Predicting the orientation of lipid cubic phase films.

Lipid cubic phase films are of increasingly widespread importance, both in the analysis of the cubic phases themselves by techniques including microscopy and X-ray scattering, and in their applications, especially as electrode coatings for electrochemical sensors and for templates for the electrodeposition of nanostructured metal. In this work we demonstrate that the crystallographic orientation adopted by these films is governed by minimization of interfacial energy. This is shown by the agreement between experimental data obtained using grazing-incidence small-angle X-ray scattering (GI-SAXS), and the predicted lowest energy orientation determined using a theoretical approach we have recently developed. GI-SAXS data show a high degree of orientation for films of both the double diamond phase and the gyroid phase, with the [111] and [110] directions respectively perpendicular to the planar substrate. In each case, this matches the lowest energy facet calculated for that particular phase.

Competition between substrate-mediated π-π stacking and surface-mediated T(g) depression in ultrathin conjugated polymer films.

We report surface and interface effects in dynamics and chain conformation in the thin film of conjugated polymer PCDTBT. To probe dynamic anomalies, we measure the glass transition temperature (T(g)) of PCDTBT films as a function of thickness, and find that there is a significant depression in T(g) for films less than 100 nm thick; a result qualitatively similar to that observed in many other polymer film systems. However, for films less than 40 nm, the T(g) converges to a constant value of 20 K below its bulk value. Grazing incidence X-ray diffraction shows depth-dependent molecular organization that is associated with the unusual thickness-dependent dynamics.

Printed Thin Magnetic Films Based on Diblock Copolymer and Magnetic Nanoparticles.

Printing techniques have been well established for large-scale production and have developed to be effective in controlling the morphology and thickness of the film. In this work, printing is employed to fabricate magnetic thin films composed of polystyrene coated maghemite nanoparticles (γ-Fe2O3 NPs) and polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer. By applying an external magnetic field during the print coating step, oriented structures with a high content of nanoscale magnetic particles are created. The morphology of the magnetic films and the arrangement of NPs within the polymer matrix are characterized with real and reciprocal space techniques. Due to the applied magnetic field, the magnetic NPs self-assemble into microscale sized wires with controlled widths and separation distances, endowing hybrid films with a characteristic magnetic anisotropy. At the nanoscale level, due to the PS coating, the NPs disperse as single particles at low NP concentrations. The NPs self-assemble into nanosized clusters inside the PS domains when the NP concentration increases. Due to a high loading of uniformly dispersed magnetic NPs across the whole printed film, a strong sensitivity to an external magnetic field is achieved. The enhanced superparamagnetic property of the printed films renders them promising candidate materials for future magnetic sensor applications.

Patterned Diblock Co-Polymer Thin Films as Templates for Advanced Anisotropic Metal Nanostructures.

We demonstrate glancing-angle deposition of gold on a nanostructured diblock copolymer, namely polystyrene-block-poly(methyl methacrylate) thin film. Exploiting the selective wetting of gold on the polystyrene block, we are able to fabricate directional hierarchical structures. We prove the asymmetric growth of the gold nanoparticles and are able to extract the different growth laws by in situ scattering methods. The optical anisotropy of these hierarchical hybrid materials is further probed by angular resolved spectroscopic methods. This approach enables us to tailor functional hierarchical layers in nanodevices, such as nanoantennae arrays, organic photovoltaics, and sensor electronics.

Entrapment of decanethiol in a hydrogen-bonded bimolecular template.

We have used scanning tunneling microscopy to investigate the deposition of 1-decanethiol onto a bimolecular self-assembled network composed of PTCDI (perylene tetracarboxylic diimide) and melamine on a Au(111) surface. A new laterally organized phase in which the pores of a parallelogram bimolecular arrangement trap two decanethiol molecules is identified. Disruption of the hexagonal PTCDI-melamine network arrangement after decanethiol deposition is also observed, providing insights about the interplay between supramolecular and substrate-adsorbate interactions.

Functionalized supramolecular nanoporous arrays for surface templating.

Controlled self-assembly and chemical tailoring of bimolecular networks on surfaces is demonstrated using structural derivatives of 3,4:9,10-perylenetetracarboxylic diimide (PTCDI) combined with melamine (1,3,5-triazine-2,4,6-triamine). Two functionalised PTCDI derivatives have been synthesised, Br(2)-PTCDI and di(propylthio)-PTCDI, through attachment of chemical side groups to the perylene core. Self-assembled structures formed by these molecules on a Ag-Si(111)sqrt3 x sqrt3R30 degrees surface were studied with a room-temperature scanning tunneling microscope under ultrahigh vacuum conditions. It is shown that the introduction of side groups can have a significant effect upon both the structures formed, notably in the case of di(propylthio)-PTCDI which forms a previously unreported unimolecular hexagonal arrangement, and their entrapment behaviour. These results demonstrate a new route of functionalisation for network pores, opening up the possibility of designing nanostructured surface structures with chemical selectivity and applications in nanostructure templating.