Piezoelectric, elastic, structural and dielectric properties of the Si1−xGexO2 solid solution: a theoretical study

We apply first principles quantum mechanical techniques to the study of the solid solution Si1−xGexO2 of α-quartz where silicon atoms are progressively substituted with germanium atoms, to different extents, as a function of the substitutional fraction x. For the first time, the whole range of the substitution (x = 0.0, 0.1 6-bar , 0. 3-bar , 0.5, 0. 6-bar , 0.8 3-bar , 1.0), including pure end-members α-SiO2 and α-GeO2, is explored. An elongated supercell (doubled along the c crystallographic axis) is built with respect to the unit cell of pure α-quartz and a set of 13 symmetry-independent configurations is considered. Their structural, energetic, dielectric, elastic and piezoelectric properties are computed and analyzed. All the calculations are performed using the CRYSTAL14 program with a Gaussian-type function basis set with pseudopotentials, and the hybrid functional PBE0; all geometries are fully optimized at this level of theory. In particular, for each configuration, fourth-rank elastic and compliance tensors and third-rank direct and converse piezoelectric tensors are computed. It has already been shown that the structural distortion of the solid solution increases, almost linearly, as the substitutional fraction x increases. The piezoelectric properties of the Si1−xGexO2 solid solution are found to increase with x, with a similar quasi-linear behavior. The electromechanical coupling coefficients are enhanced as well and the linear trend recently predicted by Ranieri et al (2011 Inorg. Chem. 50 4632) can be confirmed from first principles calculations. These doped crystals do represent good candidates for technological applications requiring high piezoelectric coupling and high thermal stability. (paper)