Stefan Walheim

Surface-induced structure formation of polymer blends on patterned substrates

Phase separation in bulk mixtures commonly leads to an isotropic, disordered morphology of the coexisting phases. The presence of a surface can significantly alter the phase-separation process, however,. Here we show that the domains of a phase-separating mixture of polymers in a thin film can be guided into arbitrary structures by a surface with a prepatterned variation of surface energies. Such a pattern can be imposed on a surface by using printing methods for depositing microstructured molecular films, thereby allowing for such patterns to be readily transferred to a two-component polymer film. This approach might provide a simple means for fabricating polymer-based microelectronic circuits or polymer resists for lithographic semiconductor processing.

The Salvinia Paradox: Superhydrophobic Surfaces with Hydrophilic Pins for Air Retention Under Water

[*] Prof. W. Barthlott, S. Wiersch, Dr. H. F. Bohn Nees-Institut für Biodiversität der Pflanzen Rheinische Friedrich-Wilhelms-Universität Meckenheimer Allee 170, 53115 Bonn (Germany) E-mail: barthlott@uni-bonn.de Prof. Th. Schimmel, Dr. M. Barczewski, Dr. S. Walheim, A. Weis, A. Kaltenmaier Institute of Applied Physics and Center for Functional Nanostructures (CFN) University of Karlsruhe Karlsruhe Institute of Technology (KIT) 76131 Karlsruhe (Germany) Institute of Nanotechnology and Center for Functional Nanostructures (CFN) Forschungszentrum Karlsruhe Karlsruhe Institute of Technology (KIT) 76021 Karlsruhe (Germany) E-mail: thomas.schimmel@physik.uni-karlsruhe.de Prof. K. Koch Biologie und Nanobiotechnologie Hochschule Rhein-Waal Landwehr 4, 47533 Kleve (Germany)

Surface plasmon polariton absorption modulator.

A new compact electrically controlled surface plasmon polariton (SPP) absorption modulator operating at communication wavelengths is introduced. The modulator is controlled by changing the free carrier density and thereby the propagation loss of the SPP.

Lipid multilayer gratings

The interaction of electromagnetic waves with matter can be controlled by structuring the matter on the scale of the wavelength of light, and various photonic components have been made by structuring materials using top-down or bottom-up approaches. Dip-pen nanolithography is a scanning-probe-based fabrication technique that can be used to deposit materials on surfaces with high resolution and, when carried out in parallel, with high throughput. Here, we show that lyotropic optical diffraction gratings--composed of biofunctional lipid multilayers with controllable heights between approximately 5 and 100 nm--can be fabricated by lipid dip-pen nanolithography. Multiple materials can be simultaneously written into arbitrary patterns on pre-structured surfaces to generate complex structures and devices, allowing nanostructures to be interfaced by combinations of top-down and bottom-up fabrication methods. We also show that fluid and biocompatible lipid multilayer gratings allow label-free and specific detection of lipid-protein interactions in solution. This biosensing capability takes advantage of the adhesion properties of the phospholipid superstructures and the changes in the size and shape of the grating elements that take place in response to analyte binding.

In situ monitoring the drying kinetics of knife coated polymer-fullerene films for organic solar cells

The efficiency of polymer based bulk heterojunction (BHJ) solar cells mainly depends on the film morphology of the absorption layer and the interface properties between the stacked layers. A comparative study using atomic force microscopy(AFM) and optical in situthin film drying measurements is performed. The strong impact of distinct drying scenarios on the polymer:fullerene BHJ layer morphology is investigated by AFM. The AFM images show a systematic dependency of structure sizes at the surface on drying kinetics. In addition thin film optical measurements for the determination of thin film drying kinetics and parameters are performed using a dedicated experimental setup. The data are used as the input for a quantitative simulation of the drying process. The film thickness decreases linearly during drying while the solvent mass fraction decreases moderately over a wide range until it drops rapidly. Subsequently the remaining solvent fraction evaporates considerably slower. Our work gives a fundamental understanding of the film formation kinetics and prerequisites for the systematic optimization of the film morphology in solution processed organic photovoltaic devices.

On the dielectric and optical properties of surface-anchored metal-organic frameworks: A study on epitaxially grown thin films

We determine the optical constants of two highly porous, crystalline metal-organic frameworks (MOFs). Since it is problematic to determine the optical constants for the standard powder modification of these porous solids, we instead use surface-anchored metal-organic frameworks (SURMOFs). These MOF thin films are grown using liquid phase epitaxy (LPE) on modified silicon substrates. The produced SURMOF thin films exhibit good optical properties; these porous coatings are smooth as well as crack-free, they do not scatter visible light, and they have a homogenous interference color over the entire sample. Therefore, spectroscopic ellipsometry (SE) can be used in a straightforward fashion to determine the corresponding SURMOF optical properties. After careful removal of the solvent molecules used in the fabrication process as well as the residual water adsorbed in the voids of this highly porous solid, we determine an optical constant of n = 1.39 at a wavelength of 750 nm for HKUST-1 (stands for Hong Kong Un...

Nanoscale twinned copper nanowire formation by direct electrodeposition.

Future microelectronic and microelectromechanical systems (MEMS) will require a decreased size as well as high electrical conductivity combined with high mechanical strength. Noble metal nanowires are ideal building blocks for these applications due to their excellent electrical and mechanical properties. Since the properties of metal nanowires strongly depend on their size and microstructure, developing an approach to produce and tune wire size and structure is highly relevant. Although a variety of methods such as electrodeposition guided by templates, hydrothermal reduction, colloidal methods, and vapor-phase deposition have been successfully used to synthesize gold, silver, and copper nanowires, most efforts have focused on size-controlling and sizedependent properties. Much less is known about tuning microstructure and about microstructure-dependent properties due to difficulties associated with controlling the microstructure within such small objects. However, it is well established that microscopic defects such as dislocations, stacking faults, twins, and grain boundaries play a key role in bulk-material properties. For example, nanoscale twinned copper foil exhibits a significantly improved strength (10-fold) while maintaining a high electrical conductivity.

Hierarchic Structure Formation in Binary and Ternary Polymer Blends

The phase morphology of multi-component polymer blends is governed by the interfacial interactions of its components. We discuss here the domain morphology in thin films of model binary and ternary polymer blends containing polystyrene, poly(methyl metacrylate), and poly(2-vinylpyridine) (PS, PMMA, PVP). When sandwiched between two non-polar surfaces, characteristic lateral phase morphologies are observed after the film formation by spin-coating. We discuss here two techniques, by which hierarchical lateral structures in polymer films can be made. The first method makes use of two simultaneously occurring interfacial instabilities. The second technique employs the effect of a variation of the enthalpic interaction parameters in a ternary polymer mixture on its lateral polymer phase morphology.

Transfer of a chemical substrate pattern into an island-forming diblock copolymer film

We investigate the transfer of a chemical pattern on a substrate into a symmetric diblock copolymer thin film of poly(styrene-2-vinylpyridine) (PS-PVP). The substrates have patterns of self-assembled monolayers (SAMs) produced by microcontact printing H3C-terminated (H3C-) SAM stripes alternating with HO-terminated (HO-) SAM stripes. The PS-PVP lamellae over the H3C-SAM have a defect structure that attracts excess PS-PVP that would normally form islands on a uniform HO-SAM stripe. We seek to understand the process that limits our ability to accommodate all excess polymers on top of the H3C-SAM. In the early stages of annealing, waves of thickness develop from the H3C/HO-SAM boundary and propagate into the film over the HO-SAM. For very short annealing times, the wavelength λ of these thickness waves is constant at any given time for all grating periodicities. Large amplitude patterns develop when λ=2d/(2n−1), where d is the width of the HO-SAM stripe and n is an integer ⩾1. Such patterns suggest construct...

Polymer blend lithography: A versatile method to fabricate nanopatterned self-assembled monolayers.

Summary A rapid and cost-effective lithographic method, polymer blend lithography (PBL), is reported to produce patterned self-assembled monolayers (SAM) on solid substrates featuring two or three different chemical functionalities. For the pattern generation we use the phase separation of two immiscible polymers in a blend solution during a spin-coating process. By controlling the spin-coating parameters and conditions, including the ambient atmosphere (humidity), the molar mass of the polystyrene (PS) and poly(methyl methacrylate) (PMMA), and the mass ratio between the two polymers in the blend solution, the formation of a purely lateral morphology (PS islands standing on the substrate while isolated in the PMMA matrix) can be reproducibly induced. Either of the formed phases (PS or PMMA) can be selectively dissolved afterwards, and the remaining phase can be used as a lift-off mask for the formation of a nanopatterned functional silane monolayer. This “monolayer copy” of the polymer phase morphology has a topographic contrast of about 1.3 nm. A demonstration of tuning of the PS island diameter is given by changing the molar mass of PS. Moreover, polymer blend lithography can provide the possibility of fabricating a surface with three different chemical components: This is demonstrated by inducing breath figures (evaporated condensed entity) at higher humidity during the spin-coating process. Here we demonstrate the formation of a lateral pattern consisting of regions covered with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) and (3-aminopropyl)triethoxysilane (APTES), and at the same time featuring regions of bare SiOx. The patterning process could be applied even on meter-sized substrates with various functional SAM molecules, making this process suitable for the rapid preparation of quasi two-dimensional nanopatterned functional substrates, e.g., for the template-controlled growth of ZnO nanostructures [1].