Reentrant polar phase induced by the ferro-ionic coupling in Bi₁₋ₓSmₓFeO₃ nanoparticles

Using the model of four sublattices, the Landau-Ginzburg-Devonshire-Kittel phenomenological approach and the Stephenson-Highland ionic adsorption model for the description of coupled polar and antipolar long-range orders in ferroics, we calculated analytically the phase diagrams and polar properties of Bi₁₋ₓSmₓFeO₃ nanoparticles covered by surface ions in dependence on their size, surface ions density, samarium content "x" and temperature. The size effects and ferro-ionic coupling govern the appearance and stability conditions of the long-range ordered ferroelectric, reentrant ferrielectric and antiferroelectric phases in the Bi1-xSmxFeO3 nanoparticles. Calculated phase diagrams are in a qualitative agreement with the X-ray diffraction phase analysis, electron paramagnetic resonance, infra-red spectroscopy and electrophysical measurements of the Bi₁₋ₓSmₓFeO₃ nanopowders sintered by the solution combustion method. The combined theoretical-experimental approach allows to establish the influence of the ferro-ionic coupling and size effects in Bi₁₋ₓSmₓFeO₃ nanoparticles on their polar properties.