| Summary: | Here, we report an anisotropic small-hole polaron in an orthorhombic structure of BiVO₄ films grown by pulsed-laser deposition on yttrium-doped zirconium oxide substrate. The polaronic state and electronic structure of BiVO₄ films are revealed using a combination of polarization-dependent x-ray absorption spectroscopy at VL[subscript 3,2] edges, spectroscopic ellipsometry, x-ray photoemission spectroscopies, and high-resolution x-ray diffraction with the support of first-principles calculations. We find that in the orthorhombic phase, which is slightly different from the conventional pucherite structure, the unoccupied V 3d orbitals and charge inhomogeneities lead to an anisotropic small-hole polaron state. Our result shows the importance of the interplay of charge and lattice for the formation of a hole polaronic state, which has a significant impact in the electrical conductivity of BiVO₄, hence its potential use as a photoanode for water splitting.
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