New analytical techniques and applications are needed to address the challenges facing the semiconductor industry as transistor feature sizes continue to decrease beyond the 100 nm technology node. Several new applications of quadrupole ion trap (QIT) and Fourier transform ion cyclotron resonance (FTICR) mass spectrometry are presented, specifically applied to process tool effluent characterization. A QIT with atmospheric pressure transfer line and pneumatically driven valves is used to characterize a dielectric etch process, with response times comparable to extractive Fourier transform infrared (FTIR) spectroscopy. The QIT allows application of collision‐induced dissociation (CID) for structure elucidation, and is useful when high‐molecular weight metal organic precursors are used in processes that evolve byproducts that are ambiguous by gas‐phase infrared analysis. Similarly, a transportable FTICR with a fixed magnet and pulsed‐valve sample introduction allows matrix ion ejection to improve the sensitivity to analyte ions. The FTICR has also been evaluated for a low‐pressure chemical vapor deposition (LPCVD) process using a high‐molecular weight precursor. Byproducts are ambiguous in FTIR spectra, but the FTICR provided structural confirmation of the effluent species, and is a useful complement to FTIR. The FTICR was also used with FTIR to characterize process tool effluent emissions in a study using SF6and Ar to plasma etch a candidate metal oxide gate electrode material, RuO2. The results confirmed that no significant amount of RuO4, a toxic byproduct, were produced in this process. © 2003 American Institute of Physics