Nanovolume analysis with secondary ion mass spectrometry using massive projectiles

A variant of secondary ion mass spectrometry is presented where the surface is bombarded with individual gold nanoparticles each resolved in time and space with a corresponding event-by-event detection of the secondary ions (SIs). The projectile used, Au400(4+), with impact energy of 136 keV, generates high SI yields. Typically, there is co-emission of multiple SIs from a single impact, i.e., emission of SIs from molecules co-located within a nanovolume with dimensions in the 10-nm range. The ability to detect co-located molecules was tested on samples consisting of alternating nanometric layers of oppositely charged polyions, poly(diallyldimethylammonium chloride), poly(styrenesulfonate) (PSS), and clay nanoplatelets. To achieve signal statistics, the chemical analysis was carried out with a sequence of stochastic impacts making this method suitable for characterization of similar nanoparticles or spots dispersed on a surface. Attomole detection sensitivity was achieved for PSS. The homogeneity of assembled layers could be assessed with approximately 10-nm resolution.