Anisotropic small-polaron hopping in W:BiVO_4 single crystals

摘要

DC electrical conductivity, Seebeck and Hall coefficients are measured between 300 and 450K on single crystals of monoclinic bismuth vanadate that are doped n-type with 0.3% tungsten donors (W:BiVO_4). Strongly activated small-polaron hopping is implied by the activation energies of the Arrhenius conductivities (about 300 meV) greatly exceeding the energies characterizing the falls of the Seebeck coefficients' magnitudes with increasing temperature (about 50meV). Small-polaron hopping is further evidenced by the measured Hall mobility in the ab-plane (10~(-1)cm~2V~(-1)s~(-1) at 300 K) being larger and much less strongly activated than the deduced drift mobility (about 5 × 10~(-5) cm~2 V~(-1) s~(-1) at 300 K). The conductivity and n-type Seebeck coefficient is found to be anisotropic with the conductivity larger and the Seebeck coefficient's magnitude smaller and less temperature dependent for motion within the ab-plane than that in the c-direction. These anisotropics are addressed by considering highly anisotropic next-nearest-neighbor (≈5 A) transfers in addition to the somewhat shorter (≈4 A), nearly isotropic nearest-neighbor transfers.