We have measured Raman and Electron-spin resonance (ESR) spectra of fluorine-doped SiO2 films deposited by two different methods. In high-density plasma (HDP) films, the Raman band at about 490 cm(-1) becomes drastically stronger as the F/Si ratio increases, whereas the Raman band from threefold ring defect is independent of the F/Si ratio. The unusual increase of the intensity of the 490 cm(-1) band in HDP films has been interpreted in terms of the existence of Si-Si clusters. From a comparison between Raman spectra of HDP film and plasma chemical vapor deposition using tetraethoxysilane (p-TEOS) film with the same F/Si ratios it has been found that HDP film has more Si-Si bonds and threefold ring defects than p-TEOS film. Furthermore, the polarized Raman spectra in the 810 cm(-1) bands indicate that inhomogeneous SiO2 clusters of various sizes should exist in the network structure of HDP film. The result of the ESR measurement shows that HDP films have fewer dangling bonds than p-TEOS films. It is considered that many Si-Si clusters, threefold ring defects, and inhomogeneous SiO2 cluster sizes, and the few dangling bonds in HDP films give rise to the film properties of low stress, good adhesion with Si substrate, and low water permeation. (C) 2007 Elsevier B.V. All rights reserved.