Programmable Metallization Cell (PMC) Random Access Memory is based on the electrochemical growth and removal of nanoscale metallic pathways in thin films of solid electrolytes. In this study, we investigate the nature of thin films formed by the photo doping of Cu into chalcogenide materials for use in programmable metallization cell devices. These devices rely on metal ion transport in the film so produced to create electrically programmable resistance states. The results imply that a Cu-rich phase separates owing to the reaction of Cu with free atoms from chalcogenide materials.