Unpinning of Energy Bands during Illumination

 
Mott–Schottky curves and therefore the flatband potentials are shifted upon illumination of the
semiconductor electrode, toward cathodic potentials with p-type electrodes and toward anodic with n-
type electrodes.
 
We have here an unpinning of bands upon illumination, and the shift of Ufb must be interpreted by an
equivalent movement of the energy bands, as illustrated for a p-type semiconductor in Figure 5.23. The
origins of this effect can be manifold. In most cases, it is explained by trapping of minority carriers in
surface states, a process which competes with the transfer of minority carriers in the electrolyte. It is
not primarily necessary, however, to make the trapping of minority carriers in surface states responsible
for the band edge movement.
 
In the first step, minority carriers produced by light excitation are drawn toward the surface because of
the electric field across the space charge region. In the case of a p-type electrode, the energy bands are
bent upward so that the electrons are moved toward the surface.
 
The accumulation of minority carriers and the resulting shift of energy bands can be avoided if a suitable
redox system is added to the electrolyte.
 
In all cases, the flatband potential occurs close to the onset of the photocurrent.