Solution processed CdTe layers are a potentially low-cost alternative for use in thin-film solar cells. We have recently reported the use of such nanocrystalline layers within ITO/CdTe/ZnO/Al device architectures. One key concern with this type of device structure is the possibility of atomic scale interdiffusion between the ITO and CdTe layers, which can result in deleterious n-type doping of the CdTe layer. Rutherford Backscattering has been used to study the chemical composition across the ITO/CdTe interface as a function of thermal annealing temperature. Through these measurements we verify that interdiffusion is observed across the interface for annealing temperatures above 200 °C, and the extent of interdiffusion increases with temperature. Ultra-thin alumina, zirconia and titania layers deposited between the ITO and CdTe layers have been studied for their potential to act as a diffusion barrier. All investigated barriers successfully suppress interdiffusion. The outcomes of these compositional studies are directly compared to solar cells fabricated under analogous processing conditions, demonstrating improved cell performance.