Atomic-scale phase-field modeling with dopants: Stochastic self-consistent harmonic approximation with fractional site occupancy

Abstract

Phase-field modeling has achieved great success in predicting pattern formation in materials, such as the formation of ferroelectric domains. However, because it is typically based on continuum mechanics, conventional phase-field modeling cannot be straightforwardly applied to atomic-scale pattern formation, such as dopant segregation and vacancy ordering, which are driven by chemical potentials. Here, we extend the phase-field concept to the atomic scale by formulating the free energy of atomic systems within stochastic self-consistent harmonic approximation (SSCHA) theory to allow fractional site occupations. Our methodology enables us to directly calculate the derivative of the free energy with respect to site occupation and thereby obtain the chemical potential, successfully reproducing Ag distributions in bulk Cu as well as the resulting lattice expansion. Furthermore, we applied our methodology to investigate dopant segregation around a {\Sigma}5(310)[001] Cu grain boundary doped with Ag atoms. We found that Ag atoms preferentially segregate at the vertices of the triangular motif of a grain boundary. As the number of dopants increases, excess Ag atoms segregate near the vertices and then at the bottom sites of the triangular motif. This study extends the phase-field concept to discrete atomic systems, enabling the identification of preferential dopant-segregation sites and thereby visualizing atomic-scale pattern formation.