Reversible tuning of a block-copolymer nanostructure via electric fields.

Block copolymers consisting of incompatible components self-assemble into microphase-separated domains yielding highly regular structures with characteristic length scales of the order of several tens of nanometres. Therefore, in the past decades, block copolymers have gained considerable potential for nanotechnological applications, such as in nanostructured networks and membranes, nanoparticle templates and high-density data storage media. However, the characteristic size of the resulting structures is usually determined by molecular parameters of the constituent polymer molecules and cannot easily be adjusted on demand. Here, we show that electric d.c. fields can be used to tune the characteristic spacing of a block-copolymer nanostructure with high accuracy by as much as 6% in a fully reversible way on a timescale in the range of several milliseconds. We discuss the influence of various physical parameters on the tuning process and study the time response of the nanostructure to the applied field. A tentative explanation of the observed effect is given on the basis of anisotropic polarizabilities and permanent dipole moments of the monomeric constituents. This electric-field-induced effect further enhances the high technological potential of block-copolymer-based soft-lithography applications.

Combinatorial preparation and characterization of thin-film multilayer electro-optical devices.

In this article we present a setup for the combinatorial vapor deposition of thin-film multilayer devices as well as methods for the fast and efficient analytic screening of the libraries obtained. The preparation setup is based on a commercially available evaporation chamber equipped with various evaporation sources for both organic and metallic materials. The combinatorial approach is realized by the combination of a rotation stage for the substrate, a five-mask sampler, and an additional mask whose position can be deliberately varied along one axis during the evaporation process. The latter is used to evaporate linear as well as step gradients by continuous or stepwise movement of a shutter mask. The mask sampler allows to define the sectors of the library and to evaporate more complex structures, e.g., an electrode layout. Finally, the simultaneous evaporation of two or more materials enables us to produce layers of varying composition ratio in general and doped materials, in particular. For the control of the evaporation process we have developed an automation software, which is particularly helpful for complex library designs and which grants excellent repeatability of experiments. Efficient and fast characterization of the obtained libraries is realized by (i) a purely optical setup and (ii) an electro-optical setup. (i) The UV/vis reader FLASHScan 530 permits to map out the UV/vis absorbance or fluorescence of the whole library. The UV/vis absorbance is primarily used to determine layer thicknesses and to confirm thickness uniformity across larger regions. The fluorescence measurements are used to determine the composition of layers containing fluorescent dyes. (ii) For a detailed short- and long-term electro-optical analysis we have developed an automated measurement system, which allows the characterization of 8x8 optoelectronic devices and to study their degradation behavior. Both solar cells and organic light-emitting diodes can be tested. Finally, we have developed a data analysis software to extract characteristic values from the huge amount of data and with this facilitate the finding of systematic dependencies.

Influence of initial order on the microscopic mechanism of electric field induced alignment of block copolymer microdomains.

We investigate the mechanism of microdomain orientation in concentrated block copolymer solutions exposed to a dc electric field by in situ synchrotron small-angle X-ray scattering (SAXS). As a model system, we use concentrated solutions of a lamellar polystyrene-b-polyisoprene block copolymer in toluene. We find that both the microscopic mechanism of reorientation and the kinetics of the process strongly depend on the initial degree of order in the system. In a highly ordered lamellar system with the lamellae being aligned perpendicular to the electric field vector, only nucleation and growth of domains is possible as a pathway to reorientation and the process proceeds rather slowly. In less ordered samples, grain rotation becomes possible as an alternative pathway, and the process proceeds considerably faster. The interpretation of our finding is strongly corroborated by dynamic self-consistent field simulations.