Current understanding and control of semiconductor contacts increasingly require measurements sensitive to defects and, chemical changes at nanoscale interfaces. We offer examples illustrating dramatic macroscopic effects occurring in semiconductor systems as a result of nanoscale interface phenomena. In some cases, there is interplay of several competing defect-driven mechanisms. Elucidating them and finding the leading ones require careful experimental approach. For single-crystalline ZnO, we study the role of near-surface defects on the formation of Au Schottky contacts. Among the factors degrading the rectifying characteristics of such contacts one should consider the following. High concentrations of shallow donors in the surface and subsurface regions lead to barrier thinning, resulting in increased tunneling. Alternatively, the presence of deep defects near contact interface promotes tunneling by defect-assisted hopping. Nanoscale electronic and chemical studies show that independent reduction of both shallow donors and deep defects significantly improves the rectifying performance of the Au/ZnO contacts. We find that processing of ZnO with remote O and H plasmas allows for controllable tailoring of chemical and physical properties of the surface. By the same token, nanoscale compositional and electrostatic variations between grain boundaries and grain interiors in thin polycrystalline films of Cu(In, Ga) Se-2, absorber layers in record-setting solar cells, show how nanoscale arrangement of near-surface stoichiometric defects may improve the overall photovoltaic efficiency. Confirming the theory, we find a 50% reduction in Cu composition from grain interior to boundary and a p-type potential barrier that acts to reduce majority-carrier hole recombination. These examples emphasize the practical significance of nanoscale chemical and electronic features at electronic material interfaces. (c) 2006 American Vacuum Society.