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We assessed two approaches for determining shell thicknesses of core-shell nanoparticles (NPs) by X-ray photoelectron spectroscopy (XPS). These assessments were based on simulations of photoelectron peak intensities for Au-core/C-shell, C-core/Au-shell, Cu-core/Al-shell, and Al-core/Cu-shell NPs with a wide range of core diameters and shell thicknesses. First, we demonstrated the validity of an empirical equation developed by Shard for determinations of shell thicknesses. Values of shell thicknesses from the Shard equation typically agreed with actual shell thicknesses to better than 10 %. Second, we investigated the magnitudes of elastic-scattering effects on photoelectron peak intensities by performing a similar series of simulations with elastic scattering switched off in our simulation software. Our ratios of the C-shell 1s intensity to the Au-core 4f intensity with elastic scattering switched off were qualitatively similar to those obtained by Torelli from a model that neglected elastic scattering. With elastic scattering switched on, the C 1s/Au 4f intensity ratios generally changed by less than 10 %, thereby justifying the neglect of elastic scattering in XPS models that are applied to organic ligands on Au-core NPs. Nevertheless, elastic-scattering effects on peak-intensity ratios were generally much stronger for C-core/Au-shell, Al-core/Cu-shell, and Cu-core/Al-shell NPs, and there were second-order dependences on core diameter and shell thickness.

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Accurate and reproducible measurement of the structure and properties of high-value nanoparticles is extremely important for their commercialization. A significant proportion of engineered nanoparticle systems consist of some form of nominally core–shell structure, whether by design or unintentionally. Often, these do not form an ideal core–shell structure, with typical deviations including polydispersity of the core or shell, uneven or incomplete shells, noncentral cores, and others. Such systems may be created with or without intent, and in either case an understanding of the conditions for formation of such particles is desirable. Precise determination of the structure, composition, size, and shell thickness of such particles can prove challenging without the use of a suitable range of characterization techniques. Here, the authors present two such polymer core–shell nanoparticle systems, consisting of polytetrafluoroethylene cores coated with a range of thicknesses of either polymethylmethacrylate or polystyrene. By consideration of surface energy, it is shown that these particles are expected to possess distinctly differing coating structures, with the polystyrene coating being incomplete. A comprehensive characterization of these systems is demonstrated, using a selection of complementary techniques including scanning electron microscopy, scanning transmission electron microscopy, thermogravimetric analysis, dynamic light scattering, differential centrifugal sedimentation, and X-ray photoelectron spectroscopy. By combining the results provided by these techniques, it is possible to achieve superior characterization and understanding of the particle structure than could be obtained by considering results separately.