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A detailed investigation using variable temperature powder neutrondiffraction demonstrates that BiFeO3 undergoes a phase transition from theferroelectric alpha phase (rhombohedral, R3c) to a paraelectric beta phase(orthorhombic, Pbnm) between 820 oC and 830 oC. Co-existence of both phasesover a finite temperature interval, together with abrupt changes in keystructural parameters, confirm that the transition is firstorder. The betaphase corresponds to the GdFeO3-type perovskite. The metastability of BiFeO3relative to Bi2Fe4O9 above 810 oC precludes observation of a reported cubicgamma phase above 925 oC under the present experimental conditions.

The ferroelectric-paraelectric phase transition in BiFeO3: crystal structure of the orthorhombic beta-phase