Comparison of primary monoatomic with primary polyatomic ions for the characterisation of polyesters with static secondary ion mass spectrometry.

Static secondary ion mass spectrometry (S-SIMS) emerges as one of the most adequate methods for the surface characterisation of polymers with an information depth of essentially one monolayer. The continuing search for increased analytical sensitivity and specificity has led to exploring the use of polyatomic primary ions as an alternative to the traditionally applied monoatomic projectiles. As part of a systematic investigation on polyatomic bombardment of organic and inorganic solids, this paper focuses on selected polyesters. Mass spectra and ion yields are compared for layers deposited on silicon wafers by spincoating solutions with different concentrations of poly(epsilon-caprolactone) (PCL), poly(butylene adipate) (PBA) and poly(ethylene adipate) (PEA). Accurate mass measurements have been used to support the assignment of the ions and link the composition of the detected ions to the analyte structure. Use of polyatomic projectiles increases the yield of structural ions with a factor of +/-15, +/-30 and +/-10 for PCL, PBA and PEA, respectively, in comparison to bombardment with Ga+ primary ions, while the molecular specificity is improved by the detection of additional high m/z ions.