A hybrid mass spectrometer consisting of a magnetic sector, two electric sectors, and a quadrupole mass filter (BEEQ) has been built for the study of polyatomic ion/surface collision phenomena over the energy range of a few electron volts to several keV. Primary ions are generated by electron ionization or by chemical ionization, and the first two sectors are used to deliver a monoenergetic beam of ions, of a selected mass‐to‐charge m/z ratio, to a decelerator which sets the desired collision energy. The target, which can be introduced into the system without breaking vacuum, is mounted on a goniometer and situated in an electrically shielded region in the center of a large scattering chamber which contains an electric sector and a quadrupole mass analyzer used for kinetic energy and mass measurements on the ejected ions. These analyzers rotate around the scattering center to allow selection of the scattering angle of ions leaving the surface.
Ultimate pressures attainable in the main scattering chamber are below 10−9 Torr allowing molecular targets, such as self‐assembled monolayers of alkyl thiols on gold, to be examined without surface contamination. Low‐energy (20–100 eV) collisions of polyatomic ions are reported, and examples are given of the effects of collision energy and scattering angle on surface induced dissociation mass spectra. The kinetic energy of the inelastically scattered ions is also measured, and in some cases, the internal energy can be estimated, the two measurements together providing information on energy partitioning associated with surface collisions. For example, it is shown that n‐butylbenzene molecular ions of 25 eV colliding with ferrocenyl‐terminated self‐assembled monolayer surfaces, rebound with 10 eV of recoil energy and 3 eV of internal energy.
The remainder of the energy goes into the surface. The capability of the BEEQ instrument to provide data on ion/surface reactive collisions is also illustrated with reactions such as alkyl group transfer at self‐assembled monolayer surfaces. In addition, data are given showing the ability of the system to provide information on the kinetic energy distributions of ions generated in the course of high‐energy collisions at the surface. Mass analysis of the sputtered products provides the instrument with secondary‐ion mass spectrometry capabilities.