The formation of previously unknown hexagonal modifications of orthoferrites RFeO3 (R = Eu−Lu) was observed on ZrO2(Y2O3) (111) substrates at 900 °C. XRD and HREM studies reveal epitaxial growth of the hexagonal film. The structure of the hexagonal RFeO3 was assigned to the ferroelectric space group P63 cm. The typical structural defects in the hexagonal RMnO3 films on ZrO2(Y2O3) (111) are described. Parallel deposition on perovskite substrates results in the stable perovskite phase. The epitaxial stabilization concept successfully explains the experimental results.

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