A detailed structural analysis of electrodeposited CdS-CdTe thin him heterojunction solar cells was undertaken. X-ray diffraction and Rutherford backscattering spectrometry were used to provide stoichiometric and microcrystalline data at increasing depths through the CdTe and CdS films. A model of the nature and extent of interdiffusion caused by a post deposition anneal is developed ii region in both preannealed and post-annealed samples which possesses a significantly different microstructure to that of the bulk CdTe, was identified. Within this region a stoichiometric gradient occurs and the grain size and preferred orientation decrease with increasing depth. Maximum CdTe film stress (post anneal) is estimated to be 140 MPa close to the interface and a shift in optical band gap of 6 x 10(-3) eV was also determined from structural measurements. We provide evidence that sulphur diffusion into CdTe is structurally rather than thermodynamically Limited within these systems.