Internal photoetnission (IPE) has been successfully applied to evaluate band offsets of heterojunctions (HJs) in crystalline silicon (c-Si)-based solar cells. Tunneling of carriers through the potential spike at HJ and the presence of a carrier conduction path in the wide-band-gap material of HJ can affect the IPE results. In other words, IPE measures the effective band discontinuity, including effects of the carrier conduction path. This feature of IPE is suited for the characterization of solar-cell structures. Results obtained for hydrogenated amorphous silicon/c-Si HJ and gallium phosphide/c-Si HJ are presented and discussed. (C) 2008 Elsevier B.V. All rights reserved.