Lead-free piezoelectrics: V ³⁺ to V ⁵⁺ ion conversion promoting the performances of V-doped Zinc Oxide

Abstract

Vanadium doped ZnO (VZO) thin films were grown by RF magnetron sputtering, starting from a ZnO:V ceramic target. The crystal structure, chemical composition, electric and piezoelectric properties of the films were investigated either on the as-grown thin films or after a post-deposition rapid thermal annealing (RTA) treatment performed at 600 °C for different lengths of time (1 and 5 min) in an oxygen atmosphere. Substitutional doping of Zn ²⁺ with V ³⁺ and V ⁵⁺ ions strongly deteriorated the hexagonal wurtzite ZnO structure of the as-grown thin films due to lattice distortion. The resulting slight amorphization led to a poor piezoelectric response and higher resistivity. After the RTA treatment, strong c-axis oriented VZO thin films were obtained, together with a partial conversion of the starting V ³⁺ ions into V ⁵⁺. The improvement of the crystal structure and the stronger polarity of both V ³⁺ – O and V ⁵⁺ – O chemical bonds, together with the corresponding easier rotation under the application of an external electric field, positively affected the piezoelectric response and increased conductivity. This was confirmed by closed-loop butterfly piezoelectric curves, by a maximum d ₃₃ piezoelectric coefficient of 85 pm·V ⁻¹, and also by ferroelectric switching domains with a well-defined polarization hysteresis curve, featuring a residual polarization of 12.5 μC∙cm ⁻².