Metal electrode materials are being extensively evaluated as potential replacements for polysilicon in order to eliminate gate depletion, reduce gate resistance, overcome equivalent oxide thickness (EOT) scaling limitations and Fermi level pinning effects associated with the reaction between Hf-based dielectric films and the polysilicon electrode. High-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) using X-ray spectra and electron energy loss spectra (EELS) were used to produce elemental profiles of dielectric and metal electrode constituents with particular emphasis on interfacial interactions. High spatial resolution chemical scan profiles of silicon, oxygen, nitrogen, and hafnium from the dielectric components in conjunction with various transition metals including hafnium, tantalum, molybdenum and ruthenium have been acquired to characterize the extent of material intermixing and crystallization as a function of deposition parameters and anneal temperature. The influence of the atomic percent Si in ternary compounds consisting of transition metal nitrides is presented within the context of Rutherford backscattering (RBS) composition data. Finally, factors influencing metal workfunction are presented based on physical and electrical characterization of high-k capacitors and transistors.