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We report on the role of oxygen octahedral tilting in the monoclinic-to-tetragonal phase transition in ultra-thin BiFeO3 films grown on (001) SrTiO3 substrates. Reciprocal space maps clearly show the disappearance of the integer-order Bragg peak splitting associated with the monoclinic phase when the film thickness decreases below 20 unit cells. This monoclinic-to-tetragonal transition is accompanied by the evolution of the half-order diffraction peaks, which reflects untilting of the oxygen octahedra around the [110] axis, proving that the octahedral tilting is closely correlated with the transition. This structural change is thickness-dependent, and different from a strain-induced transition in the conventional sense

Untilting BiFeO3: The influence of substrate boundary conditions in ultra-thin BiFeO3 on SrTiO3