Resonant Raman signatures of exciton polarons in a transition metal oxide: BiVO$_4$

In this work we investigate the delocalized excitons and excitons trapped by a polaron formation in \BVO{} by means of resonant Raman spectroscopy. We record Raman spectra with 16 laser lines between 1.9 and \SI{2.6}{\eV} and analyze intensity variations of the Raman peaks for different vibrational modes. The resonant Raman cross sections of the \Ag{} modes contain two types of resonances. The first high-energy resonance near \SI{2.45}{\eV} belongs to a transition between delocalized states; it is close to absorption edge measured at \SI{2.3}{\eV} and exhibits a characteristic \SI{50}{\meV} anisotropy between polarization parallel and perpendicular to the $c$ axis. The high energy Raman resonance occurs inside the gap at \SI{1.94}{\eV} for all crystallographic directions. The in-gap resonance can involve a localized transition. We attribute it to an exciton-polaron, formed by a small localized electron polaron of Holstein type and delocalized holes. It manifests in the vibrations of vanadium and oxygen atoms where polaron localization occurs and the resonance energy matches theoretical predictions. The vibrational modes couple to the polaron with different efficiency determined from resonant Raman profiles.
Comment: main: 8 pages, 4 figures, supporting: 4 pages, 3 figures