Atomic layer deposition (ALD) is an important technology for depositing functional coatings on accessible, reactive surfaces with precise control of thickness and nanostructure. Unlike conventional chemical vapour deposition, where growth rate is dependent on reactant flux, ALD employs sequential surface chemical reactions to saturate a surface with a (sub-) monolayer of reactive compounds such as metal alkoxides or covalent halides, followed by reaction with a second compound such as water to deposit coatings layer-by-layer. A judicious choice of reactants and processing conditions ensures that the reactions are self-limiting, resulting in controlled film growth with excellent conformality to the substrate. This paper investigates the deposition and characterisation of multi-layer TiO2 /Al2O3 films on a range of substrates, including silicon <100>, soda glass and polycarbonate, using titanium tetrachloride/water and trimethylaluminium/water as precursor couples. Structure-property correlations were established using a suite of analytical tools, including transmission electron microscopy (TEM), secondary ion mass spectrometry (SIMS), X-ray reflectometry (XRR) and spectroscopic ellipsometry (SE). The evolution of nanostructure and composition of multi-layer high/low refractive index stacks are discussed as a function of deposition parameters.