Modeling of the perovskite nickelate SmNiO3 nucleation from amorphous thin films: A Volmer's thermodynamical approach

Abstract

We present a thermodynamical model based on Volmer's nucleation theory adapted to the case of the perovskite nickelate SmNiO₃ crystallization (SNO) from an amorphous (aSNO) thin film. This amorphous phase is synthesized via reactive magnetron sputtering and then subsequently annealed in air at temperatures between 725 and 925 K to crystallize it. This model allows to predict the theoretical nucleation rate of the crystallized perovskite phase according to the annealing temperature, the type of the nucleation (homogeneous and heterogeneous mechanisms) and to estimate some physical and thermodynamical data related to this transformation. A theoretical evaluation of the nucleation rate shows that the optimum temperature for crystallization is close to 800 K for which the nucleation rate can reach 10²¹ m^-3.s^-1 if considering both homogeneous and heterogeneous nucleation mechanisms. As the annealing temperature moves away from 800 K, the theoretical nucleation rate drops drastically, as observed experimentally by X-ray Diffraction (XRD) when we annealed 200 nm thick aSNO films. The good agreement between the presented model and the experimental crystallization results allows us to numerically evaluate some physical parameters not yet reported to date in the literature for SNO perovskites such as the surface energy between the amorphous and the crystallized SNO phases, the strain energy when the crystallization occurs and the enthalpy associated with crystallization.