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Thermal excitations typically reduce the electric polarization inferroelectric materials. Here, we show by means of first-principlescalculations that multiferroic BiFe$_{1-x}$Co$_{x}$O$_{3}$ solid solutions with$0.25 \le x \le 0.50$ (BFCO) represent a noteworthy exception to thisbehaviour. In particular, we find that at room temperature and for moderatepressures of $0.1$-$1.0$ GPa, depending on the composition, the electricpolarization of bulk BFCO increases by $\sim 200$%. The origin of such anexceptional behavior is a phase transformation involving a low-$T$ rhombohedral(${\cal R}$) phase and a high-$T$ super-tetragonal (${\cal T}$) phase. Both${\cal R}$ and ${\cal T}$ phases are ferrimagnetic near room temperature withan approximate net magnetization of $0.13$$\mu_{B}$ per formula unit.Contrarily to what occurs in either bulk BiFeO$_{3}$ or BiCoO$_{3}$, the ${\calT}$ phase is stabilized over the ${\cal R}$ by increasing temperature due toits higher vibrational entropy. This extraordinary $T$-induced ${\cal R} \to{\cal T}$ phase transition is originated by polar phonon modes involvingconcerted displacements of transition-metal and oxygen ions.

Giant Thermal Enhancement of the Electric Polarization in Ferrimagnetic BiFe$_{1-x}$Co$_{x}$O$_{3}$ Solid Solutions Near Room Temperature