Analysis of the potential distribution

 
Germanium Electrodes
 
Any variation of the electrode potential occurs across the space charge layer.
 
Fig. 5.9 and Fig. 5.10: The flat band potential is in the minimum of the curves.
 
The capacity and the surface conductivity curves depend on the pH of the solution.
 
Using a certain scan rate the potential scale also corresponds to a time scale. Since current flows only
within a certain potential range or within a limited time interval, the charge transferred in this process
must be limited.
 
Concerning the charge distribution at the interface the formation of a surface radical (dangling bond) is
of special interest. This surface species is equivalent to a surface state, and its energy position is
expected to occur somewhere within the bandgap of the semiconductor and to be detectable either as
an additional capacity (see Eq. (5.39)) or by surface recombination measurements (see Section 4.3).
 
Compound Semiconductor Electrodes
 
The flatband potential of many semiconductor electrodes depends on the pH. This indicates that many
semiconductor surfaces exhibit a strong interaction with water.
 
It is interesting to note that the flatband potential may depend on the crystal faces.
 
Flatband Potential and Position of Energy Bands at the Interface
 
As previously mentioned, the flatband potential of many systems depends on the pH of the electrolyte.
An increase of pH always leads to a cathodic shift of Ufb and a corresponding change of ΔφH. Accordingly,
the energy bands of the semiconductor at the surface are always shifted upward by an increase of pH.
 
Another important result is that the flatband potentials and therefore the position of the energy bands
at the semiconductor surface contacting an aqueous electrolyte are usually independent of any redox
system added to the solution. Hence, the interaction between semiconductor and H2O determines the
Helmholtz layer and the position of the energy bands. Therefore, it is reasonable to characterize
semiconductor electrodes by their positioning of energy bands at the surface for a given pH. The
situation is quite different for nonaqueous electrolytes.
 
Fermi level pinning by surface states may occur in a similar fashion to that at semiconductor-metal
junctions. Such an effect would lead to an unpinning of bands at the interface.