Hf-C体系的高压结构预测及电子性质第一性原理模拟

本论文中, 采用晶体结构预测软件USPEX结合第一性原理方法全面地搜索了Hf-C体系在高压下的晶体结构, 预测得到了两种新的化合物及HfC在高压下的相变路径. 压力低于100 GPa 时, 除了常压下的结构HfC, Hf₃C₂, Hf₆C₅, 并没有得到新的热力学稳定结构. 在200 GPa时, 预测得到了一种新化合物——Hf₂C, 空间群为I4/m; 且HfC的结构发生了相变, 空间群由Fm3m变为C2/m. 在300 GPa时, 预测得到了另一种新化合物——HfC₂, 空间群为Immm. 而在400 GPa时, HfC的结构再次发生相变, 空间群为Pnma. 通过能量计算, 得到了Hf-C体系的组分-压力相图: 在压力分别低于15.5 GPa和37.7 GPa时, Hf₃C₂和Hf₆C₅是稳定的; 压力分别大于102.5 GPa和215.5 GPa时, Hf₂C和HfC₂变成稳定化合物; HfC的相变路径为Fm3m→C2/m→Pnma, 相变压力分别为185.5 GPa 和322 GPa. 经结构优化后, 得到了这四种高压新结构的晶体学数据, 如晶格常数、原子位置等, 并分析了其结构特点. 对于Hf-C 体系中的高压热力学稳定结构, 分别计算了其弹性性质和声子谱曲线, 证明是力学稳定和晶格动力学稳定的. 采用第一性原理软件VASP模拟高压结构的能带结构、态密度、电子局域函数和Bader 电荷分析, 发现HfC(C2/m, Pnma结构), Hf₂C 和HfC₂ 中Hf-C 键具有强共价性、弱金属性和离子性, 且C-C 间存在共价作用.

High-pressure structure prediction of Hf-C system and first-principle simulation of their electronic properties

Hafnium carbides (Hf-C system), known as ultra-high temperature ceramics, have attracted growing attention because of their unique features. In this paper, we carry out researches on the stable crystal structures in the Hf-C system at high pressures, using a variable-composition ab initio evolutionary algorithm implemented in the USPEX code. In addition to the ambient-pressure structures HfC (Fm3m), there are two new compounds Hf₃C₂ and Hf₆C₅ and two high-pressure structures of HfC. When pressures are lower than 100 GPa, no new structures are found other than those at ambient pressure, and Hf₃C₂ and Hf₆C₅ become metastable at 20 GPa and 100 GPa, respectively. At 200 GPa, a new compound Hf₂C is found, and the stable structure HfC has changed from Fm3m to C2/m. At 300 GPa, another new compound HfC₂ is found. At 400 GPa, the stable structure of HfC has changed again to the space group Pnma. And at 500 GPa, the stable structures are Hf₂C, HfC₂ and HfC (Pnma), no new structures are found except those at 400 GPa. The composition-pressure phase diagram that shows the pressure range of stable structures in Hf-C system is simulated by calculation of their enthalpies. When the pressures are lower than 15.5 GPa and 37.7 GPa, Hf₃C₂ and Hf₆C₅ are stable, respectively, and their space groups are both of C2/m. And Hf₂C and HfC₂, with space group I4/m and Immm, respectively become stable structures when the pressure is higher than 102.5 GPa and 215.5 GPa, respectively. The phase-transition route of HfC is Fm3m→C2/m→Pnma, and the two phase-transition pressures are 185.5 GPa and 322 GPa, respectively, which are different from the conclusion of Zhao. Then we will show and discuss the newly predicted high-pressure structures and their crystallographic data, such as volume, lattice constants and atom positions. The crystal structures of HfC are described in the literature. The structure of Hf₂C contains 12 atoms in the conventional cell, and carbon atoms lie at the center of decahedron consisting of 8 hafnium atoms. In the structure of HfC₂, carbon atoms form the quasi-graphite sheets and hafnium atoms lie betweent the two sheets. The dynamical and mechanical stabilities of the high-pressure structures have been verified by calculations of their phonon dispersion curves and elastic constants. And the bulk modulus and shear modulus of HfC₂ are larger than those of the other three high-pressure structures. Finally we will study their electronic properties, band structures, density of states (DOS), electron localization functions (ELFs), and the Bader charge analyses of these structures are simulated based on the first-principle. The band structure and density of states show that these four high-pressure structures have weak metallic and strong Hf-C covalent bond. The Bader charge analysis further proves the strong Hf-C covalent bond and weak ionic bond. And ELF shows the existence of C—C covalent bond. In summary, the Hf—C bond shows strong covalence, weak metallicity and ionicity, and the C—C bond is covalent.