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Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. ABSTRACT: Growth experiments show significant differences in the crystallization of ultrathin CaTiO 3 layers on polycrystalline Pt surfaces. While the deposition of ultrathin layers below crystallization temperature inhibits the full layer crystallization, local epitaxial growth of CaTiO 3 crystals on top of specific oriented Pt crystals occurs. The result is a formation of crystals embedded in an amorphous matrix. An epitaxial alignment of the cubic CaTiO 3 ⟨111⟩ direction on top of the underlying Pt {111} surface has been observed. A reduced forming energy is attributed to an interplay of surface energies at the {111} interface of both materials and CaTiO 3 nanocrystallites facets. The preferential texturing of CaTiO 3 layers on top of Pt has been used in the preparation of ultrathin metal−insulator−metal capacitors with 5−30 nm oxide thickness. The effective CaTiO 3 permittivity in the capacitor stack increases to 55 compared to capacitors with amorphous layers and a permittivity of 28. The isolated CaTiO 3 crystals exhibit a passivation of the CaTiO 3 grain surfaces by the surrounding amorphous matrix, which keeps the capacitor leakage current at ideally low values comparable for those of amorphous thin film capacitors.