RESUMO
Technological progress has spurred the development of increasingly sophisticated analytical devices. The full characterization of structures in terms of sample volume and composition is now highly complex. Here, a highly improved solution for 3D characterization of samples, based on an advanced method for 3D data correction, is proposed. Traditionally, secondary ion mass spectrometry (SIMS) provides the chemical distribution of sample surfaces. Combining successive sputtering with 2D surface projections enables a 3D volume rendering to be generated. However, surface topography can distort the volume rendering by necessitating the projection of a nonflat surface onto a planar image. Moreover, the sputtering is highly dependent on the probed material. Local variation of composition affects the sputter yield and the beam-induced roughness, which in turn alters the 3D render. To circumvent these drawbacks, the correlation of atomic force microscopy (AFM) with SIMS has been proposed in previous studies as a solution for the 3D chemical characterization. To extend the applicability of this approach, we have developed a methodology using AFM-time-of-flight (ToF)-SIMS combined with an empirical sputter model, "dynamic-model-based volume correction", to universally correct 3D structures. First, the simulation of 3D structures highlighted the great advantages of this new approach compared with classical methods. Then, we explored the applicability of this new correction to two types of samples, a patterned metallic multilayer and a diblock copolymer film presenting surface asperities. In both cases, the dynamic-model-based volume correction produced an accurate 3D reconstruction of the sample volume and composition. The combination of AFM-SIMS with the dynamic-model-based volume correction improves the understanding of the surface characteristics. Beyond the useful 3D chemical information provided by dynamic-model-based volume correction, the approach permits us to enhance the correlation of chemical information from spectroscopic techniques with the physical properties obtained by AFM.
RESUMO
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a high performance tool for molecular depth profiling of polymer films, in particular when they are structured in microphases. However, a major issue is the degradation of polymer materials under ion irradiation in reactions such as cross-linking, chain breaking, or reorganization processes of polymers which have been demonstrated for materials such as polystyrene (PS) and poly(methyl methacrylate) (PMMA). This work aims at comparing ToF-SIMS molecular depth profiling of structured polymers (polystyrene (PS)-b-polymethyl methacrylate (PMMA) block copolymers (BCP)) using either ultralow energy cesium or the more recently introduced C60++ (under NO dosing and with sample cooling) and argon cluster ion beams (using Ar1500+ ions at 5 keV). The latter improved the quality of the depth profiles, especially the argon cluster ion beam, as it is characterized by a greater homogeneity for the sputter yields of PS and PMMA. No significant artifacts were observed, and this was confirmed by the comparison of depth profiles obtained from films with variable thickness, annealing time, and morphology (cylindrical blocks vs spherical blocks). Comparison to a theoretical model (hexagonal centered pattern) ensured that the ToF-SIMS depth profiles described the real morphology and may thus be a relevant characterization tool to verify the morphology of the films as a function of the deposition parameters.
