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The crystal structure of a new homologous compound series, Ga2O3(ZnO)m (m = integer), is determined by high-resolution lattice imaging and high spatial resolution energy-dispersive X-ray spectroscopy (EDS) analysis in a field-emission analytical transmission electron microscope. This work was carried out mainly on the compound with m = 9 (digallium nonazinc dodecaoxide), which belongs to the orthorhombic system and has lattice constants ao = 0.33, bo = 2.0 and co = 3.4 nm. From the extinction rules three possible space groups are selected and from them a unique space group is assigned as noncentrosymmetric Cmc21 (No. 36) on the basis of structural requirements. Ga2O3(ZnO)m is a layered structure consisting of Ga-O and m + 1 Ga/Zn-O layers stacked alternately along the c axis. It is shown that the structure of Ga2O3(ZnO)m differs from that of M2O3(ZnO)m (M = In, Fe; m = integer) reported previously. In Ga2O3(ZnO)m the Ga atoms occupy the tetrahedral sites in the Ga-O layers, whereas the M atoms in the M-O layers occupy the octahedral sites in M2O3(ZnO)m (M = In, Fe).

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