CdGeAs2晶体的热膨胀行为研究

doi:10.15541/jim20150232

摘要/Abstract

摘要：

采用WinTA 100热膨胀仪研究了四方黄铜矿CdGeAs₂晶体在320~620 K温度范围内的热膨胀行为, 探索了CdGeAs₂晶体热膨胀各向异性的物理机制。测定晶体a轴和c轴方向的热膨胀系数α_a和α_c发现, α_a>>α_c>0, 表现出强烈的各向异性热膨胀特性。利用最小二乘法, 拟合出CdGeAs₂晶体的晶格常数(a, c)与温度(T)的函数关系式, 与文献报道值吻合。分别计算出不同温度下的四方畸变因子δ=2-c/a, Cd-As 键长(l_Cd-As)和 Ge-As 键长(l_Ge-As)以及相应的热膨胀系数α_Cd-As和α_Ge-As。结果表明, a、c、δ、l_Cd-As、l_Ge-As和α_Cd-As均随着温度的升高而增大, c/a和α_Ge-As则随着温度的升高而减小。当T=360 K时,α_Cd-As是α_Ge-As的6.36倍, 是造成CdGeAs₂晶体强烈热膨胀各向异性的主要原因。

关键词: CdGeAs2晶体, 热膨胀, 四方畸变

Abstract:

Thermal expansion measurements by WinTA 100 on tetragonal chalcopyrite cadmium germanium arsenide (CdGeAs₂) crystal were carried out in the temperature range between 320 K and 620 K. Based on these measurements, the mechanisms of thermal expansion anisotropy is proposed. It is found that the axial thermal expansion coefficients (α_a and α_c) are both positive, and α_a>>α_c, which exhibits anisotropic thermal behavior intensively. By the least squares method, the functional relationship between structural parameters (a, c) and temperature (T) is set up, which are coincident with published literature. Furthermore, the tetragonal distortion δ=2-c/a, the interatomic distances (l_Cd-As and l_Ge-As) and the bond expansion coefficients (α_Cd-As and α_Ge-As) are calculated at different temperatures, respectively. Simultaneously, it is also found that a, c, δ, l_Cd-As,l_Ge-As, and α_Ge-As increase with temperature increase, while c/a and α_Ge-As are just the opposite. When T=360 K, α_Cd-As is 6.36 times of α_Ge-As. Hence, the difference between α_Cd-As and α_Ge-As is the main reason for the signiﬁcant anisotropy of thermal expansion.

Key words: CdGeAs2, thermal expansion, tetragonal distortion

中图分类号:

O736

甄珍, 赵北君, 朱世富, 何知宇, 陈宝军, 黄巍, 蒲云肖, 钟义凯. CdGeAs₂晶体的热膨胀行为研究[J]. 无机材料学报, 2016, 31(2): 165-170.

ZHEN Zhen, ZHAO Bei-Jun, ZHU Shi-Fu, HE Zhi-Yu, CHEN Bao-Jun, HUANG Wei, PU Yun-Xiao, ZHONG Yi-Kai. Thermal Expansion Behaviors of CdGeAs₂ Crystal[J]. Journal of Inorganic Materials, 2016, 31(2): 165-170.

图/表 9

图1 CdGeAs2单晶照片

Fig. 1 Photograph of CdGeAs2 single crystal

图2 CdGeAs2晶体的X射线衍射图谱

Fig. 2 XRD spectrum of the CdGeAs2 single crystal (a) {100} faces; (b) {001} faces

图3 CdGeAs2晶体的轴向热膨胀系数随温度的变化曲线

Fig. 3 Variation of the axial thermal expansion coefﬁcients with temperature for CdGeAs2 (a) αa; (b) αc

图4 CdGeAs2的晶格常数随温度的变化曲线

Fig. 4 Variation of lattice parameters with temperature for CdGeAs2 (a) Lattice parameter a; (b) Lattice parameter c

表1 CdGeAs2晶体在不同温度下的晶格参数

Table 1 Lattice parameters of CdGeAs2 at various temperatures

Temperature/℃	Structural parameters
Temperature/℃	a/nm	This work	c/nm	This work	k	This work
25	0.59448	5.9432	1.12126	11.2172	1.8861	1.8874
100	0.59473	5.9467	1.12172	11.2175	1.8861	1.8863
200	0.59542	5.9521	1.12200	11.2179	1.8844	1.8847
300	0.59714	5.9581	1.12244	11.2184	1.8797	1.8829
400	0.59771	5.9648	1.22560	11.2190	1.8781	1.8809
450	0.59798	5.9684	1.12261	11.2194	1.8774	1.8798

图5 四方黄铜矿CdGeAs2的晶胞结构示意图

Fig. 5 The tetragonal chalcopyrite unit cell for the ternary CdGeAs2 compound

图6 CdGeAs2的四方畸变(δ)随温度的变化曲线

Fig. 6 Variation of tetragonal distortion (δ) with temperature for CdGeAs2

图7 CdGeAs2晶体中键长lCd-As、lGe-As随温度的变化曲线

Fig. 7 Variation of bond lengths lCd-As、lGe-As with temperature for CdGeAs2

图8 CdGeAs2晶体热膨胀系数αCd-As、αGe-As随温度的变化曲线

Fig. 8 Variation of the thermal expansion coefﬁcients αCd-As、αGe-As with temperature for CdGeAs2

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CdGeAs₂晶体的热膨胀行为研究

Thermal Expansion Behaviors of CdGeAs₂ Crystal

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