Prof. Dr. Tobias Kraus

Nanocomposites consisting of conductive polymers and functional nanoparticles have recently been employed in photodetectors and imagers. Here, we present a novel hybrid-organic photodetector (HPD) that was optimized for the detection of X-rays meeting the specific needs of medical imaging. Devices were fabricated using inorganic lead sulfide (PbS) nanocrystal (NC) quantum dots (QDs) and a blend of poly (3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Quantum dots convert X-rays directly into charge-carriers that then migrate through the organic blend to the contacting electrodes. The performance of such devices depends on the thickness and probably on the morphology of the active layer. We discuss the synthesis and characterization of the PbS quantum dots, their incorporation into a HPD, and the performance of the HPD in X-ray sensing. Scanning electron microscopy and transmission electron microscopy show the PbS-QD distribution in the organic matrix. We find a strong tendency of the QDs to phase-separate from the organic blend.

We present an elegant route for the fabrication of ordered arrays of vertically-aligned silicon nanowires with tunable geometry at controlled locations on a silicon wafer. A monolayer of transparent microspheres convectively assembled onto a gold-coated silicon wafer acts as a microlens array. Irradiation with a single nanosecond laser pulse removes the gold beneath each focusing microsphere, leaving behind a hexagonal pattern of holes in the gold layer. Owing to the near-field effects, the diameter of the holes can be at least five times smaller than the laser wavelength. The patterned gold layer is used as catalyst in a metal-assisted chemical etching to produce an array of vertically-aligned silicon nanowires. This approach combines the advantages of direct laser writing with the benefits of parallel laser processing, yielding nanowire arrays with controlled geometry at predefined locations on the silicon surface. The fabricated VA-SiNW arrays can effectively transfect human cells with a plasmid encoding for green fluorescent protein.

Novel types of Transparent Conductive Materials (TCMs) based on metal nanostructures are discussed. Dispersed metal nanoparticles can be deposited from liquids with moderate thermal budgets to form conductive films that are suitable for thin-film solar cells, displays, touch screens, and nanoelectronics. We aim at new TCMs that combine high electrical conductivity with optical transparency and mechanical flexibility. Wet-processed films of randomly arranged metallic nanowires networks are commercially established and provide a relatively cost-effective, scalable production. Ultrathin gold nanowires (AuNWs) with diameters below 2nm and high aspect ratios have recently become available. They combine mechanical flexibility, high optical transparency, and chemical inertness. AuNWs carry oleylamine capping ligands from synthesis that cause high contact resistances at their junctions. We investigated different annealing processes based on temperature and plasma treatment, to remove the ligands after deposition and to allow electrical conductivity. Their effect on the resulting nanostructure and on the material properties was studied. Scanning Electron Microscopy (SEM) and optical spectroscopy revealed changes in the microstructure for the different post-treatments. We found that the conductivity and the stability of the TCM depended strongly on its final microstructure. We demonstrate that the best results are obtained using H2-plasma treatment.

Flow field-flow fractionation is a powerful method for the analysis of nanoparticle size distributions, but its widespread use has been hampered by large analyte losses, especially of metal nanoparticles. Here, we report on the colloidal mechanisms underlying the losses. We systematically studied gold nanoparticles (AuNPs) during asymmetrical flow field-flow fractionation (AF4) by systematic variation of the particle properties and the eluent composition. Recoveries of AuNPs (core diameter 12 nm) stabilized by citrate or polyethylene glycol (PEG) at different ionic strengths were determined. We used online UV–vis detection and off-line elementary analysis to follow particle losses during full analysis runs, runs without cross-flow, and runs with parts of the instrument bypassed. The combination allowed us to calculate relative and absolute analyte losses at different stages of the analytic protocol. We found different loss mechanisms depending on the ligand. Citrate-stabilized particles degraded during analysis and suffered large losses (up to 74%). PEG-stabilized particles had smaller relative losses at moderate ionic strengths (1–20%) that depended on PEG length. Long PEGs at higher ionic strengths (≥5 mM) caused particle loss due to bridging adsorption at the membrane. Bulk agglomeration was not a relevant loss mechanism at low ionic strengths ≤5 mM for any of the studied particles. An unexpectedly large fraction of particles was lost at tubing and other internal surfaces. We propose that the colloidal mechanisms observed here are relevant loss mechanisms in many particle analysis protocols and discuss strategies to avoid them.

Binary mixtures of nanoparticles self-assemble in the confinement of evaporating oil droplets and form regular supraparticles. We demonstrate that moderate pressure differences on the order of 100 kPa change the particles' self-assembly behavior. Crystalline superlattices, Janus particles, and core-shell particle arrangements form in the same dispersions when changing the working pressure or the surfactant that sets the Laplace pressure inside the droplets. Molecular dynamics simulations confirm that pressure-dependent interparticle potentials affect the self-assembly route of the confined particles. Optical spectrometry, small-angle X-ray scattering and electron microscopy are used to compare experiments and simulations and confirm that the onset of self-assembly depends on particle size and pressure. The overall formation mechanism reminds of the demixing of binary alloys with different phase diagrams.

Ultrathin gold nanowires (AuNWs) show prospects as components of materials for transparent and flexible electronics that exploit the wires’ high aspect ratio and mechanical flexibility. High junction resistances that are caused by the insulating oleylamine ligand shells and the wires’ intrinsic susceptibility to decomposition by the Rayleigh instability impede their use in the as-synthesized state. Treatment by H2/Ar  plasma has been shown to improve conductivity and stability. We study the effects of a plasma treatment on morphology, chemistry, and temperature stability of AuNW layers by electron microscopy, X-ray diffraction, and Raman spectroscopy. Plasma treatment effectively removes oleylamine and sinters the individual ultrathin wires to superstructures with enhanced conductivity and temperature stability. Bundles of single ultrathin AuNWs can be sintered to continuous superstructures with enhanced conductivity and stability by H2/Ar plasma treatment.

We fabricated flexible, transparent, and conductive metal grids as transparent conductive materials (TCM) with adjustable properties by direct nanoimprinting of self-assembling colloidal metal nanowires. Ultrathin gold nanowires (diameter below 2 nm) with high mechanical flexibility were confined in a stamp and readily adapted to its features. During drying, the wires self-assembled into dense bundles that percolated throughout the stamp. The high aspect ratio and the bundling yielded continuous, hierarchical superstructures that connected the entire mesh even at low gold contents. A soft sintering step removed the ligand barriers but retained the imprinted structure. The material exhibited high conductivities (sheet resistances down to 29 Ω/sq) and transparencies that could be tuned by changing wire concentration and stamp geometry. We obtained TCMs that are suitable for applications such as touch screens. Mechanical bending tests showed a much higher bending resistance than commercial ITO: conductivity dropped by only 5.6% after 450 bending cycles at a bending radius of 5 mm.

This study outlines the synthetic and purification process used to obtain hyperbranched polyglycerol (HPG) within a molecular weight range not previously obtainable. Purified fractions with low polydispersity are achieved via successive precipitations from acetone. Furthermore, the use of the initiator molecule 5-hexyne-1-ol introduces alkyne functionality at the core of each HPG molecule. Alkyne-azide cycloaddition chemistry in combination with NMR and field flow fractionation analysis is used to verify the availability of the alkyne core for bioconjugation across the range of molecular weights.

We analyze the structure diagram for binary clusters of Lennard-Jones particles by means of a global optimization approach for a large range of cluster sizes, compositions, and interaction energies and present a publicly accessible database of 180 000 minimal energy structures (http://softmattertheory.lu/clusters.html). We identify a variety of structures such as core-shell clusters, Janus clusters, and clusters in which the minority species is located at the vertices of icosahedra. Such clusters can be synthesized from nanoparticles in agglomeration experiments and used as building blocks in colloidal molecules or crystals. We discuss the factors that determine the formation of clusters with specific structures.