Manipulation of gold colloidal nanoparticles with atomic force microscopy in dynamic mode: influence of particle-substrate chemistry and morphology, and of operating conditions.

One key component in the assembly of nanoparticles is their precise positioning to enable the creation of new complex nano-objects. Controlling the nanoscale interactions is crucial for the prediction and understanding of the behaviour of nanoparticles (NPs) during their assembly. In the present work, we have manipulated bare and functionalized gold nanoparticles on flat and patterned silicon and silicon coated substrates with dynamic atomic force microscopy (AFM). Under ambient conditions, the particles adhere to silicon until a critical drive amplitude is reached by oscillations of the probing tip. Beyond that threshold, the particles start to follow different directions, depending on their geometry, size and adhesion to the substrate. Higher and respectively, lower mobility was observed when the gold particles were coated with methyl (-CH(3)) and hydroxyl (-OH) terminated thiol groups. This major result suggests that the adhesion of the particles to the substrate is strongly reduced by the presence of hydrophobic interfaces. The influence of critical parameters on the manipulation was investigated and discussed viz. the shape, size and grafting of the NPs, as well as the surface chemistry and the patterning of the substrate, and finally the operating conditions (temperature, humidity and scan velocity). Whereas the operating conditions and substrate structure are shown to have a strong effect on the mobility of the particles, we did not find any differences when manipulating ordered vs random distributed particles.

Complex aggregation patterns in drying nanocolloidal suspensions: size matters when it comes to the thermomechanical stability of nanoparticle-based structures.

We report the results of a model study on the interrelation among the occurrence of complex aggregation patterns in drying nanofluids, the size of the constitutive nanoparticles (NPs), and the drying temperature, which is a critical issue in the genesis of complex drying patterns that was never systematically reported before. We show that one can achieve fine control over the occurrence and topological features of these drying-mediated complex structures through the combination of the particle size, the drying temperature, and the substrate surface energy. Most importantly, we show that a transition in the occurrence of the patterns appears with the temperature and the particle size, which accounts for the size dependence of the thermomechanical stability of the aggregates in the nanoscale range. Using simple phenomenological and scaling considerations, we showed that the thermomechanical stability of the aggregates was underpinned by physical quantities that scale with the size of the NPs (R) either as R(-2) or R(-3). These insights into the size-dependent dissipation mechanisms in nanoclusters should help in designing NPs-based structures with tailored thermomechanical and environmental stability and hence with an optimized morphological stability that guarantees their long-term functional properties.