The results of investigating $SiL_{2,3}$/ X-ray emission valence spectra of amorphous silicon films irradiated by excimer laser are presented. It is found that laser annealing leads to crystallization of amorphous silicon films and the crystallinity increases with the laser energy density from 250 to 400 mJ/$ extrm{cm}^2$. The vertical structure of the film is investigated by changing the accelerating voltage on the X-ray tube, and the chemical and structural state of Si$_3$N$_4$ buffer layer is found not to be changed by the excimer laser treatment.