The angle-resolved Si 2p photoelectron spectra arising from a interfacial transition layer formed on a Si(100) were measured with a probing depth of nearly 2 nm. The novel analytical procedure of these spectra was developed by considering that one SiO2 monolayer, two compositional transition layers (CTLs), and one Si monolayer constituting the Si substrate surface are continuously connected with each other to maintain the areal density of Si atoms. It was found for thermally grown transition layers that two CTLs are formed on the oxide side of the CTL/Si interface and the chemical structures correlated with the residual stress appear on the Si substrate side of the interface. The effects of oxidation temperature in the range from 900 to 1050 degrees C, annealing in the forming gas, and oxidation using oxygen radicals on the chemical structures of transition layers formed on both sides of the interface were also clarified. (c) 2013 The Japan Society of Applied Physics