PNNL

Abstract

Rational design and optimization of efficient photovoltaics requires fundamental knowledge of both the materials properties of the individual components and the conduction and valence band alignments at the materials interfaces. Efficient collection of electrons photogenerated in the absorber material requires a small or zero conduction band offset at both the absorber/n-type semiconductor and the n-type semiconductor/electrode interfaces. Negative conduction band offsets result in an energy barrier to electron injection, while large positive conduction band offsets (a “cliff” arrangement) result in too much energy lost during injection. However, it is difficult to predict heterojunction band offsets from bulk materials properties. Experimental band alignments of semiconductor heterojunctions rarely conform to the Anderson model,1 which assumes the band alignments are determined solely by differences in the electron affinity of the two semiconductors. Chemical bonds at the heterojunction interface give rise to an interfacial dipole which influences the interfacial band alignment. Thus, the complex interplay between electron affinity differences, Fermi level matching, interface-induced gap states, and band bending determine heterojunction band alignments.2-5 Band alignments can also be modified by doping, point defects, or control of non-stoichiometry at the interface; since these parameters can be affected by processing conditions, they offer a mechanism to modify the band alignments of a given heterojunction system.