In this work, MBE growth of GaAs on CaF2/Si (111) substrates has been studied with both Rutherford backscattering spectrometry, transmission electron microscopy and atomic force Microscopy. It has been observed that, under certain conditions, a chemical reaction between As adatoms and the CaF2 layers can be induced, by which a more stable As layer on the CaF2 surface is formed. The existence of the As layer modifies the CaF2 surface free energy, which, if properly controlled, leads to two-dimensional (2D) nucleation of GaAs on the CaF2/Si (111) surface as opposed to the more commonly observed three-dimensional (3D) growth. Artificial Modification of the CaF2 (111) surface by introducing Ca prior to GaAs growth is also discussed as a promising way to achieve 2D nucleation. In subsequent growth, two kinds of twins have been observed. All samples were observed to have Micro-twins near the GaAs/CaF2 interface. These twins can be suppressed during the first 1000Å, if the layer is grown in a narrow optimal growth window. Otherwise, the growth will be in a 3D Mode at lower temperatures, or it will suffer from the formation of large rotational twins at higher temperatures. It has been observed that growth on vicinal substrates tilted toward [1
12] azimuth is helpful in suppressing the development of rotational twins so that growth on these substrates have a wider optimal growth window. Surface Morphology of CaF2 epitaxial layers grown on Si (111) substrates with different vicinal angles has also been investigated. It May have significant impact on the twin development during subsequent GaAs growth.