Nanobubble and nanodroplet template growth of particle nanorings versus nanoholes in drying nanofluids and polymer films.

Here we demonstrate how confined nanobubbles and nanodroplets, which can either form spontaneously at the suspension/substrate interface, or can more interestingly be purposely introduced in the system, allow assembly of nanoparticles (NPs) into nanoring-like structures with a flexible control of both the size and distribution. As with most wetting-mediated nanopatterning methods, this approach provides an alternative to direct replication from templates. The formation of two-dimensional ring-shaped nanostructures was obtained by drying a nanocolloidal gold (Au) suspension drop confining nanobubbles (or nanodroplets) that are settled at a solid substrate. AFM investigation of the dry nanostructures showed the formation of isolated Au NPs rings having diameters ranging from 200 nm to 500 nm along the dewetting-drying path of the suspension drop. The flexibility of these wetting processes for the variation of the spatial features of the nanoring (size and shape resolution) essentially depends on physical parameters such as the nanobubble/nanodroplet size and concentration, the wettability, and the evaporation rate of the nanofluid drop on the substrate. Furthermore, we show that the underpinning mechanism of this evaporation-assisted assembly of Au NPs into supported functional nanoring patterns is fairly similar to that at work in the spontaneous formation of nanoholes in drying polymer thin films. Finally, the method proves to be a simple and flexible nanofabrication tool to be extended to various nanosize objects, towards specific optical and sensing applications.

The analytical relations between particles and probe trajectories in atomic force microscope nanomanipulation.

Analytical expressions relating the trajectories of spherical nanoparticles pushed by an atomic force microscope tip to the scan pattern of the tip are derived. In the case of a raster scan path, the particles are deflected in a direction defined by the geometries of tip and particles and the spacing b between consecutive scan lines. In the case of a zigzag scan path, the particles are deflected in a range of directions around 90 degrees, also depending on the parameter b. Experimental results on gold nanoparticles manipulated on silicon surfaces in ambient conditions confirm the predictions of our model.

Thermal stability and reconstruction of nanoparticulate Au film on model molecular surfaces.

Thermally activated morphological reconstruction of nanoparticulate gold films deposited onto model molecular surfaces was investigated at 200 degrees C as a function of the annealing time. Results show a strong correlation of the spatial reorganization of the metallic particles to the surface chemistry of the underlying substrate. On the nonpolar surface, the thin nanoparticulate Au film dewets by the formation of randomly distributed nucleation holes. Two morphological reconstruction kinetics were observed. The first kinetics characterized by a sigmoid growth describes the time-evolution of the dewetted spots and particle size inside the spots, and the second corresponds to the number density of particles and displays an exponential decay with time. Ultimately our results show that even at temperatures well below the bulk metal melting point, nanoparticulate metal structures can undergo drastic morphological reconstructions which can irreversibly affect their functional properties and performance (catalysis, electronic).

Manipulation of gold nanoparticles: influence of surface chemistry, temperature, and environment (vacuum versus ambient atmosphere).

We have manipulated raw and functionalized gold nanoparticles (with a mean diameter of 25 nm) on silicon substrates with dynamic atomic force microscopy (AFM). Under ambient conditions, the particles stick to silicon until a critical amplitude is reached by the oscillations of the probing tip. Beyond that threshold, the particles start to follow different directions, depending on their geometry and adhesion to the substrate. Higher and lower mobility were observed when the gold particles were coated with methyl- and hydroxyl-terminated thiol groups, respectively, which suggests that the adhesion of the particles to the substrate is strongly reduced by the presence of hydrophobic interfaces. Under ultrahigh vacuum conditions, where the water layer is absent, the particles did not move, even when operating the atomic force microscope in contact mode. We have also investigated the influence of the temperature (up to 150 degrees C) and of the geometrical arrangement of the particles on the manipulation process. Whereas thermal activation has an important effect in enhancing the mobility of the particles, we did not find differences when manipulating ordered versus random distributions of particles.

Construction of a tethered poly(ethylene glycol) surface gradient for studies of cell adhesion kinetics.

Surface gradients can be used to perform a wide range of functions and represent a novel experimental platform for combinatorial discovery and analysis. In this work, a gradient in the coverage of a surface-immobilized poly(ethylene glycol) (PEG) layer is constructed to interrogate cell adhesion on a solid surface. Variation of surface coverage is achieved by controlled transport of a reactive PEG precursor from a point source through a hydrated gel. Immobilization of PEG is achieved by covalent attachment of the PEG molecule via direct coupling chemistry to a cystamine self-assembled monolayer on gold. This represents a simple method for creating spatial gradients in surface chemistry that does not require special instrumentation or microfabrication procedures. The structure and spatial distribution of the PEG gradient are evaluated via ellipsometry and atomic force microscopy. A cell adhesion assay using bovine arteriole endothelium cells is used to study the influence of PEG thickness and chain density on biocompatibility. The kinetics of cell adhesion are quantified as a function of the thickness of the PEG layer. Results depict a surface in which the variation in layer thickness along the PEG gradient strongly modifies the biological response.