Extending the scalability of deep trench capacitor dynamic random access memories requires introduction of a high-k dielectric-based storage capacitor structure. Pr-enriched Al2O3 dielectrics with TiN electrodes appear as a promising materials system for this application. Electrical measurements performed on this materials combination show, however, that achieving a very low capacitance equivalent thickness and low leakage current requires very careful control of the electrode/dielectric interface properties. In particular, formation of a parasitic interface layer has to be avoided. For this purpose, we carried out a systematic synchrotron radiation x-ray photoelectron spectroscopy study to non-destructively investigate the interface reactivity of the PrxAl2-xO3 (x = 0, 1, 2)dielectrics with TiN metal electrodes. The depth profiling study shows that the TiN substrate is covered with a native TiO2. Additionally, a thin interfacial Ti oxynitride layer is present between these compounds, resulting in a TiN/TiNO/TiO2 materials stack. Molecular beam deposition of Al2O3 onto substrates of this structure leads to a remarkable reduction of the native oxide. In contrast, in the same way deposited PrAlO3 and Pr2O3 dielectrics are significantly less reactive towards TiO2. As a consequence, the native TiON/TiO2 remains the main component of the interface layer in the TiN/PrAlO3 and TiN/Pr2O3 capacitor stacks. Such a configuration poses severe scalability problems to the Pr aluminate dielectrics.