GaSe, a member of the III-VI compound semiconductors, and its related compounds have recently gained an considerable attention because of their high non-linear optical coefficients in the infrared ranges, making them candidates for second harmonic generation (SHG) materials[l,2]. While the optical properties of those materials in bulk form are quite promising, poor thermal and mechanical properties preclude their easy applications. In thin film devices, the thermal and mechanical properties are dominated by those of the substrate, therefore, heteroepitaxially grown thin films of GaSe and related materials on substrates such as GaAs, Si and A12O3 should enable their application in device structures. Development of such new generation of materials, however, require fundamental knowledge about the surface and interface structure that play decisive roles in the thin film crystallinity and materials properties.