Impact of quenched random fields on the ferroelectric-to-relaxor crossover in the solid solution (1-x)BaTiO3-xDyFeO3

Lead-based perovskite relaxor ferroelectrics are widely used as materials for numerous applications due to their extraordinary dielectric, piezoelectric, and electrostrictive properties. While the mechanisms of relaxor behavior are disputable, the importance of quenched (static) random electric fields created at nanoscale by the disordered heterovalent cations has been well recognized. Meanwhile, an increasing amount of scientific and technological efforts has been concentrated on lead-free perovskites, in particular, solid solutions of classical ferroelectric BaTiO3 (BT), which better meet ecological requirements. Among BT-based solutions the homovalent systems are elaborately studied where strong random electric fields are absent, while the solubility limit of heterovalent solutions is typically too low to fully reveal the peculiarities of relaxor behavior. In this paper, we prepare a perovskite solid solution system (1 - x)Ba2+Ti4+O3-xDy(3+)Fe(3+)O(3) (0 <= x <= 0.3) and study it as a model heterovalent lead-free system. We determine crystal structure, ferroelectric, and dielectric properties of ceramics in a wide range of temperatures and concentrations, construct a phase diagram, and find and analyze the concentration-induced crossover from normal ferroelectric to relaxor behavior. We demonstrate that quenched random electric fields of moderate strength promote the ferroelectric-to-relaxor crossover, but do not change qualitatively the peculiarities of relaxor behavior, while strong enough fields destroy the relaxor state, so that the material becomes an ordinary linear dielectric. The experimental results are compared with the predictions of known theories of relaxor ferroelectricity.