Julian Schneider

Direct printing of nanostructures by electrostatic autofocussing of ink nanodroplets

Nanotechnology, with its broad impact on societally relevant applications, relies heavily on the availability of accessible nanofabrication methods. Even though a host of such techniques exists, the flexible, inexpensive, on-demand and scalable fabrication of functional nanostructures remains largely elusive. Here we present a method involving nanoscale electrohydrodynamic ink-jet printing that may significantly contribute in this direction. A combination of nanoscopic placement precision, soft-landing fluid dynamics, rapid solvent vapourization, and subsequent self-assembly of the ink colloidal content leads to the formation of scaffolds with base diameters equal to that of a single ejected nanodroplet. The virtually material-independent growth of nanostructures into the third dimension is then governed by an autofocussing phenomenon caused by local electrostatic field enhancement, resulting in large aspect ratio. We demonstrate the capabilities of our electrohydrodynamic printing technique with several examples, including the fabrication of plasmonic nanoantennas with features sizes down to 50 nm.

Specific Material Recognition by Small Peptides Mediated by the Interfacial Solvent Structure

We present evidence that specific material recognition by small peptides is governed by local solvent density variations at solid/liquid interfaces, sensed by the side-chain residues with atomic-scale precision. In particular, we unveil the origin of the selectivity of the binding motif RKLPDA for Ti over Si using a combination of metadynamics and steered molecular dynamics simulations, obtaining adsorption free energies and adhesion forces in quantitative agreement with corresponding experiments. For an accurate description, we employ realistic models of the natively oxidized surfaces which go beyond the commonly used perfect crystal surfaces. These results have profound implications for nanotechnology and materials science applications, offering a previously missing structure-function relationship for the rational design of materials-selective peptide sequences.

Hole scavenger redox potentials determine quantum efficiency and stability of Pt-decorated CdS nanorods for photocatalytic hydrogen generation

We use Pt-decorated CdS nanorods for photocatalytic hydrogen generation in the presence of sacrificial hole scavengers. Both the quantum efficiency for hydrogen generation and the stability of the colloidal nanocrystals in solution improve with increasing redox potential of the hole scavenger. The higher redox potential leads to faster hole scavenging, which increases quantum efficiency and stability since electron hole recombination and oxidation of the CdS become less important. The quantum efficiencies can be tuned over more than an order of magnitude. This finding is important for choosing hole scavengers and for comparing efficiencies and stabilities for different photocatalytic nanosystems.

Luminescent colloidal carbon dots: optical properties and effects of doping [Invited].

We review the effect of doping on the optical properties of luminescent colloidal carbon dots. They are considered as a hybrid material featuring both molecular and semiconductor-like characteristics, where doping plays an important role. Starting from the short overview of synthetic strategies, we consider the evolution of carbon dots from molecular precursors to fluorescent nanoparticles, and the relevant structural properties of carbon dots. Choice of the reactant materials, dopant atoms and reaction parameters provide carbon dots with varying optical properties. High chemical stability, bright luminescence and customizable surface functionalization of carbon dots open their use in a broad range of applications, which are exemplary presented at the end of this review.

A Classical Potential to Model the Adsorption of Biological Molecules on Oxidized Titanium Surfaces.

The behavior of titanium implants in physiological environments is governed by the thin oxide layer that forms spontaneously on the metal surface and mediates the interactions with adsorbate molecules. In order to study the adsorption of biomolecules on titanium in a realistic fashion, we first build up a model of an oxidized Ti surface in contact with liquid water by means of extensive first-principles molecular dynamics simulations. Taking the obtained structure as reference, we then develop a classical potential to model the Ti/TiOx/water interface. This is based on the mapping with Coulomb and Lennard-Jones potentials of the adsorption energy landscape of single water and ammonia molecules on the rutile TiO2(110) surface. The interactions with arbitrary organic molecules are obtained via standard combination rules to established biomolecular force fields. The transferability of our potential to the case of organic molecules adsorbing on the oxidized Ti surface is checked by comparing the classical potential energy surfaces of representative systems to quantum mechanical results at the level of density functional theory. Moreover, we calculate the heat of immersion of the TiO2 rutile surface and the detachment force of a single tyrosine residue from steered molecular dynamics simulations, finding good agreement with experimental reference data in both cases. As a first application, we study the adsorption behavior of the Arg-Gly-Asp (RGD) peptide on the oxidized titanium surface, focusing particularly on the calculation of the free energy of desorption.

Electrokinetic framework of dielectrophoretic deposition devices

Numerical modeling and experiments are performed investigating the properties of a dielectrophoresis-based deposition device, in order to establish the electrokinetic framework required to understand the effects of applied inhomogeneous electric fields while moving particles to desired locations. By capacitively coupling electrodes to a conductive substrate, the controlled large-scale parallel dielectrophoretic assembly of nanostructures in individually accessible devices at a high integration density is accomplished. Thermal gradients in the solution, which give rise to local permittivity and conductivity changes, and velocity fields are solved by coupling electric, thermal, and fluid-mechanical equations. The induced electrothermal flow (ETF) causes vortices above the electrode gap, attracting particles, such as single-walled carbon nanotubes (SWNTs), before they are trapped by the dielectrophoretic force and deposit across the electrodes. Long-range carbon nanotube transport is governed by hydrodynamic...

High-yield dielectrophoretic assembly of two-dimensional graphene nanostructures

Graphene handling is still dominated by serial mechanical exfoliation, which may well facilitate measurements in a laboratory environment but does not allow reliable larger-scale integration. Herein we demonstrate the controlled, high-yield (>90%), site-selective deposition of ultrathin few-layer (three to ten) graphene oxide by dielectrophoresis between prefabricated electrodes. Individual layers are found near the edges. Initially insulating, thermal reduction at 450 °C thins out the two-dimensional few-atom thick films and dramatically reduces electrical resistances down to 40 kΩ. Conductivities between 15 and 36 S/cm are obtained. The introduced method permits the nonintrusive, parallel, large-scale assembly of soluble two-dimensional nanostructures and sheets.

Aqueous dispersion and dielectrophoretic assembly of individual surface-synthesized single-walled carbon nanotubes

The successful dispersion and large-scale parallel assembly of individual surface-synthesized large-diameter (1-3 nm) single-walled carbon nanotubes (SWNTs), grown by chemical vapor deposition (CVD), is demonstrated. SWNTs are removed from the growth substrate by a short, low-energy ultrasonic pulse to produce ultrapure long-term stable surfactant-stabilized solutions. Subsequent dielectrophoretic deposition bridges individual, straight, and long SWNTs between two electrodes. Electrical characterization on 223 low-resistance devices (R(average) approximately 200 kOmega) evidences the high quality of the SWNT raw material, prepared solution, and contact interface. The research reported herein provides an important framework for the large-scale industrial integration of carbon nanotube-based devices, sensors, and applications.

Dielectrophoretic integration of single- and few-layer graphenes

The dielectrophoretic integration of single- and few-layered graphenes from three distinct graphene suspensions is presented, enabling the parallel assembly of individual two-dimensional nanostructures at predefined locations. The first suspension is an aqueous solution of graphene oxide, the second is ultrasonically exfoliated pristine graphene in N-methyl-pyrrolidone (NMP), and the third is exfoliated graphene in surfactant-stabilized 1 wt % aqueous SDBS solutions. The most crucial aspect for the successful thin flake deposition is the solution quality of the exfoliated graphene. After dielectrophoresis, single-layer graphene oxide is placed between the electrodes, which, while initially insulating, recovers its electrical conductivity following thermal reduction. From the chemically unmodified graphene-NMP solutions, the directed assembly of electrically active few-layer graphene flakes is realized, with flake thicknesses in the range 8–30 nm. Liquid phase exfoliation in water-surfactant solutions yiel...

Combination of Photoinduced Alignment and Self-Assembly to Realize Polarized Emission from Ordered Semiconductor Nanorods

One-dimensional semiconductor nanorods are a very promising class of materials for applications in modern optoelectronic devices, such as light-emitting diodes, solar cells, displays, and lasers. Their ability to emit linearly polarized light is considered to simplify device structures and improve the overall efficiencies. To ensure macroscopic polarization in such devices, the biggest challenge is the long-range alignment of nanorods by controllable means. We propose a technique that combines photoinduced alignment with nanorods self-assembly. With this approach, we are able to actively control the alignment directions of highly emissive semiconductor nanorods in both microscopic and macroscopic scale with the order parameter as high as 0.87. As a result, polarized emission has been achieved with the degree of polarization of 0.62. Furthermore, patterned alignment of nanorods with spatially varying local orientations has been realized to demonstrate the great flexibility of this approach. Besides opportunities for applications, our method of alignment offers insights into host-guest interactions governing self-assembly of colloidal nanocrystals within the host molecular matrix.