Effect of Crystal Structure on Hole Carrier Generation in Wide-gap P-type Tin-Niobate

Sn2Nb2O7 and SnNb2O6 are promising candidates for wide-gap p-type conducting oxides with high mobility, because their valence-band maximum are composed of Sn 5s orbital with large spatial spreading and isotropic nature. Though hole carriers were generated by Sn4+ substitutional defects on Nb5+ site (Sn' (Nb)) in the substructure of Nb2O6 octahedra in both tin niobates, the generation efficiency of hole carriers in SnNb2O6 was larger than that of Sn2Nb2O7. From the variation in bond length of Nb-O in the Nb2O6 octahedra calculated by Rietveld analysis, the difference in carrier generation efficiency of two tin niobates was examined. The bond length of Nb-O in p-type Sn2Nb2O7 with large amounts of Sn' Nb was smaller than that of n-type Sn2Nb2O7 with small amounts of Sn' Nb. The holes generated by Sn' Nb were considered to be captured by the negative charge of oxygen anions consisting of the Nb2O6 octahedra, resulting in low carrier generation efficiency. In SnNb2O6 showing higher efficiency, Nb-O was 8.6 % larger than that of p-type Sn2Nb2O7. It is considered that the large Nb-O bond length provide the preferred environment for the generation of positive holes, resulting in the higher carrier generation efficiency.