Prof. Dr. Tobias Kraus

Ultrathin gold nanowires (AuNWs) with diameters below 2 nm and high aspect ratios are considered to be a promising base material for transparent electrodes. To achieve the conductivity expected for this system, oleylamine must be removed. Herein we present the first study on the conductivity, optical transmission, stability, and structure of AuNW networks before and after sintering with different techniques. Freshly prepared layers consisting of densely packed AuNW bundles were insulating and unstable, decomposing into gold spheres after a few days. Plasma treatments increased the conductivity and stability, coarsened the structure, and left the optical transmission virtually unchanged. Optimal conditions reduced sheet resistances to 50 Ω/sq.

We demonstrate microwave-induced heating of gold nanoparticles and nanorods. An appreciably higher and concentration-dependent microwave-induced heating rate was observed with aqueous dispersions of the nanomaterials as opposed to pure water and other controls. Grafted with the thermoresponsive polymer poly(N-isopropylacrylamide), these gold nanomaterials react to microwave-induced heating with a conformational change in the polymer shell, leading to particle aggregation. We subsequently covalently immobilize concanavalin A (Con A) on the thermoresponsive gold nanoparticles. Con A is a bioreceptor commonly used in bacterial sensors because of its affinity for carbohydrates on bacterial cell surfaces. The microwave-induced thermal transitions of the polymer reversibly switch on and off the display of Con A on the particle surface and hence the interactions of the nanomaterials with carbohydrate-functionalized surfaces. This effect was determined using linear sweep voltammetry on a methyl-α-d-mannopyranoside-functionalized electrode.

Alkylthiol-coated gold nanoparticles spontaneously segregate from dispersion in toluene to the toluene-vapor interface. We show that surface tension drops during segregation with a rate that depends on particle concentration. Mono- and multilayers of particles form depending on particle concentration, time, and temperature. X-ray reflectometry indicates fast monolayer formation and slow multilayer formation. A model that combines diffusion-limited segregation driven by surface energy and heterogeneous agglomeration driven by dispersive van der Waals particle interactions is proposed to describe film formation.

We present a method to combine the functional features of poly(diethyl vinylphosphonate) (PDEVP) and photoluminescent silicon nanocrystals. The polymer-particle hybrids were synthesized in three steps through surface-initiated group transfer polymerization using Cp2YCH2TMS(thf) as a catalyst. This pathway of particle modification renders the nanoparticle surface stable against oxidation. Although SiNC properties are known to be sensitive toward transition metals, the hybrid particles exhibit red photoluminescence in water. The temperature-dependent coiling of PDEVP results in a change of the hydrodynamic radius of the hybrid particles in water. To the best of our knowledge, this is the first example of controlled catalytic polymerization reactions on a silicon nanocrystal surface.

The distribution of narrowly dispersed gold nanoparticles in hexane-in-water emulsions was studied for different surfactants. Good surfactants such as SDS and Triton X-100 block the oil-water interfaces and confine particles in the droplet. Other surfactants (Tween 85 and Span 20) form synergistic mixtures with the nanoparticles at the interfaces that lower the surface tension more than any component. Supraparticles with fully defined particle distribution form in the droplets only for surfactants that block the interface. Other surfactants promote the formation of fcc agglomerates. Nanoparticles in emulsions behave markedly different from microparticles-their structure formation is governed by free energy minimization, while microparticles are dominated by kinetics.

Traditionally, organosilica nanoparticles have been prepared inside micelles with an external silica shell for mechanical support. Here, we compare these hybrid core-shell particles with organosilica particles that are robust enough to be produced both inside micelles and alone in a sol-gel process. These particles form from octadecyltrimethoxy silane as silica source either in microemulsions, resulting in water-dispersible particles with a hydrophobic core, or precipitate from an aqueous mixture to form particles with both hydrophobic core and surface. We examine size and morphology of the particles by dynamic light scattering and transmission electron microscopy and show that the particles consist of Si–O–Si networks pervaded by alkyl chains using nuclear magnetic resonance, infrared spectroscopy, and thermogravimetric analysis.

Crystalline monolayers of polymer particles are useful templates for surface microstructuring. Here, the authors discuss the use of oxygen plasma to tune interparticle distances in such films. A systematic evaluation of the etch process depending on particle size, plasma power, etching time and particle density was performed. The size evolution of individual particles was analyzed using scanning electron microscopy and compared with different models of the etching process. The authors conclude that none of the existing etch models fit the data very well. Analysis of the particle shape throughout the etching process indicates that changes in particle geometry occur depending on their original size and density. In dense films, bridges form between the particles’ original contact points. Particles increasingly deviate from a spherical geometry. Such shape changes are not captured by current models of the etching process. The authors propose a mechanism to explain the formation of bridges between the particles and their role in the preservation of long-range order. This paper is supplemented by supporting information. The associated files are available online for published issues or can be obtained directly from the managing editor (sohini.banerjee@icepublishing.com) for Ahead of Print articles.

We report a novel fabrication method for ordered arrays of metal nanoparticles that exploits the uniform arrangement of polymer beads deposited as close-packed monolayers. In contrast to colloidal lithography that applies particles as masks, we used thermal decomposition of the metal-covered particles to precisely define metal structures. Large arrays of noble metal (Au, Ag, Pt) nanoparticles were produced in a three-step process on silicon, fused silica and sapphire substrates, demonstrating the generality of this approach. Polystyrene spheres with diameters ranging between 110 nm and 1 µm were convectively assembled into crystalline monolayers, coated with metal and annealed in a resistive furnace or using an ethanol flame. The thermal decomposition of the polymer microspheres converted the metal layer into particles arranged in hexagonal arrays that preserved the order of the original monolayer. Both the particle size and the interparticle distance were adjusted via the thickness of the metal coating and the sphere diameter, respectively.

The growth of nanoscale gold dendrites was studied in situ in a thin liquid film with transmission electron microscopy (TEM) using a liquid cell with silicon nitride (SiN) windows. Gold nanoparticle seeds were covered by a thin liquid layer containing precursor solution. Dendrite nucleation was induced by the electron beam leading to an initial burst of growth. The growth then settled at tip velocities between 0.1 and 2.0 nm/s for different dendrites. Tip velocities fluctuated as different dendrite geometries grew from the tips. Those dendrites showing granularities in their structure experienced the largest growth speed. Comparison of the observed velocities with diffusion-limited growth rates suggests that dendrite growth in thin films at this scale is limited by diffusion. The described method may find application in research on the mechanisms behind dendrite growth and also to study other types of anisotropic growth of nanomaterials driven by crystal and twin geometries.

The stability of nanoparticle suspensions and the details of their agglomeration depend on the interactions between particles. We study this relationship in gold nanoparticles stabilized with different alkyl thiols in heptane. Temperature-dependent interactions were inferred from small-angle x-ray scattering, agglomeration kinetics from dynamic light scattering, and agglomerate morphologies from transmission electron microscopy. We find that the particles precipitate at temperatures below the melting temperatures of the dry ligands. Agglomerates grow with rates that depend on the temperature: Around precipitation temperature, globular agglomerates form slowly, while at lower temperatures, fibrilar agglomerates form rapidly. All agglomerates contain random dense packings rather than crystalline superlattices. We conclude that ligand-ligand and ligand-solvent interactions of the individual particles dominate suspension stability and agglomeration kinetics. The microscopic packing is dominated by interactions between the ligands of different nanoparticles.