Dynamics of molecular self-ordering in tetraphenyl porphyrin monolayers on metallic substrates.

A molecular model system of tetraphenyl porphyrins (TPP) adsorbed on metallic substrates is systematically investigated within a joint scanning tunnelling microscopy/molecular modelling approach. The molecular conformation of TPP molecules, their adsorption on a gold surface and the growth of highly ordered TPP islands are modelled with a combination of density functional theory and dynamic force field methods. The results indicate a subtle interplay between different contributions. The molecule-substrate interaction causes a bending of the porphyrin core which also determines the relative orientations of phenyl legs attached to the core. A major consequence of this is a characteristic (and energetically most favourable) arrangement of molecules within self-assembled molecular clusters; the phenyl legs of adjacent molecules are not aligned parallel to each other (often denoted as pi-pi stacking) but perpendicularly in a T-shaped arrangement. The results of the simulations are fully consistent with the scanning tunnelling microscopy observations, in terms of the symmetries of individual molecules, orientation and relative alignment of molecules in the self-assembled clusters.

The development of self-assembled liquid crystal display alignment layers.

From simple pocket calculators to mobile telephones and liquid crystal display (LCD)-TV, over the past few decades, devices based on LCD technology have proliferated and can now be found in all conceivable aspects of everyday life. Although used in cutting-edge technology, it is surprising that a vital part in the construction of such displays, namely the alignment layer, relies essentially on a mechanical rubbing process, invented almost 100 years ago. In this paper efforts to develop alignment layers (also called command layers) by processes other than rubbing, namely self-assembly of molecular and macromolecular components will be discussed. Two topics will be presented: (i) tuneable command layers formed by stepwise assembling of siloxane oligomers and phthalocyanine dyes on indium tin oxide surfaces and (ii) command layers formed by self-assembly of porphyrin trimers. The potential use of these layers in sensor devices will also be mentioned.

Macroscopic hierarchical surface patterning of porphyrin trimers via self-assembly and dewetting.

The use of bottom-up approaches to construct patterned surfaces for technological applications is appealing, but to date is applicable to only relatively small areas (approximately 10 square micrometers). We constructed highly periodic patterns at macroscopic length scales, in the range of square millimeters, by combining self-assembly of disk-like porphyrin dyes with physical dewetting phenomena. The patterns consisted of equidistant 5-nanometer-wide lines spaced 0.5 to 1 micrometers apart, forming single porphyrin stacks containing millions of molecules, and were formed spontaneously upon drop-casting a solution of the molecules onto a mica surface. On glass, thicker lines are formed, which can be used to align liquid crystals in large domains of square millimeter size.

Increased alignment of electronic polymers in liquid crystals via hydrogen bonding extension.

Crucial for the development of enhanced electrooptic materials is the construction of highly anisotropic materials. Nematic liquid crystals are able to control the chain conformation and alignment of poly(phenylene ethynylene)s (PPEs), producing electronic polymers with chain-extended planar conformations for improved transport properties. Here, we show that the dichroic ratio, and hence polymer alignment, increases dramatically when interpolymer interactions are introduced by end capping the PPE with hydrogen bonding groups. This increased order can be readily turned off by the introduction of a competing monofunctionalized hydrogen bonding compound. The formation of hydrogen bonds between the polymers results in the formation of gels and elastomers which may be of interest for future applications.

LCD-based detection of enzymatic action.

By incorporating an ester-containing substrate in a self-assembled alignment layer for liquid crystal cells, the presence of a lipase (CALB) can be directly detected through its enzymatic action on the alignment layer, without the need for fluorescent labelling or enzyme assays.

Tunable command layers for liquid crystal alignment.

A simple method for the construction of a stable, tunable, self-assembled command layer for liquid crystal display purposes is described. A pyridine-functionalized oligosiloxane spontaneously forms an anisotropic, grooved surface on indium-tin-oxide, enabling it to align liquid crystalline molecules. The pyridine functions act as seeds for the epitaxial growth of stacks of highly ordered zinc phthalocyanines, the height of which can be controlled. These stacks increase the interaction between the surface and the liquid crystalline matrix by amplifying the surface ordering into the liquid crystal bulk. By varying the height of the stacks, direct control over the properties of the liquid crystal domains is achieved. These properties can be further tuned by adding to the liquid crystal, micro- and nanomolar concentrations of nitrogen-containing compounds, which are capable of interacting with and dissolving the stacks. The procedures we describe offer possibilities to use such tunable systems in LCD-based sensor devices as well as in solar-cell applications.

Novel alignment technique for LCD-biosensors.

The directional drying of a low-salt Tris-EDTA (TE)-buffer to give an alignment layer offers a simple, one-step, non-contact procedure for the construction of parallel liquid crystal displays (LCDs), which can be used to amplify the presence of DNA to scales visible to the naked eye, opening up possibilities for easy detection of bio recognition events.