Theoretical investigation on the adsorption and dissociation behaviors of TiCl4 on pyrolytic carbon surface

We present a theoretical investigation of the reaction mechanism of TiCl4 dissociation on pyrolytic carbon surface and discuss the influence of H atom on adsorption and dissociation behaviors of TiCl4 by using density functional theory. The adsorption behaviors of TiClx (x = 4-0) and the interactions between pre-adsorbed H atom and TiClx are studied by calculating adsorption energies Eads and interaction energies HTi, respectively. The pre-adsorbed H atom significantly facilitates the adsorption of TiClx on pyrolytic carbon surface. Specially, TiCl3 adsorption on pyrolytic carbon surface converts from an endothermic process into an exothermic process due to the present of pre-adsorbed H atom. The calculation results of HTi show that the interactions between pre-adsorbed H atom and TiClx are attractive. The dissociation of TiCl4 on pre-adsorbed H pyrolytic carbon surface is an exothermic process, and TiCl4 → TiCl3 is the limited step. The dissociation barriers of each step are less than 1.5 eV except for TiCl → Ti, which does not need to overcome any barriers, that is to say, once TiCl is adsorbed on pre-adsorbed H surface the reaction of TiCl → Ti spontaneously occurs. It thus can be concluded that the dissociation of TiCl4 on pyrolytic carbon surface is a favorable process as long as H2 molecular have decomposed into atomic H and adsorbed on pyrolytic carbon surface, and the intermediate species (TiCl3, TiCl2 and TiCl) play an important role on the titanium CVD deposition. We also study the adsorption behavior of H atom and the dissociation behavior of H2 molecular on pyrolytic carbon surface.