Bulk Photovoltage Effect in Ferroelectric BaTiO₃

Due to the unusual charge separation mechanism and anomalous photovoltaic effects, the bulk photovoltage effect in ferroelectric semiconductors has attracted a great deal of attention in solar energy conversion, especially in attempts to utilize nonthermalized carriers. Among the various mechanisms that have been proposed for interpreting the photovoltaic effect, a shift mechanism was derived from quantum phenomena, which have been modeled and studied for many years. However, the concurrent shift and ballistic mechanism make investigating the ferroelectric bulk photovoltage effect complex and challenging. Here, taking a tetragonal ferroelectric BaTiO₃ single crystal as a prototype, we report an approach for distinguishing the shift and ballistic mechanism-induced surface photovoltage. The results indicate different effects on the charge separation of the ballistic mechanism and shift mechanisms, as evidenced by surface photovoltage measurement. Interestingly, the shift and ballistic mechanisms afford charge separation in two opposite directions but on the same order of magnitude under monochromatic superband illumination. Our results provide facile and efficient methods for clarifying the shift and ballistic mechanisms in ferroelectrics.