Results are presented of a photoemission study of the electronic structure of SiON layers formed by a pulsed-RF decoupled plasma nitration (DPN) of ultra-thin SiO2 grown base layers approximately 1.0 nm thick. The optical thickness of these device grade nitrided dielectric layers was in the range 1.4-1.6 nm. X-ray photoelectron spectroscopy (XPS) studies indicate that the nitrogen is incorporated in a single chemical environment at concentration levels in the range 15-17%. Angle resolved XPS measurements show that the nitrogen is distributed through the layer, with the binding energy of the N 1s peak at 398.3 eV which is indicative of a Si3N4-like chemical species in an oxide environment. High resolution core level photoemission studies of the spin orbit stripped Si 2p(4+) peak revealed full width half maximum values in the range 1.4-1.55 eV, which are significantly larger than the 1.15 eV value reported for SiO2 layers. Synchrotron radiation photoemission studies of the valence band spectra enable the valence band off-set at the Si/SON interface to be evaluated as 2.3 eV and to infer a conduction band off-set of 2.1 eV. (c) 2005 Elsevier B.V. All rights reserved.