Elastic, piezoelectric, and dielectric properties of rare-earth calcium oxoborates RCa4O(BO3)3 (R = Er, Y, Dy, Gd, Sm, Nd, La)

Large single crystals of rare-earth calcium oxoborates R Ca4O(BO3 )(3) with R = Er, Y, Dy, Gd, Sm, Nd, La ( R C O B) were grown by the Czochralski method. Complete sets of dielectric, piezoelectric stress, and elastic stiffness coefficients of the R C O B crystal species were determined at ambient conditions using a combination of resonant ultrasound spectroscopy and the substitution method. The results are inherently consistent and reveal clear crystal chemical trends, with the size of the trivalent cation playing an important role. In particular, the longitudinal and shear aggregate elastic stiffnesses, c(11)(iso) and c(44)(iso), decrease from about 165 to 154 GPa and, respectively, 45 to 41 GPa from the smallest to the largest R3+ cation of the investigated crystal species, while the dielectric coefficients e(22) and e(33) increase. However, the maximum longitudinal piezoelectric effect peaks with 8.6 pCN(-1) at NdCOB, the species where the radius of R3+ best matches the one of Ca2+. Increasing differences in the size of R3+ and Ca2+ lead to anisotropic stresses in the crystal lattice, which are partially relaxed by an increasing degree of cation disorder.

Automated summary

Large single crystals of rare-earth calcium oxoborates R Ca4O(BO3 )(3) were grown using the Czochralski method. The study determined dielectric, piezoelectric stress, and elastic stiffness coefficients of the crystals, showing clear crystal chemical trends with the size of the trivalent cation playing a crucial role. Anisotropic stresses in the crystal lattice caused by increasing differences in the size of R3+ and Ca2+ were partially relaxed by an increasing degree of cation disorder.