Single-shot Excimer Laser Annealing (ELA) was performed onto Si surface that was previously B+ implanted with or without Ge+ pre-amorphization. As a result, p+ type USJ (Ultra-Shallow Junction) has been formed. In process analysis, using Infrared Spectroscopic Ellipsometry (IR-SE) has been performed and compared with conventional 4-point probe method. Also, the corresponding crystallinity for the USJ of Si surface has been studied using Ultraviolet-Visible (UV-Vis) Spectroscopic Ellipsometry. In the case of pre-amorphization by Ge+ implantation, the laser energy density threshold required for melting the surface, and therefore for electrical activation, decreased drastically because of the difference in the thermodynamic properties of the amorphized Si. Estimation of the junction depth shows a shallower junction when using UV-SE, as compared to IR-SE. This can be explained by the fact that, in the UV range, the crystallinity of the top layer is predominant while IR-SE is more sensitive to dopant activation. This efficient single-shot ELA is a candidate for the USJ formation for sub-0.1 νm CMOS transistors. The effective method for investigating the activation state related to the crystallinity by using UV-SE and IR-SE is expected to apply as a non-contact analytical tool for USJ formation.