We investigated the electronic chemical properties and film structures in SiN passivation layers on crystalline Si by X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry (XRR). From XPS analyses, a N-rich component (N-Si-N) and oxygen mixing were observed at the interface. The longest lifetime was obtained after post deposition annealing at 600 °C, where the N-rich layer was the thinnest with small peak height. Therefore, longer lifetime could be obtained as the N concentration at the interface decreased. The film consisted of three SiN layers and one SiO 2 layer, as confirmed by XRR profile fitting. From the density profiles, a longer lifetime was obtained when the density gradient in the oxygen mixing layer was small. Results of XPS and XRR suggested that N at the interface significantly affected the lifetime. We believe it is important to understand the electronic chemical properties at the passivation interface to realize high-efficiency Si solar cells.