Submillimeter-wavelength linear-absorption spectroscopy has been applied to the chemical diagnostics of reactive-ion etching plasmas in a modified capacitively coupled gaseous electronics conference reactor. Approximately 1 mW of narrow-band (≪10 kHz) submillimeter radiation between 450 and 750 GHz is produced using a backward-wave oscillator (BWO). The BWO is frequency stabilized to a harmonic of a 78–118 GHz frequency synthesizer. The submillimeter method offers high sensitivity for the ≈1 MHz linewidth, Doppler-broadened absorption lines typical of gas-phase molecules at a total pressure of less than 133 Pa (1 Torr). A large number of molecules can be detected, limited primarily by the need for a permanent electric dipole moment and for accurate line frequency predictions, the latter of which are often available in the literature. The capabilities of the diagnostic method have been demonstrated by the following three applications: (1) the measurement of water-vapor contamination in the reactor and in the precursor gas by monitoring a rotational transition of H2O in the reactor just prior to the initiation of the plasma; (2) the assessment of progress in the cleaning of the reactor by an O2/Ar plasma after a fluorocarbon plasma etch by monitoring the build up of the concentration of O3 and the depletion of the concentration of CF2O in the plasma; and (3) the determination of the endpoint in the etching of a SiO2 thin film on silicon by an octafluorocyclobutane/O2/Ar plasma by monitoring the decrease in the concentration of SiO in the - - plasma. The last observation is made possible by the large electric dipole moment for SiO of 1×10-29 C m (3.1 D), which gives a low minimum detectable number density for the radical of 2×107 cm-3 for an optical pathlength of 39 cm. © 2003 American Vacuum Society.