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We investigated the crystal structure and ferroelectric domains of BiTiO (BTO) by means of transmission electron microscopy (TEM) and single-crystal X-ray diffractometry. From the extinction rule, we determined that the space group in the ferroelectric phase of BTO is 11 rather than 2 and 11 which have been proposed previously. We successfully refined the crystal structure based on the space group 11. The 180° and 90° ferroelectric domain structures were observed by the [001]-zone dark-field TEM imaging. In the 180° domain structure, we determined that one component of the polarization vector is parallel to the -axis. An annular bright-field scanning transmission electron microscopy (ABF-STEM) was performed for the direct observation of the crystal structures. The ABF-STEM images displayed the contrasts with respect to every atomic position in spite of the highly distorted structure of BTO. We could evaluate the tilting and distortion of the [TiO] octahedra relatively. Therefore, we directly observed the ferroelectric displacements of Bi and Ti ions.


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