The adsorption and desorption kinetics for SiCl4 and SiCl2H2 on Si(111) 7×7 were studied using laser-induced thermal desorption (LITD) and temperature programmed desorption (TPD) techniques. Both LITD and TPD experiments monitored SiCl2 as the main desorption product at 950 K at all coverages of SiCl4 and SiCl2H2 on Si(111) 7×7.HC1 desorption at 850 K and H2 desorption at 810 K were also observed following SiCl2H2 adsorption. Isothermal LITD measurements of SiCl4 and SiCl2H2) adsorption on Si(111) 7×7 revealed that the initial reactive sticking coefficient decreased with increasing surface temperature for both molecules. The temperature-dependent sticking coefficients were consistent with precursor-mediated adsorption kinetics. Isothermal LITD studies of SiC12 desorption revealed second-order SiCl2 desorption kinetics. The desorption kinetics were characterizedby a desorption activation energy of Ed = 67 kcal/mol and a preexponential of vd = 3.2 cm2/s. TPD studies observed that the HCI desorption yield decreased relative to H2 and SiCl2 desorption as a function of surface coverage following SiCl2H2 exposure. These results indicate that when more hydrogen desorbs as H2 at higher coverages, The remaining chlorine is forced to desorb as SiCl 2.