When a semiconductor comes into contact with a liquid (redox species), to maintain electrostatic equilibrium, there will be a charge transfer between the semiconductor and liquid phase if formal redox potential of redox species lies inside semiconductor band gap. At thermodynamic equilibrium, the Fermi level of semiconductor and the formal redox potential of redox species are aligned at the interface between semiconductor and redox species. This introduces an upward band bending in a n-type semiconductor for n-type semiconductor/liquid junction (Figure 1(a)) and a downward band bending in a p-type semiconductor for a p-type semiconductor/liquid junction (Figure 1(b)). This characteristic of semiconductor/liquid junctions is similar to a rectifying semiconductor/metal junction or Schottky junction. Ideally to get a good rectifying characteristics at the semiconductor/liquid interface, the formal redox potential must be close to the valence band of the semiconductor for a n-type semiconductor and close to the conduction band of the semiconductor for a p-type semiconductor. The semiconductor/liquid junction has one advantage over the rectifying semiconductor/metal junction in that the light is able to travel through to the semiconductor surface without much reflection; whereas most of the light is reflected back from the metal surface at a semiconductor/metal junction. Therefore, semiconductor/liquid junctions can also be used as photovoltaic devices similar to solid state p–n junction devices. Both n-type and p-type semiconductor/liquid junctions can be used as photovoltaic devices to convert solar energy into electrical energy and are called photoelectrochemical cells. In addition, a semiconductor/liquid junction could also be used to directly convert solar energy into chemical energy by virtue of photoelectrolysis at the semiconductor/liquid junction.