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The microstructures present in a thin film of La0.7Sr0.3MnO3, grown by computer-controlled laser molecular beam epitaxy on a SrTiO3 (001) substrate, were characterized by means of cross-section and plan-view transmission electron microscopy. Four kinds of rhombohedral-oriented domains and two types of domain boundaries were identified in the film. The crystallographic relationships between each domain and the substrate were established on the basis of a hexagonal unit cell using Miller-Bravais indices. A mechanism for the formation of the oriented domains is proposed from the viewpoint of the evolution of strain relaxation during film preparation.

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