Markus Retsch

Advances in Colloidal Assembly : The Design of Structure and Hierarchy in Two and Three Dimensions

This Review highlights the large number of methods to exploit colloidal assembly of comparably simple particles with nano- to micrometer dimensions in order to access complex structural hierarchies from nanoscopic over microscopic to macroscopic dimensions

High strain rate deformation of layered nanocomposites

Insight into the mechanical behaviour of nanomaterials under the extreme condition of very high deformation rates and to very large strains is needed to provide improved understanding for the development of new protective materials. Applications include protection against bullets for body armour, micrometeorites for satellites, and high-speed particle impact for jet engine turbine blades. Here we use a microscopic ballistic test to report the responses of periodic glassy-rubbery layered block-copolymer nanostructures to impact from hypervelocity micron-sized silica spheres. Entire deformation fields are experimentally visualized at an exceptionally high resolution (below 10 nm) and we discover how the microstructure dissipates the impact energy via layer kinking, layer compression, extreme chain conformational flattening, domain fragmentation and segmental mixing to form a liquid phase. Orientation-dependent experiments show that the dissipation can be enhanced by 30% by proper orientation of the layers.

Visible Mie Scattering in Nonabsorbing Hollow Sphere Powders

Hollow silica nanoparticles (HSNP) with diameters comparable to visible wavelengths and with thin shells (<15 nm) feature an unexpected color effect. Single particle and powder spectroscopy, as well as calculations based on Mie theory were used to investigate this phenomenon. The use of HSNPs increases the transport mean free path of light significantly, which reduces multiple scattering, and thus the Mie resonances become visible to the bare eye.

Confined Diffusion in Periodic Porous Nanostructures

We performed fluorescence correlation spectroscopy measurements to assess the long-time self-diffusion of a variety of spherical tracer particles in periodic porous nanostructures. Inverse opal structures with variable cavity sizes and openings in the nanometer domain were employed as the model system. We obtained both the exponent of the scaling relation between mean-square displacement and time and the slow-down factors due to the periodic confinement for a number of particle sizes and confining characteristics. In addition, we carried out Brownian dynamics simulations to model the experimental conditions. Good agreement between experimental and simulation results has been obtained regarding the slow-down factor. Fickian diffusion is predicted and seen in almost all experimental systems, while apparent non-Fickian exponents that show up for two strongly confined systems are attributed to polydispersity of the cavity openings. The utility of confining periodic porous nanostructures holds promise toward understanding of constrained diffusion with a wide range of applications ranging from water purification and drug delivery to tissue engineering.

Reusable Localized Surface Plasmon Sensors Based on Ultrastable Nanostructures

Nanoparticle arrays created by nanosphere lithography are widely used in sensing applications since their localized surface plasmon resonances are extremely sensitive to changes in the local dielectric environment. A major drawback for any biologically oriented sensing application of conventionally produced particle arrays is the lack of stability of the nanoparticles in aqueous media and buffer solutions. Here, a robust and reusable nanoscale sensing platform based on localized surface plasmon resonances of gold nanoparticles embedded in a silicon dioxide matrix is presented. The architecture exhibits extremely high stability in aqueous environments and can be regenerated several times by simple mechanical cleaning of the surface. The platforms surface is ultraflat by design, thus making it an ideal substrate for any bio-oriented sensing application.

Parallel Preparation of Densely Packed Arrays of 150-nm Gold-Nanocrescent Resonators in Three Dimensions

Metallic nanostructures show interesting optical properties due to their plasmonic resonances, and when arranged in three-dimensional (3D) arrays hold promise for optical metamaterials with negative refractive index. Towards this goal a simple, cheap, and parallel method to fabricate large-area, ordered arrays of 150-nm gold nanocrescents supporting plasmonic resonances in the near-infrared spectral range is demonstrated. In this process hexagonally ordered monolayers of monodisperse colloids are prepared by a simple floating technique, and subsequently the individual particles are size-reduced in a plasma process and used as a shadow mask with the initial lattice spacing. The resulting two-dimensional array of plasmonic resonators is coated with a transparent silica layer, which serves as a support for a second layer prepared by the identical process. The mutual orientation of the nanostructures between the individual layers can be freely adjusted, which determines the polarization-dependent absorption of the array and opens the possibility to introduce chirality in this type of 3D metamaterial. The iteration of this simple and efficient methodology yields 3D arrays with optical features as sharp as those of the individual nanocrescents, and shows strong potential for large-scale production of high-quality optical metamaterials.

Colloidal systems: a promising material class for tailoring sound propagation at high frequencies

In this paper we report on the phononic properties of mesoscopic colloidal materials. Using high resolution Brillouin light scattering (BLS) the resonance modes of submicron particles as well as the dispersion relations of their ordered assemblies in a liquid matrix are studied. Two different kinds of very recently realized acoustic bandgaps are presented. In colloidal mixtures, the particle acoustic resonances are independent of composition.

The swelling behaviour of thermoresponsive hydrogel/silica nanoparticle composites

A new responsive nanocomposite material consisting of a poly-(N-isopropylacrylamide) hydrogel and “super-crosslinking” silica nanoparticles was prepared by mixing both components in solution, spincoating a thin film, and photocrosslinking by UV irradiation. Detailed analysis of the thermal response of these water-swollen films by means of surface plasmon resonance and optical waveguide spectroscopy revealed that the composite is very stable and has excellent responsive properties; it is of high optical homogeneity; admixture of the nanoparticles (up to 50%-wt) does not affect the critical volume collapse temperature; and swell-collapse cycles are highly reproducible and display only limited hysteresis. Thus, the composite is promising as a scaffold for further functionalisation and incorporation in sensors or actuators.

The "Music" of Core-Shell Spheres and Hollow Capsules: Influence of the Architecture on the Mechanical Properties at the Nanoscale

We report on the first measurement of elastic vibrational modes in core-shell spheres (silica-poly(methyl methacrylate), SiO2-PMMA) and corresponding spherical hollow capsules (PMMA) with different particle size and shell thickness using Brillouin light scattering, supported by numerical calculations. These localized modes allow access to the mechanical moduli down to a few tens of nanometers. We observe reduced mechanical strength of the porous silica core, and for the core-shell spheres a striking increase of the moduli in both the SiO2 core and the PMMA shell. The peculiar behavior of the vibrational modes in the hollow capsules is attributed to antagonistic dependence on overall size and layer thickness in agreement with theoretical predictions.

Synthesis of Dense Poly(acrylic acid) Brushes and Their Interaction with Amine-Functional Silsesquioxane Nanoparticles

Poly(acrylic acid) polyelectrolyte brushes were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) of tert-butyl acrylate on planar gold surfaces and subsequent hydrolysis. Three types of monolayers with different numbers of thiol binding sites per initiating unit were used. The binding strength to the gold surface turned out to be of crucial importance for the formation of uniform brush layers after acidic hydrolysis. The monolayers and polymer brushes were characterized by ellipsometry, infrared spectroscopy, water contact angle measurements, atomic force microscopy, and X-ray photoelectron spectroscopy. Their interaction with [(diglycidylamino)propyl]silsesquioxane nanoparticles at various pH values was studied by surface plasmon resonance.