Raphaël Pugin

Nanodispenser for attoliter volume deposition using atomic force microscopy probes modified by focused-ion-beam milling

In this letter, we describe the on-demand dispensing of single liquid droplets with volumes down to a few attoliters and submicrometric spacing. This dispensing is achieved using a standard atomic force microscope probe, with a 200 nm aperture at the tip apex, opened by focused ion beam milling. The inside of the tip is used as reservoir for the liquid. This maskless dispensing, realized in ambient environment, permits the direct creation of droplet arrays. Nanoparticles, suspended in the liquid, were organized on a surface.

Naked Au55 Clusters: Dramatic Effect of a Thiol‐Terminated Dendrimer

Reaction of the thiol-terminated fourth-generation dendrimer 2-G4 (96 SH groups) with the gold cluster compound Au55(PPh3)12Cl6 in a 3:1 molar ratio in dichloromethane results in the formation of bare Au55 clusters. The cuboctahedrally shaped Au55 particles coalesce to well-formed microcrystals (Au55) infinity. The role of the dendrimer is not only to remove the phosphine and chlorine ligands but also to act as an ideal matrix for perfect crystal growth. Transmission electron microscopy (TEM), small- and wide-angle X-ray diffraction (SAXRD and WAXRD) measurements indicate a structure where rows of edge-linked Au55 building blocks form a distorted cubic lattice. The X-ray data fit best if a 5% reduction of the Au-Au bond length in the Au55 clusters is assumed, in agreement with previous extended X-ray absorption fine structure (EXAFS) measurements. Energy-dispersive X-ray spectroscopy (EDX) analyses and IR investigations show the absence of PPh3 and Cl in the microcrystals.

Gold nanoring arrays from responsive block copolymer templates

We report a pH-mediated synthetic route for the production of ordered and size-tuneable arrays of gold nanorings using responsive block copolymer micelles as templates.

Fabrication of nanopore arrays and ultrathin silicon nitride membranes by block-copolymer-assisted lithography

Here we show a method for patterning a thin metal film using self-assembled block-copolymer micelles monolayers as a template. The obtained metallic mask is transferred by reactive ion etching in silicon oxide, silicon and silicon nitride substrates, thus fabricating arrays of hexagonally packed nanopores with tunable diameters, interspacing and aspect ratios. This technology is compatible with integration into a standard microtechnology sequence for wafer-scale fabrication of ultrathin silicon nitride nanoporous membranes with 80 nm mean pore diameter.

J-aggregation of cyanine dyes by self-assembly

The importance of highly ordered surfaces, containing adsorptive surface states, is discussed for J-aggregation by self-assembly. Such nucleating surfaces are nanometer-sized edges and corners of cubic AgBr microcrystals, or surface iodide-clusters located along edges and corners of AgBr:I microcrystals. Of particular interest are dendrimers, monoatomic steps on terraced silver halide microcrystals and fullerene derivatives as nucleating surfaces. Molecular organisation into J-aggregates by self-assembly was realized using aprotic, apolar solvents for fullerenes, and polar solvents for dendrimers and monoatomic surface steps. By using dendrimers as nucleating agents in mesopores of metal oxide nanoparticle coatings, size-controlled and stable J-aggregates with high optical densities and strong fluorescence were obtained reproducibly. Such films may be useful for sensors, opto-electronics, lighting and photovoltaics.

Piezoresistive cantilever array for life sciences applications

Atomic Force Microscopy (AFM) techniques are used with one- or two-dimensional arrays of piezoresistive probes for parallel imaging. We present a newly designed AFM platform to drive these passivated piezoresistive cantilever arrays in air and liquid environments. Large area imaging in liquid as well as qualitative and quantitative analysis of biological cells are demonstrated by the means of piezoresistive cantilever for the first time to our knowledge. Noise limitations in topography and force resolutions of these piezolevers are quantified.

Hierarchical positioning of gold nanoparticles into periodic arrays using block copolymer nanoring templates.

We report a simple and versatile self-assembly method for controlling the placement of functional gold nanoparticles on silicon substrates using micellar templates. The hierarchical positioning of gold nanoparticles is achieved in one-step during the spontaneous phase inversion of spherical poly(styrene)-block-poly(2-vinylpyridine) copolymer micelles into nanoring structures. The placement is mainly driven by the establishment of electrostatic interactions between the nanoparticle ligands and the pyridine groups exposed at the interface. In particular, we show the formation of ordered arrangements of single gold nanoparticles or nanoparticle clusters and demonstrate that their morphologies, densities and periodicities can be tuned by simply varying the initial block copolymer molecular weight or the deposition conditions. Besides gold nanoparticles, the method can be used for controlling the assembly of a large variety of nanoscale building blocks, thus opening an attractive pathway for generating functional hybrid surfaces with periodic nanopatterns.

Molecular transport through nanoporous silicon nitride membranes produced from self-assembling block copolymers

To achieve fast and selective molecular filtration, membrane materials must ideally exhibit a thin porous skin and a high density of pores with a narrow size distribution. Here, we report the fabrication of nanoporous silicon nitride membranes (NSiMs) at the full wafer scale using a versatile process combining block copolymer (BCP) self-assembly and conventional photolithography/etching techniques. In our method, self-assembled BCP micelles are used as templates for creating sub-100 nm nanopores in a thin low-stress silicon nitride layer, which is then released from the underlying silicon wafer by etching. The process yields 100 nm thick free-standing NSiMs of various lateral dimensions (up to a few mm(2)). We show that the membranes exhibit a high pore density, while still retaining excellent mechanical strength. Permeation experiments reveal that the molecular transport rate across NSiMs is up to 16-fold faster than that of commercial polymeric membranes. Moreover, using dextran molecules of various molecular weights, we also demonstrate that size-based separation can be achieved with a very good selectivity. These new silicon nanosieves offer a relevant technological alternative to commercially available ultra- and microfiltration membranes for conducting high resolution biomolecular separations at small scales.

Inexpensive and fast wafer-scale fabrication of nanohole arrays in thin gold films for plasmonics

In this paper, a fast and inexpensive wafer-scale process for the fabrication of arrays of nanoscale holes in thin gold films for plasmonics is shown. The process combines nanosphere lithography using spin-coated polystyrene beads with a sputter-etching process. This allows the batch fabrication of several 1000 microm(2) large hole arrays in 200 nm thick gold films without the use of an adhesion layer for the gold film. The hole size and lattice period can be tuned independently with this method. This allows tuning of the optical properties of the hole arrays for the desired application. An example application, refractive index sensing, is demonstrated.

Optimizing the osteogenicity of nanotopography using block co-polymer phase separation fabrication techniques

Both temporary and permanent orthopedic implants have, by default or design, surface chemistry, and topography. There is increasing evidence that controlling nanodisorder can result in increased osteogenesis. Block co‐polymer phase separation can be used to fabricate a nanotopography exhibiting a controlled level of disorder, both reproducibly and cost‐effectively. Two different topographies, produced through the use of block co‐polymer phase separation, were embossed onto the biodegradable thermoplastic, polycaprolactone (PCL). Analysis of the topography itself was undertaken with atomic force microscopy, and the topographys effect on human osteoblasts studied through the use of immunocytochemistry and fluorescence microscopy. Planar controls had a surface roughness 0.93 nm, and the substrates a high fidelity transfer of a disordered pattern of 14 and 18 nm. Cytoskeletal organization and adhesion, and increased expression of Runx2 were significantly greater on the smallest nanotopography. Expression of osteopontin and osteocalcin protein, and alizarin red staining of bone nodules were greatest on the smallest feature nanopatterns. Highly osteogenic, disordered nanotopographies can be manufactured into thermoplastics in a rapid and cost‐effective way through the use of block co‐polymer phase separation. Osteogenic topographies reproducibly and cost‐effectively produced have a potentially useful application to the fields of implant technology and regenerative orthopedics.