Reciprocating Phase Transitions Behavior of Germanium under High Pressure
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摘要: 利用基于六面顶压机的二级6-8型高压装置和金刚石对顶砧技术，结合北京同步辐射光源高压原位X射线衍射技术，对锗在高压下的相演化行为以及晶粒尺寸变化规律进行了系统的研究，发现往复压致相变对锗的晶粒细化有明显效果，同时在经历往复压致相变5次的块体样品中发现了非晶区域，为纳米结构和非晶材料制备提供了一种新的思路。Abstract: Based on a two-stage multi anvil apparatus, with diamond anvil cell device, combined with the high-pressurein situX-ray diffraction (XRD) technology of Beijing Synchrotron Radiation Light Source, the phase transitions and grain size variation behaviors of germanium under high pressure were systematically investigated. It is found that the reciprocating phase transitions indeed have obvious effects on the grain refinement of germanium. At the same time, the amorphous regions are found in the bulk samples that have undergone five times reciprocating phase transitions, which provides a new way for the preparation of nanostructured and amorphous materials.
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图 2 立方金刚石结构锗的晶胞图(a)以及初始样品的XRD谱(b)和光学照片(c)
Figure 2. (a) Unit cell diagram of cubic diamond-structured germanium, (b) XRD pattern of the initial sample, (c) optical microscope photograph of the initial sample
图 3 (a) 实验组装示意图（用MgO八面体对样品进行包裹）；(b) 含有二级增压装置的6×8 MN六面顶压机示意图（组装好的样品和MgO八面体放置在由8个碳化钨硬质合金截角立方块合围成的八面体压腔的中心位置，通过二级增压装置对样品施加高压）；(c) 实验中的压力-时间曲线（5次往复加压-卸压实验曲线）
Figure 3. (a) Schematic diagram of the assembly used in the experiment, the sample was wrapped within a magnesia octahedron; (b) schematic diagram of a 6×8 MN cubic press with a secondary booster device, the assembled sample was placed in the center of the carbide blocks, and subjected to high pressure through a secondary booster device; (c) pressure-time curve used during the experiment (the above figure is the curve of the five-cycle reciprocating experiment)
图 4 (a) 经历3次往复压致相变样品的 SEM 图像（晶粒细化到几百纳米）；(b) 经历5次往复压致相变样品的SEM图像（最小晶粒细化到几十纳米）；(c) 初始样品的 SEM 图像
Figure 4. (a) SEM image of the sample undergoing three cycles of reciprocating pressure-induced phase transitions, and the grains have been refined to several hundreds of nanometers; (b) SEM image of the sample undergoing five cycles of reciprocating pressured-induced phase transitions, and the smallest grains have been refined to several tens of nanometers; (c) SEM image of the initial sample
图 5 往复5次所得样品的XRD谱和Rietveld拟合曲线
Figure 5. XRD pattern and Rietveld fitting curve of the sample undergoing five cycles of reciprocating pressing
图 6 (a) 往复5次所得样品的TEM图像（可见大片非晶区域）；(b) 图6(a)中红圈区域的SAED图像（出现明显的非晶环）；(c) 图6(b)对应的HRTEM图像（原子呈长程无序状态）；(d) HRTEM图像的iFFT图像；(e)～(f) 低倍数下的非晶区域
Figure 6. (a) TEM topographic image of the sample undergoing five cycles of reciprocating pressing, and a large amorphous region was found; (b) SAED image of the red circle region shown in (a), an obvious amorphous ring appears; (c) HRTEM image of the region in (b), where atoms were observed to exhibit long-range disorder; (d) iFFT image of the HRTEM image region; (e)–(f) amorphous regions of random distributions observed at low magnifications
图 7 (a)原位电阻测量实验所用组装示意图；(b) 3～6次往复压致相变实验测得的原位压力-电压（电阻）曲线
Figure 7. (a) Schematic diagram of the assembly used in electric resistance measurement experiments; (b) in situ pressure-voltage (resistance) curves corresponding to three to six cycles of reciprocating pressure-induced phase transitions experiments
图 8 3~6次往复压致相变过程中Avrami指数的变化规律
Figure 8. Variation of the Avrami index during the experimental process of three to six cycles of reciprocating pressure-induced phase transitions
图 9 高Avrami指数对应的升卸压过程的压力区间
Figure 9. Maximum Avrami index corresponding to the pressure range
图 10 DC Ge (a)、β-Sn Ge (b)、ST12 Ge (c)晶格的(001)面示意图
Figure 10. Schematic diagrams of the (001) planes: (a) DC Ge, (b) β-Sn Ge, and (c) ST12 Ge
图 11 (a)第5次往复相变升卸压过程采集的原位XRD谱（在 0～15 GPa压力区间完成了 ST12 Ge—β-Sn Ge—ST12 Ge两次相变）；(b) 往复2～5次后卸压到 0 GPa 时样品的XRD谱；(c) 图11(b)中 XRD谱中特征峰的峰宽变化
Figure 11. (a) In-situ XRD patterns collected during the fifth reciprocating phase transition compressing (0–15 GPa) and decompressing (15–0 GPa) process, two phase transitions of ST12 Ge–β-Sn Ge–ST12 Ge were completed; (b) XRD patterns collected after two to five cycles of experimental pressure uploading and decompressing to 0 GPa; (c) the full width at half maxima (FWHM) of characteristic peaks of XRD patterns in (b)
图 13 (a) 往复5次后样品另一区域的SEM图像（在该区域观测到了微米级晶粒）；(b) 往复5次后样品晶态区的SAED图像（观测到明显的多晶环）；(c) 多晶区域的HRTEM图像（在多晶区域仍然存在部分非晶区，A和B分别为非晶区和多晶区的iFFT图像）；(d) ST12 Ge样品加热的DSC曲线（发现1个吸热峰，对应ST12 Ge到DC Ge的相变温度）；(e) 在相变温度加热1 h后的XRD谱（表明样品已经全部转化为DC Ge）
Figure 13. (a) SEM image of another area in the sample with five cycles of reciprocation, in which grains in the size of micrometers were observed; (b) SAED pattern of the crystal region in the sample undergoing five cycles of reciprocation, showing the obvious polycrystalline ring; (c) HRTEM image of the polycrystalline region, in which some amorphous regions still exist, A and B are the iFFT images of the amorphous and polycrystalline regions, respectively; (d) DSC curve of the ST12 Ge sample heated, an endothermic peak was found, corresponding to the phase transition temperature from ST12 Ge to DC Ge; (e) XRD pattern after heating for 1 h at the phase transition temperature, the sample has been completely transformed into DC Ge
表 1 Avrami 指数与时间和压力的对应关系
Table 1. Avrami index corresponding to time and pressure
Process n ln t p/GPa Process n ln t p/GPa 3CD-D 13.92a 8.06–8.20 9.07–8.43 5CD-D 18.55a 8.46–8.58 9.22–8.32 4.50b 7.69–8.06 10.52–9.07 7.13b 8.14–8.46 11.23–9.22 2.14c 7.08–7.69 12.02–10.52 4.90c 7.70–8.14 12.73–11.23 4CD-C 27.30a 7.75–7.81 11.81–12.06 6CD-C 22.09a 7.46–7.60 11.08–11.31 8.22b 7.81–8.00 12.06–12.62 5.43b 7.60–7.94 11.31–12.58 3.86c 8.00–8.48 12.62–14.82 3.16c 7.94–8.52 12.58–14.97 4CD-D 21.90a 8.45–8.57 8.99–8.25 6CD-D 45.00a 8.48–8.52 8.79–8.40 6.87b 8.16–8.45 11.10–8.99 21.15b 8.03–8.48 9.81–8.79 3.12c 7.48–8.16 13.37–11.10 5.40c 7.71–8.33 12.60–9.81 5CD-C 17.73a 31.87–33.14 11.31–11.81 5.26b 33.14–37.00 11.81–13.17 3.39c 37.00–44.87 13.17–15.13 Note: Superscript lowercase letters a, b and c represent the maximum, the median and the minimum values of the Avrami index during the compression and decompression process, respectively. 
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