
- 高压 /
- CsGeBr₃ /
- 结构相变 /
- 卤化物钙钛矿
Abstract: In recent years, pressure-induced physical properties of halide perovskites have attracted significant research interests due to their excellent optical and electronic properties. The study of the structural evolution of perovskite under compression is the foundation and key point of all physical property researches. In this paper, we systematically investigated the structural evolution of the all-inorganic halide perovskite CsGeBr₃ under compression using in situ high-pressure synchrotron X-ray diffraction, in situ high-pressure Raman spectroscopy, ultraviolet/visible/near-infrared spectrophotometry, and first-principles calculations. Our results show that CsGeBr₃ undergoes a reversible rhombohedral $ R3m $ to cubic $ Pm\overline{3}m $ structural phase transition at 1 GPa, and the cubic $ Pm\overline{3}m $ phase maintains at higher pressures. This study provides important scientific basis for further exploration of the properties and applications of halide perovskites under compression.
- high pressure /
- CsGeBr₃ /
- structural phase transition /
- halide perovskite

HTML全文

图 1 (a) CsGeBr₃的SEM和EDS图像，(b) 常压下CsGeBr₃的XRD谱与PDF标准卡的对比结果

Figure 1. (a) SEM and EDS images of CsGeBr₃；(b) XRD pattern of CsGeBr₃ under ambient pressure compared with PDF card

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图 2 (a) CsGeBr₃的原位XRD谱随压力的变化，(b) 不同压力下CsGeBr₃的XRD环，(c) 不同压力下CsGeBr₃的XRD谱的Rietveld精修结果

Figure 2. (a) In situ XRD patterns of CsGeBr₃ as a function of pressure; (b) XRD rings of CsGeBr₃ at different pressures; (c) results of Rietveld refinement of XRD patterns of CsGeBr₃ at different pressures

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图 3 (a) CsGeBr₃的晶胞体积随压力的变化（低压相和高压相的p-V曲线均用Birch-Murnaghan状态方程拟），(b) CsGeBr₃的α、β和d_Ge-Br/(a/2)随压力的变化，(c) CsGeBr₃在常压和高压下的晶体结构

Figure 3. (a) Formula unit cell volume of CsGeBr₃ as a function of pressure (The p-V curves for low-pressure phase and high-pressure phase are both fitted with the Birch-Murnaghan equation of state); (b) α, β and d_Ge-Br/(a/2) of CsGeBr₃ at various pressures; (c) crystal structure of CsGeBr₃ under ambient pressure and high-pressure

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图 4 (a) 不同压力下CsGeBr₃的原位拉曼光谱，(b) 30～250 cm⁻¹范围内拉曼峰位随压力的变化，(c) 单晶CsGeBr₃的原位紫外-可见-近红外吸收谱，(d) CsGeBr₃在不同压力下的光学带隙（插图为常压下的Tauc图），(e) 加压过程中CsGeBr₃的光学影像

Figure 4. (a) In situ Raman spectra of CsGeBr₃ at diffrent pressures; (b) pressure dependence of the Raman peak positions in the wavenumber range of 30–250 cm⁻¹; (c) in situ ultraviolet-visible-near infrared (UV-Vis-NIR) absorption spectra of single crystal CsGeBr₃ under compression; (d) pressure dependence of the bandgaps of CsGeBr₃ (the illustration shows the Tauc plot for ambient pressure); (e) optical photos of CsGeBr₃ during compression

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图 5 (a) 3阶Birch-Murnaghan状态方程拟合的E-V曲线，(b) $ R3m $和$ Pm\overline{3}m $相的焓差ΔH与压力的变化关系

Figure 5. (a) E-V curve fitted by third-order Birch-Murnaghan EOS；(b) relative enthalpies ΔH of $ R3m $ and $ Pm\overline{3}m $ phases vs. pressure

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表 1 不同压力下 CsGeBr₃的XRD谱的Rietveld精修结果

Table 1. Rietveld refinement results of XRD patterns for CsGeBr₃ at different pressures

Pressure/GPa	Crystal system	Space group	a/Å	α/(°)		β/(°)
0.80	Rhombohedral	R3m	5.54443(12)	89.1376(33)		94.0181(30)
1.43	Cubic	${ Pm\overline{3}m }$	5.46294(19)	90		90
3.01	Cubic	$ {Pm\overline{3}m }$	5.35809(14)	90		90

Pressure/GPa	d_Ge-Br/Å	d'_Ge-Br/Å	V/Å³	Z	R_p/%	R_wp/%
0.80	2.58519(6)	2.96827(6)	170.382(11)	1	1.16	1.89
1.43	2.73147(10)		163.034(17)	1	1.53	2.45
3.01	2.67905(7)		153.826(12)	1	1.12	1.82

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