Molecular Surface Imaging of Particles Using Microprobe Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS)

Abstract

The objective of this research is to develop imaging time-of-flight secondary ion mass spectrometry (TOF-SIMS) to characterize ultra-thin organic films on microscopic particles. An initial application is to evaluate the surface chemistry of polycyclic organic matter (POM) on combustion-generated particles as an area of fundamental interest in the assessment of the environmental fate and impact of carcinogenic pollutants.Controlled deposition of POM monolayers was achieved using either gas or solution phase coating on model particles such as silica, as well as on authentic environmental particles such as coal flyash or soot. Another aspect of the work was to monitor surface transformations of adsorbed POM involving photochemical degradation or reactions with gaseous pollutants such as nitrogen oxides. For the first time, variations in POM adsorption and reactivity have been probed as a function of particle type by the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) to perform surface analysis on single particles. Results using a pulsed gallium microbeam source on a TOF-SIMS indicated that 0.1 monolayer coverages of individual POM species can be detected as quasimolecular ions from single particles with diameters typically in the 5 μm range. Primary ion doses were <1013 ions/cm2 to minimize surface damage during a typical 10 min spectrum acquisition from an 40x40 ftm image field. Correlation of in situ measurements using TOF-SIMS with traditional solvent extraction and chromatographic results, including LC or GC-MS, allowed for more detailed assessments of the sensitivity and quantitative capabilities of TOF-SIMS. The combination of monolayer analysis with microanalysis creates severe challenges to sensitivity since the total number of molecules within the analytical volume is so small (< 107 POM molecules on a lμm2 particle area)