Roles of Charge Carriers in the Excited State Dynamics of BiVO4 Photoanodes

Photogenerated charge carrier dynamics of BiVO4 have been investigated by ultrafast transient absorption spectroscopy (TAS), and a numerical modeling has been applied to reveal the origins of the dynamical behavior. The numerical model, based on rate equations, presents the possibility of both photogenerated hole and electron absorption dynamics below 500 nm, as opposed to the generally suggested photogenerated hole absorption mechanism. The investigations done in the ultrafast time regime show that the positive transient absorption peak at 470 nm exhibits inverse behavior as compared to the broad-band feature represented at 550 nm under anodic bias, in the presence of a hole scavenger and at increasing excitation pump power. A combination of TAS findings under various conditions with the numerical modeling reveals that both electron and hole absorption are possible in the spectral region above 500 nm whereas electron absorption at the excited state is the dominant process at shorter wavelengths. Moreover, the major changes in transient absorption response take place in the ultrafast time scale, and overall recombination dynamics is a reflection of the ultrafast recombination mechanism.