We explore the potential of Time-Of-Flight Medium Energy Ion Scattering (TOFMEIS) for thin film analysis and analyze possible difficulties in evaluation of experimental spectra. Issues regarding different combinations of composition and stopping power as well as the influence of channeling are discussed. As a model system high-k material stacks made from ultra-thin films of HfO2 grown on a p-type Si (100) substrate with a 0.5 nm SiO2 interface layer have been investigated. By comparison of experimental spectra and computer simulations TOF-MEIS was employed to establish a depth profile of the films and thus obtaining information on stoichiometry and film quality. Nominal film thicknesses were in the range from 1.8 to 12.2 nm. As a supporting method Rutherford-Backscattering spectrometry (RBS) was employed to obtain the areal density of Hf atoms in the films.