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We show that epitaxial (001) thin films of multiferroic bismuth ferriteBiFeO3 are monoclinic at room temperature instead of tetragonal or Rhombohedralas reported earlier . We report a orthorhombic order-disorder beta-phasebetween 820C and 950C contrary to the earlier report. The transition sequencemonoclinic-orthorhombic phase in (001)BiFeO3 thin film(rhombohedral-orthorhombic transition in single crystal) resembles that ofBaTiO3 or PbSc1/2Ta1/2O3. The transition to the cubic $\gamma$-phase causes anabrupt collapse of the bandgap toward zero (insulator-metal transition) at theorthorhombic-cubic beta-gamma transition around 950C. This transition issimilar to the metal-insulator transition in Ba0.6K0.4BiO3.

The beta Phase of Multiferroic Bismuth Ferrite and its beta-gamma Metal-Insulator Transition