Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

[Image: see text] Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH(4), CO(2), and O(2) into an Ar cluster projectile, Ar(n)(+) (n = 1000–10,000) to form a mixed cluster. The ‘tailored beam’ has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H(+) and Cl(−), allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D(2)O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. Protonation and H–D exchange in the trehalose molecule M was monitored upon deposition of D(2)O on the target surface, leading to the observation of [M(n)* + H](+) or [M(n)* + D](+) ions, where n = 1–8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield