The development of a mass spectrometry-based technique that uses low energy ion-surface collisions to characterize surfaces

Abstract

Low energy (tens of eV) ion-surface collisions carried out in a tandem mass spectrometer are investigated as a tool to characterize self-assembled monolayer (SAM) films. The target films are prepared by spontaneous chemisorption of thiol-based (HS-R) compounds onto Au (111) substrates. Most of the films used as targets contain alkane or fluoro-alkane backbones, some with unique groups in the terminal position (e.g., -CD₃, -OH, -OC(O)CF₃). Pyrazine is the most frequently used probe ion, however in certain cases other small organic molecules are also used. Common interactions between the impinging ion and the target film that vary as a function of film characteristics include, but are not limited to, reactive scattering, neutralization and T → V conversion. Pyrazine ion readily reacts when colliding with hydrocarbon films at 20-eV, forming product ions that incorporate a hydrogen atom or a methyl group. Several examples of the utility of these processes to characterize film properties are presented. For hydrocarbon films, ion-surface reactions of pyrazine ion resulting in addition of a hydrogen atom or a methyl group are shown to vary with the quality, chemical composition and orientation of the target film. Experiments with isotopically labeled films show that the ion beam interacts predominantly with the end groups of the film, however interactions with underlying groups increase as the film or substrate quality decreases. The orientation difference of odd and even chain length n-alkanethiols produces a measurably different degree of hydrogen addition with the higher free energy odd chain length orientation being more reactive. The composition of mixed component films (H, D or H, F) is tracked by measuring the abundance of unique reaction products, energy transfer (translational to vibrational conversion) and charge exchange properties. When mixed films containing deuterium labeled and unlabeled n-alkanethiols are subjected to collisions of 20-eV pyrazine ion, the D-addition ion abundance increases linearly with the surface concentration of D-containing alkane chains. When mixed films containing different ratios of H and F components are the target, several processes track with the changing population of surface species. As the target films become more fluorocarbon in nature H-addition decreases, total ion current reaching the detector increases, and dissociation increases. Several properties of electron transfer from the film to the ion are examined. When the probe ion and collision energy remain consant, charge exchange is shown to be primarily governed by the work function of the film and the thickness of the adsorbed layer. Fluorocarbon films, which have a higher work function than hydrocarbon films, consistently show less charge exchange. When comparing hydrocarbon films of varying chain lengths (ranging from 15 to 18 carbons), a increase of ∼1% in total ion current measured at the detector is observed for each additional methylene in the chain.