Surface and Interface Analysis, April 2016, Volume 48, Issue 4

The statistics of ToF-SIMS data revisited and introduction of the empirical Poisson
correction

Michael R. Keenan, Vincent S. Smentkowski

Abstract

Generation of time-of-flight secondary ion mass spectrometry (ToF-SIMS) data involves two
overarching processes: secondary ion production and secondary ion detection. The interpretation of
ToF-SIMS data is facilitated if the intensities of the as-measured mass spectra are proportional to the
abundances of the species under investigation. While secondary ion yield is normally taken to be a
linear process, ion detection is not owing to detector dead-time effects. Consequently, methods have
been devised that attempt to linearize, or correct, data that are affected by the dead time. In this
article, we review the statistics of ToF-SIMS data generation and confirm a report in the literature
that abundance estimates from so-called Poisson corrections are biased. We show that these
corrections are only unbiased asymptotically and that a rigorous probabilistic analysis can
quantitatively account for the observed bias. Two sources of bias are identified, one having a
statistical basis and one due to the form of the correction equation at high ion detection rates. Based
on insights gained from this analysis, we propose a new correction equation, the empirical Poisson
correction, which largely eliminates the statistical bias. The performance of the proposed correction
is illustrated by reanalyzing 14 experimentally measured datasets that suffer from varying levels of
dead-time effects.

ToF-SIMS analysis of a polymer microarray composed of poly(meth)acrylates with

C6derivative pendant groups

Andrew L. Hook, David J. Scurr

Abstract

Surface analysis plays a key role in understanding the function of materials, particularly in biological
environments. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) provides highly surface
sensitive chemical information that can readily be acquired over large areas and has, thus, become
an important surface analysis tool. However, the information-rich nature of ToF-SIMS complicates
the interpretation and comparison of spectra, particularly in cases where multicomponent samples
are being assessed. In this study, a method is presented to assess the chemical variance across 16
poly(meth)acrylates. Materials are selected to contain C6 pendant groups, and ten replicates of each
are printed as a polymer microarray. SIMS spectra are acquired for each material with the most
intense and unique ions assessed for each material to identify the predominant and distinctive
fragmentation pathways within the materials studied. Differentiating acrylate/methacrylate pairs is
readily achieved using secondary ions derived from both the polymer backbone and pendant groups.
Principal component analysis (PCA) is performed on the SIMS spectra of the 16 polymers, whereby
the resulting principal components are able to distinguish phenyl from benzyl groups, mono-
functional from multi-functional monomers and acrylates from methacrylates. The principal
components are applied to copolymer series to assess the predictive capabilities of the PCA. Beyond
being able to predict the copolymer ratio, in some cases, the SIMS analysis is able to provide insight
into the molecular sequence of a copolymer. The insight gained in this study will be beneficial for
developing structurefunction relationships based upon ToF-SIMS data of polymer libraries.
March 2016, Volume 48, Issue 3, Pages 115178

Effect of formulation of silica-based solution on corrosion resistance of silicate coating on

hot-dip galvanized steel

Shuang-hong Zhang, Gang Kong, Zi-wen Sun, Chun-shan Che, Jin-tang Lu

Abstract

Several silica-based solutions with 50g/l of SiO2 were prepared from sodium silicate solutions and
silica sol; the silicate conversion coatings were obtained by immersing hot-dip galvanized steel sheets
in these solutions. These solutions were characterized using high-resolution transmission electron
microscopy and 29Si nuclear magnetic resonance; the morphology of the coatings was observed by
SEM and atomic force microscopy while the corrosion resistance was evaluated by electrochemical
measurements as well as neutral salt spray tests. The results show that the coatings obtained from
the single silica sol solution had poor adhesion and the coating obtained from the sodium silicate
solution with low SiO2/Na2O molar ratio was uneven. By adding the silica sol to the silicate solution
with low molar ratio, uniform coatings with better protection property were obtained. According to
the results of 29Si nuclear magnetic resonance spectra, the effects of the distribution of silicate
anions with various polymerization degrees in the silica-based solutions on the microstructure and
corrosion resistance of the silicate coatings are discussed.

Film thickness measurement and contamination layer correction for quantitative XPS

J. Walton, M. R. Alexander, N. Fairley, P. Roach, A. G. Shard

Abstract

In order to determine the most appropriate method of measuring film thickness using imaging XPS, a
series of thin polymer films have been prepared and analysed using spectroscopy. The thickness of
these thin polymer films has been determined using peak shape analysis and by using photoelectron
peak areas compared with a bulk reference and by using relative sensitivity factors. These results
have been compared with values obtained using ellipsometry. The values obtained by measuring
photoelectron peak areas were seen to be influenced by the chemistry of the film, so that a bulk
reference of similar chemistry to the film is required for accurate thickness measurement. The values
obtained using peak shape analysis, both interactive and non-interactive, were not dependent on the
chemistry of the film and showed good agreement with ellipsometry. Imaging of a patterned
polymer film was successfully carried out, and the polymer cross section was shown to provide a
reasonable description of the inelastic background from the carbonaceous contamination layer. An
image of the substrate photoelectron intensity was successfully corrected for attenuation in both the
carbonaceous contamination layer and the polymer film simultaneously using an image of the film
thickness determined by non-interactive peak shape analysis. This procedure is suitable for
automated film thickness measurement and correction for attenuation in the carbonaceous
contamination layer in both spectroscopy and imaging.