Pressure-Induced Structural Phase Transition in Halide Perovskite CsGeBr3
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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。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.-
Key words:
- high pressure /
- CsGeBr3 /
- structural phase transition /
- halide perovskite
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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dGe-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 dGe-Br/(a/2) of CsGeBr3 at various pressures; (c) crystal structure of CsGeBr3 under ambient pressure and high-pressure
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
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 dGe-Br/Å d'Ge-Br/Å V/Å3 Z Rp/% Rwp/% 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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