In this work, we study the growth features, as well as the structural and optical properties of CaSi2 layers formed in the process of successive deposition of Si and CaF2 on a Si (111) substrate with simultaneous irradiation with high energy electron beam. The Raman spectra recorded in the regions of the electron beam action showed peaks characteristic of crystalline CaSi2 layers. The study of the surface morphology of the grown structures demonstrated that, under the chosen synthesis conditions, the formation of CaSi2 layers during electron irradiation occurs according to a two-dimensional layer mechanism. The photoluminescence spectra measured in the region modified by the electron beam have significant differences from the spectra measured outside this region.