In this study, we use first principles density functional theory (DFT) to investigate the atomistic mechanism of the growth of titanium containing hybrid films known as "titanicones" deposited by MLD. We investigate in detail the chemistry of the MLD process between the TiCl4 or Ti(DMA)4 inorganic precursors and EG or GL organic molecules. We use anatase TiO2, rutile TiO2 and Al2O3 surface models.