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

Sn2Nb2-xTaxO7 (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.