The effect of water plasma treatment of both hydrophobic and hydrophilic Si(1 0 0) surfaces has been studied using infrared spectroscopy to monitor the various surface species present. Exposure to a water plasma results in a significant increase in the concentration of H-bonded hydroxyls and hydrides. Both atomic force microscopy (AFM) and cross-sectional transmission electron microscopy (XTEM) of TiO2 films deposited by atomic layer deposition at 300 degreesC, show that the morphology of the films is dependent on the nature of the initial surface. XTEM of the early stages of growth showed that coatings on hydrophilic substrates deposited as initially amorphous and continuous films, which crystallised with further growth. However, the hydrophobic substrate produced island growth of small, crystalline grains. AFM images of 23-nm thick films showed that films deposited on hydrophobic and hydrophilic Si consisted of 35-100 and 150-350 nm crystallites, respectively. A film on water plasma treated Si, closely resembled that on the hydrophilic surface, indicating that hydroxyl groups are responsible for directing the film growth. (C) 2003 Elsevier Science B.V. All rights reserved.