Analytical TEM techniques have been used to characterize the structure and chemistry of chalcopyrite solar cell devices produced by elemental evaporation using a bi-layer process at Ts=400°C and Ts=550°C. Dislocations, stacking faults, twins and voids exist in both materials but at a reduced density at the higher deposition temperature. The higher processing temperature also improved the density and structure of the grain boundaries and created a less rough surface. The CdS layer coats the surface conformally, although the roughness impacts the structure. CdS fills the grooves in the surface and infiltrates lower density grain boundaries to significant depths. The chemistry of the grain boundaries does not appear to be significantly impacted by the presence of the Cd and S.