Prof. Dr. Tobias Kraus

Metal-assisted chemical etching (MACE) affords porous silicon nanostructures control over size, shape, and porosity in a single step. Simplicity and flexibility are potential advantages over more traditional silicon bulk micromachining techniques. MACE-generated porous micro- and nanostructures are suitable as biomaterials through their length scales and biocompatibility. This work provides a comprehensive overview of the MACE reaction mechanism that yields biomedically relevant silicon nanostructures – from nanowires, nanopillars, to sub-micrometer holes and pores. We discuss their biomedical applications in biosensors, cell capture and transfection arrays, and drug delivery vectors. We assess the reported benefits of the various nanostructures and discuss whether MACE provides clear and distinct advantages over other techniques. The flexibility and simplicity of MACE comes at a cost. The reaction parameters are many and inter-related, and we lack a full model of the etching mechanism. While the cathode reaction is well understood, the anode reaction involving dissolution of the silicon remains controversial. Such uncertainties impede rational design of specific structures that address biomedical requirements. We summarize current understanding to provide design guidelines for structures used in biomedicine and review the effects of key parameters on the morphological attributes of the etched features.

The statistical anionic copolymerisation of the biobased monomer β-myrcene with styrene in cyclohexane was investigated via in situ near-infrared (NIR) spectroscopy, focusing on the influence of the modifiers (i.e., Lewis bases) tetrahydrofuran (THF) and 2,2-di(2-tetrahydrofuryl)propane (DTHFP) on the reactivity ratios. With increasing [modifier]/[Li] ratio, the reactivity ratios in the system myrcene/styrene are adjustable from rS ≪ rMyr via rS ≈ rMyr to rS ≫ rMyr. The bidentate modifier DTHFP affects the reactivity ratios much more than THF: minute amounts only (0.35 equivalent relative to Li) are required to randomize the copolymer, and one equivalent to invert the reactivity ratios. Using these reactivity ratios, copolymer composition profiles are obtained, which upon increasing the modifier concentration vary from tapered, block-like copolymers to random to inversely tapered copolymers. 1H-NMR spectroscopy was used to determine the microstructure of the myrcene units in the copolymers. With increasing [modifier]/[Li] ratio, the content of 1,4-units decreases and the content of 3,4- and 1,2-units increases. DTHFP as a modifier minimizes the content of 1,2-units. The glass transition temperatures also depend on the [modifier]/[Li] ratio, but less strongly than in the copolymer poly(styrene-co-isoprene). Although all copolymers have the same composition (33%mol myrcene, corresponding to 39.6%weight and 45%vol), very similar molecular weights (about 90 kg mol−1) and low dispersities (1.06 to 1.10), different morphologies could be obtained. Lamellar, cylindrical and gyroid structures were identified by TEM and SAXS measurements. The mechanical properties vary in a wide range from hard and brittle to soft and flexible. The gyroid structure showed the highest Young's modulus and no viscoelastic deformation.

Abstract A one-pot approach for the preparation of diblock copolymers consisting of polystyrene and polymyrcene blocks is described via a temperature-induced block copolymer (BCP) formation strategy. A monomer mixture of styrene and myrcene is employed. The unreactive nature of myrcene in a polar solvent (tetrahydrofuran) at −78 °C enables the sole formation of active polystyrene macroinitiators, while an increase of the temperature (−38 °C to room temperature) leads to poly(styrene-block-myrcene) formation due to polymerization of myrcene. Well-defined BCPs featuring molar masses in the range of 44–117.2 kg mol−1 with dispersities, Ð, of 1.09–1.21, and polymyrcene volume fractions of 30–64% are accessible. Matrix assisted laser desorption ionization-time of flight mass spectrometry measurements reveal the temperature-controlled polymyrcene block formation, while both transmission electron microscopy and small-angle X-ray scattering measurements prove the presence of clearly microphase-separated, long range-ordered domains in the block copolymers. The temperature-controlled one-pot anionic block copolymerization approach may be general for other terpene-diene monomers.

Nanoparticle superlattice films form at the solid-liquid interface and are important for mesoscale materials, but are notoriously difficult to analyze before they are fully dried. Here, the early stages of nanoparticle assembly were studied at solid-liquid interfaces using liquid-phase electron microscopy. Oleylamine-stabilized gold nanoparticles spontaneously formed thin layers on a silicon nitride (SiN) membrane window of the liquid enclosure. Dense packings of hexagonal symmetry were obtained for the first monolayer independent of the nonpolar solvent type. The second layer, however, exhibited geometries ranging from dense packing in a hexagonal honeycomb structure to quasi-crystalline particle arrangements depending on the dielectric constant of the liquid. The complex structures formed by the weaker interactions in the second particle layer were preserved, while the surface remained immersed in liquid. Fine-tuning the properties of the involved materials can thus be used to control the three-dimensional geometry of a superlattice including quasi-crystals.

Hybrid electronic materials combine inorganic metals and semiconductors with π-conjugated polymers. The orientation of the polymer molecules in relation to the inorganic components is crucial for electrical material properties and device performance, but little is known of the configuration of π-conjugated polymers that bind to inorganic surfaces. Highly curved surfaces are common when using nanoscale components, for example, metal nanocrystal cores covered with conductive polymers. It is important to understand their effect on molecular arrangement. Here, we compare the molecular structures and electrical conductivities of well-defined nanoscale gold spheres and rods with shells of the covalently bound polythiophene PTEBS (poly[2-(3-thienyl)-ethyloxy-4-butylsulfonate]). We prepared aqueous sinter-free inks from the particles and printed them. The particles formed highly conductive films immediately after drying. Films with spherical metal cores consistently had 40% lower conductivities than films based on nanorods. Raman and X-ray photoelectron spectroscopy revealed differences in the gold–sulfur bonds of PTEBS on rods and spheres. The fractions of bond sulfur groups implied differences in the alignment of PTEBS with the surface. More polymer molecules were bound in an edge-on configuration on spheres than on rods, where almost all polymers aligned “face-on” with the metal surface. This leads to different interface resistances: gold–polythiophene–gold interfaces between rods with π–π-tacked face-on PTEBS apparently foster electron transport along the surface-normal direction, while edge-on PTEBS does not. Molecular confinement thus increases the conductivity of hybrid inks based on highly curved nanostructures.

Aqueous redox flow batteries using electroactive organic materials are currently attracting significant attention. However, the influence of supporting electrolytes on the aqueous solubility, electrochemical reversibility and chemical stability of the organic components has rarely been investigated. Here, a new electrolyte design strategy towards enhanced solubility and chemical stability of active materials is proposed by using interaction-mediating species. 3 molality aqueous imidazolium chlorides, with high ionic conductivity and water-like flowability, enable a record aqueous solubility of 4.3 M for a commercially available nitroxyl radical and reversible 2e− reaction of unmodified methyl viologen at moderate concentrations. With 0.6 M electrolyte, flow cell shows remarkable chemical stability of the nitroxyl radical, excellent cycling stability over 250 cycles at 80 mA cm−2, and a peak power density of 121.6 mW cm−2 at 175 mA cm−2. Furthermore, nitroxyl radical catholyte with a concentration of 3 M is tested in a flow cell. It maintains an impressive steady energy efficiency of 65% at 30 mA cm−2. This work paves a new way for the development of high performance aqueous electrolytes based on organic materials.

Abstract Conductive inkjet printing with metal nanoparticles is irreversible because the particles are sintered into a continuous metal film. The resulting structures are difficult to remove or repair and prone to cracking. Here, a hybrid ink is used to obviate the sintering step and print interconnected particle networks that become highly conductive immediately after drying. It is shown that reversible conductive printing is possible on low-cost cardboard samples after applying standard paper industry coats that are adapted in terms of surface energy and porosity. The conductivity of the printed films approaches that of sintered standard inks on the same substrate, but the mobility of the hybrid particle film makes them less sensitive to cracks during bending and folding of the substrate. Damages that occur can be partially repaired by wetting the film such that particle mobility is increased and particles move to bridge insulating gaps in the film. It is demonstrated that the conductive material can be recovered from the cardboard at the end of its life time and be redispersed to recycle the particles and reuse them in conductive inks.

Hybrid electronic materials combine the excellent electronic properties of metals and semiconductors with the mechanical flexibility, ease of processing, and optical transparency of polymers. This talk will discuss hybrids that combine organic and inorganic components at different scales. Metallic and semiconductor nanoparticle cores are coated with conductive polymer shells to create “hybrid inks” that can be inkjet-printed and form conductive leads without any sintering step. Transparent electrodes are printed using ultrathin metal nanowires with core diameters below 2 nm. The chemically synthesized wires spontaneously form percolating structures when patterned with a soft stamp; this rapidly yields optically transparent grid electrodes, even on demanding soft substrates. These new hybrid electronic materials enable the fabrication of soft electronics, including flexible sensors on polymer foils, radio-frequency identification (RFID) antennae on cardboard, and soft human–machine interfaces. Selected devices will be covered at the end of the talk.

Abstract Gold nanoparticles (AuNP) are frequently used in surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) for analysis of biomolecules because they exhibit suitable thermal and chemical properties as well as strong surface plasmonic effects. Moreover, the structures of AuNP can be controlled by well-established synthesis protocols. This was important in the present work, which studied the influence of the nanoparticles’ structures on atmospheric pressure (AP)-SALDI-MS performance. A series of AuNP with different core sizes and capping ligands were investigated, to examine the desorption/ionization efficiency (DIE) under AP-SALDI conditions. The results showed that both the AuNP core size as well as the nature of the surface ligand had a strong influence on DIE. DIE increased with the size of the AuNP and the hydrophobicity of the ligands. Chemical interactions between ligand and analytes also influenced DIE. Moreover, we discovered that removing the organic ligands from the deposited AuNP substrate layer by simple laser irradiation prior to LDI further amplified DIE values. The optimized AuNP were successfully used to analyze a wide arrange of different low molecular weight biomolecules as well as a crude pig brain extract, which readily demonstrated the ability of the technique to detect a wide range of lipid species within highly complex samples.

Semiconductor nanoplatelets exhibit spectrally pure, directional fluorescence. To make polarized light emission accessible and the charge transport effective, nanoplatelets have to be collectively oriented in the solid state. We discovered that the collective nanoplatelets orientation in monolayers can be controlled kinetically by exploiting the solvent evaporation rate in self-assembly at liquid interfaces. Our method avoids insulating additives such as surfactants, making it ideally suited for optoelectronics. The monolayer films with controlled nanoplatelets orientation (edge-up or face-down) exhibit long-range ordering of transition dipole moments and macroscopically polarized light emission. Furthermore, we unveil that the substantial in-plane electronic coupling between nanoplatelets enables charge transport through a single nanoplatelets monolayer, with an efficiency that strongly depends on the orientation of the nanoplatelets. The ability to kinetically control the assembly of nanoplatelets into ordered monolayers with tunable optical and electronic properties paves the way for new applications in optoelectronic devices.