Disorders and oxygen vacancies in p-type Sn2B2O7 (B = Nb,Ta): Role of the B-site element

Sn₂Nb_2?xTa_xO₇ (x = 0.0–2.0) with pyrochlore structure is a promising material for p-type oxide semiconductors. A systematic study of its Nb/Ta ratio indicated that the hole–generation efficiency of the Nb end (Sn₂Nb₂O₇) was an order of magnitude lower than that of the Ta end (Sn₂Ta₂O₇). Although this occurs due to differences in oxygen-vacancy formation, the origins of the hole–generation efficiencies remain unclear due to limited information on local and global crystal-structure disorders in pyrochlore Sn₂Nb₂O₇ and Sn₂Ta₂O₇. In this study, the crystal structures of Sn₂B₂O₇ (B = Nb, Ta), composed of BO₆ octahedra and Sn₄O tetrahedra, were investigated using X-ray absorption spectroscopy and X-ray diffraction. A detailed investigation of the local and global crystal structures indicated a larger amount of disorder in the Sn₄O tetrahedra in Sn₂Nb₂O₇ compared to Sn₂Ta₂O₇; disorder in the BO₆ octahedra occurred only in Sn₂Ta₂O₇. This study indicates that an appropriate selection of the B-site element is vital for suppressing defect and disorder formation in Sn₄O tetrahedra and subsequently improving the hole–carrier–generation efficiency.