High resolution transmission electron microscopy of lattice-matched 7nSeo.94So.o6 layers grown by organometallic chemical vapour deposition in the temperature range 275 to 350 ~ C onto GaAs has shown that under specific growth conditions, layers of ZnS can form at the heterojunction interface. Chemical data from secondary ion mass spectrometry and energy dispersive X-ray analyses confirm the enhancement in sulphur content at the interface and also establish that gallium can diffuse into the I I-VI layer from the II I-V substrate. Growth conditions which eliminate the formation of the intermediate ZnS layer and the gallium diffusion have been identified.