Alternating layers of two different organic materials, Irganox1010 and Irganox3114, have been created using vapor deposition. The layers of Irganox3114 were very thin ( approximately 2.5 nm) in comparison to the layers of Irganox1010 ( approximately 55 or approximately 90 nm) to create an organic equivalent of the inorganic 'delta-layers' commonly employed as reference materials in dynamic secondary ion mass spectrometry. Both materials have identical sputtering yields, and we show that organic delta layers may be used to determine some of the important metrological parameters for cluster ion beam depth profiling. We demonstrate, using a C(60) ion source, that the sputtering yield, S, diminishes with ion dose and that the depth resolution also degrades. By comparison with atomic force microscopy data for films of pure Irganox1010, we show that the degradation in depth resolution is caused by the development of topography. Secondary ion intensities are a well-behaved function of sputtering yield and may be employed to obtain useful analytical information. Fragments characteristic of highly damaged material have intensity proportional to S, and those fragments with minimal molecular rearrangment exhibit intensities proportional to S(2). We demonstrate quantitative analysis of the amount of substance in buried layers of a few nanometer thickness with an accuracy of approximately 10%. Organic delta layers are valuable reference materials for comparing the capabilities of different cluster ion sources and experimental arrangements for the depth profiling of organic materials.

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The aim of this paper is twofold: first to report on the lateral and vertical characterisation of a surface chemical gradient of carboxylic-acid functionality and second, to demonstrate the use of said gradient to probe the passive adsorption of immunoglobulin G (IgG) as a function of the density of surface carboxylic-acid groups.A surface chemical gradient of carboxylic-acid functionality was fabricated by the plasma copolymerisation of octadiene (OD) and acrylic acid (AA). The plasma-polymerised gradient was over 12 mm, with 2 mm of plasma-polymerised OD at one end and 2 mm of plasma-polymerised AA at the other. By means of linescan angle resolved x-ray photoelectron spectroscopy (ARXPS) it is shown precisely how acid functionality varies from the 2 mm position (OD end) on the gradient to the 10 mm position (AA end). By recording data from 16 angles at each of the 25 sampling points along the gradient, it is shown that the surface gradient also changes vertically, most notably in the thickness of the plasma polymer. At the OD end the plasma-polymerised layer is 6.3 nm thick, while at the AA end the plasma-polymerised layer is 5 nm. More subtle changes in chemistry through the plasma-polymerised layer are shown at the 7.5 and 10 mm points.An identical gradient is used to probe IgG adsorption along the length of the gradient. ARXPS is used to monitor the nitrogen 1s (N1s) signal at 25 points, the N1s signal being unique to adsorbed IgG. It is demonstrated that IgG adsorbs in far greater amount (IgG per unit area) at the OD end, and the amount of adsorbed IgG decreases along the length of the gradient. It is estimated that >200 ng/cm 2 adsorbed at the OD, while at the AA the amount adsorbed was <20 ng/cm 2 .

Sputter-depth profiles of model organic thin films on silicon using C 60 primary ions have been employed to measure sputtering yields and depth resolution parameters. We demonstrate that some materials (polylactide, Irganox 1010) have a constant and high sputtering yield, which varies linearly with the primary ion energy, whereas another material (Alq 3 ) has lower, fluence-dependent sputtering yields. Analysis of multi-layered organic thin films reveals that the depth resolution is a function of both primary ion energy and depth, and the sputtering yield depends on the history of sputtering. We also show that ∼30% of repeat units are damaged in the steady-state regime during polylactide sputtering.  Crown

The accurate characterization of submicrometer and nanometer sized particles presents a major challenge in the diverse applications envisaged for them including cosmetics, biosensors, renewable energy, and electronics. Size is one of the principal parameters for classifying particles and understanding their behavior, with other particle characteristics usually only quantifiable when size is accounted for. We present a comparative study of emerging and established techniques to size submicrometer particles, evaluating their sizing precision and relative resolution, and demonstrating the variety of physical principles upon which they are based, with the aim of developing a framework in which they can be compared. We used in-house synthesized Stöber silica particles between 100 and 400 nm in diameter as reference materials for this study. The emerging techniques of scanning ion occlusion sensing (SIOS), differential centrifugal sedimentation (DCS), and nanoparticle tracking analysis (NTA) were compared to the established techniques of transmission electron microscopy (TEM), scanning mobility particle sizing (SMPS), and dynamic light scattering (DLS). The size distributions were described using the mode, arithmetic mean, and standard deviation. Uncertainties associated with the six techniques were evaluated, including the statistical uncertainties in the mean sizes measured by the single-particle counting techniques. Q-Q plots were used to analyze the shapes of the size distributions. Through the use of complementary techniques for particle sizing, a more complete characterization of the particles was achieved, with additional information on their density and porosity attained.

This paper describes a simple and direct method to calculate the shell thickness of spherical core–shell nanoparticles from X-ray photoelectron spectroscopy data. In contrast to existing methods, it is not iterative and involves a simple forward calculation that is accurate to a typical error of 4%. The method is applicable to any core–shell material pair, but the accuracy becomes worse when the kinetic energy of photoelectrons arising from the core and the shell are widely separated. Application of the method to two example systems from the literature is demonstrated: silicon oxide on silicon and carbon on gold. In both cases, accuracy in shell thickness that is significantly better than an atomic diameter is demonstrated. An accurate direct equation to calculate the thickness of overlayers on planar samples is also provided.

The depth profiling of organic materials with argon cluster ion sputtering has recently become widely available with several manufacturers of surface analytical instrumentation producing sources suitable for surface analysis. In this work, we assess the performance of argon cluster sources in an interlaboratory study under the auspices of VAMAS (Versailles Project on Advanced Materials and Standards). The results are compared to a previous study that focused on C(60)(q+) cluster sources using similar reference materials. Four laboratories participated using time-of-flight secondary-ion mass spectrometry for analysis, three of them using argon cluster sputtering sources and one using a C(60)(+) cluster source. The samples used for the study were organic multilayer reference materials consisting of a ∼400-nm-thick Irganox 1010 matrix with ∼1 nm marker layers of Irganox 3114 at depths of ∼50, 100, 200, and 300 nm. In accordance with a previous report, argon cluster sputtering is shown to provide effectively constant sputtering yields through these reference materials. The work additionally demonstrates that molecular secondary ions may be used to monitor the depth profile and depth resolutions approaching a full width at half maximum (fwhm) of 5 nm can be achieved. The participants employed energies of 2.5 and 5 keV for the argon clusters, and both the sputtering yields and depth resolutions are similar to those extrapolated from C(60)(+) cluster sputtering data. In contrast to C(60)(+) cluster sputtering, however, a negligible variation in sputtering yield with depth was observed and the repeatability of the sputtering yields obtained by two participants was better than 1%. We observe that, with argon cluster sputtering, the position of the marker layers may change by up to 3 nm, depending on which secondary ion is used to monitor the material in these layers, which is an effect not previously visible with C(60)(+) cluster sputtering. We also note that electron irradiation, used for charge compensation, can induce molecular damage to areas of the reference samples well beyond the analyzed region that significantly affects molecular secondary-ion intensities in the initial stages of a depth profile in these materials.