Metal-assisted secondary ion mass spectrometry using atomic (Ga⁺ , In⁺ ) and fullerene projectiles

The advantages and drawbacks of using either monatomic or buckminsterfullerene primary ions for metal-assisted secondary ion mass spectrometry (MetA-SIMS) are investigated using a series of organic samples including additive molecules, polyolefins, and small peptides. Gold deposition is mostly performed by sputter-coating, and in some cases, the results are compared to those of thermal evaporation (already used in a previous article: Delcorte, A.; Médard, N.; Bertrand, P. Anal. Chem. 2002, 74, 4955). The microstructure of the gold-covered sample surfaces is assessed by scanning and transmission electron microscopies. The merits of the different sets of experimental conditions are established via the analysis of fragment and parent-like ion yields. For most of the analyzed samples, the highest yields of fragment and parent-like ions are already reached with the sole use of C projectiles. Metallization of the sample does not lead to a significant additional enhancement. For polyethylene and polypropylene, however, gold metallization associated with Ga/In projectiles appears to be the only way to observe large canonized, sample-specific chain segments (m/z ∼ 1000-2000). A detailed study of the polypropylene mass spectra as a function of gold coverage shows that the dynamics of yield enhancement by metal nanoparticles is strongly dependent on the choice of the projectile, e.g., a pronounced increase with Ga and a slow decay with C. The cases of Irganox 1010, a polymer antioxidant, and leucine enkephalin, a small peptide, allow us to investigate the specific influence of the experimental conditions on the emission of parent-(like) ions such as M, (M + Na), and (M + Au). The results show a dependence on both the type of sample and the considered secondary ion. Using theoretical and experimental arguments, the discussion identifies some of the mechanisms underlying the general trends observed in the results. Guidelines concerning the choice of the experimental conditions for MetA-SIMS are provided.