Kinetic and X-ray Photoelectron Spectroscopic Studies of the Thermal Nitridation of Si(100)

Abstract

ABSTRACTThe thermal nitridation of Si(100) by NH3 and N2H4 has been studied by X-ray photoelectron (XPS) and Auger electron (AES) spectroscopies. The pressure dependence of the rates as a function of reaction time has been measured. It has been found that the growth of the first monolayer (ML) of nitride is mediated by a surface reaction step. For subsequent growth, diffusion of one or more of the reacting species becomes an important process in determining the rate of reaction. Such species may be substrate Si diffusing to the vacuum/Si3N4 interface, or possibly network nitrogen diffusing into the Si substrate. The independence of the reaction rate on NH3 or N2H4 pressure at long reaction times rules out a mechanism involving molecular diffusion of the nitriding gas to the Si3N4/Si interface in a manner similar to the oxidation of Si by O2 or H2O. Careful analysis of the Si(2p) XPS spectra reveals the presence of a unique Si species with a Si(2p) binding energy intermediate between elemental Si and Si in Si3N4. Further, the relative intensity of the Si(2p) features due to this species, and the angular dependence of the XPS peaks indicate that they result from a ML of Si at the outermost surface layer, on top of the growing Si3N4 film.