The authors have addressed the application of advanced ion beam–based analytical techniques to various physical characterization aspects in sub-32-nm semiconductor front-end-of-line materials and processes. We have presented the application of 18O-isotope labeling in combination with SIMS depth profiling to follow O-migration in high-k/metal gate stacks. We have also demonstrated the application of complementary low-energy ion scattering and time-of-flight SIMS surface analysis to determine high-k thin film closure and growth mode for different deposition techniques. We have also proposed alternative Dynamic Secondary Ion Mass Spectrometry (DSIMS) protocols for the quantitative analysis of phosphorous ultra-shallow junctions, resulting in more accurate near-surface P-profile and in situ B-doped Si1−xGex epitaxial films with explicit correction of sputter and ionization yield variations as function of [Ge]. We have demonstrated the feasibility of backside SIMS on appropriate III–V high-mobility channel stacks, resulting in unprecedented depth resolution at the source/drain metal–contact/III–V interface. Copyright © 2012 John Wiley & Sons, Ltd.