Epitaxial growth of ultrathin palladium films on Re{0001}

Ultrathin bimetallic layers create unusual magnetic and surface chemical effects through the modification of electronic structure brought on by low dimensionality, polymorphism, reduced screening, and epitaxial strain. Previous studies have related valence and core-level shifts to surface reactivity through the d-band model of Hammer and Nørskov, and in heteroepitaxial films this band position is determined by competing effects of coordination, strain, and hybridization of substrate and overlayer states. In this study we employ the epitaxially matched Pd on Re{0001} system to grow films with no lateral strain. We use a recent advancement in low-energy electron diffraction to expand the data range sufficiently for a reliable determination of the growth sequence and out-of-plane surface relaxation as a function of film thickness. The results are supported by scanning tunneling microscopy and X-ray photoemission spectroscopy, which show that the growth is layer-by-layer with significant core-level shifts due to changes in film structure, morphology, and bonding.

The surface structure of BaO on Pt(111): (2x2)-reconstructed BaO(111)

The surface structure of BaO(111) has been determined using STM and computer modelling. The BaO(111) surface was prepared in thin film form on Pt(111) and presents a surface with twice the lattice parameter expected for that of the bulk termination, i.e. a (2 x 2) reconstruction. Computer modelling indicates that the bulk termination is unstable, but that the (2 x 2) reconstructed BaO(111) surface has a low surface energy and is hence a stable surface reconstruction. The (2 x 2) reconstruction consists of small, three-sided pyramids with (100) oriented sides and either oxygen or barium ions at the apices. Less regular surface reconstructions containing the same pyramids are almost equally stable, indicating that we may also expect less regular regions to appear with a fairly random distribution of these surface species. The simulations further suggest that a regular (4 x 4) reconstruction built up of bigger pyramids is even more energetically favourable, and some evidence is found for such a structure in the STM. (c) 2006 Elsevier B.V. All rights reserved.

Effect of Stretching on the Structure of Cylinder- and Sphere-Forming Styrene-Isoprene-Styrene Block Copolymers

Two styrene-isoprene-styrene block copolymers Vector 4111 and 4113, exhibiting cylindrical (18 wt % PS) and spherical (16 wt % PS) morphology, respectively, have been examined under uniaxial elongation up to 200% strain. On the basis of stress-strain data, mechanical properties are compared for isotropic and oriented polystyrene domains. The structure at various stages of deformation has been determined from SAXS patterns in three planes and two principal deformation directions with respect to orientation. Samples showed a very high degree of hexagonal packing, resulting in an X-ray pattern taken parallel to the cylinder alignment approaching single crystal ordering. Cylinders were aligned with the closest packed planes parallel to film surface. Particular attention has been paid to a lattice deformation process occurring during the first stretching and relaxation cycle. For a copolymer with oriented cylindrical morphology the deformation was affine up to 120% strain. The microdomain spacing was calculated parallel and perpendicular to the stretching direction. The cylindrical microstructure orientation, quantified by Hermans' orientation factor reduced during elongation of oriented polymer, while the elongation of isotropic sample caused an increase of orientation. Deformation of all studied morphologies was reversible.

Synthesis and fabrication of a thin film containing silica-encapsulated face-centered tetragonal FePt nanoparticles

Self-assembly of monodisperse, silica-encapsulated, face-centered tetragonal FePt nanoparticles forms closely packed 2D arrays (see figure). Placing monodisperse FePt nanoparticles in silica nanocapsules allows the transition from a disordered face-centered cubic phase to a ferromagnetic crystalline face-centered tetragonal structure at elevated temperature without severe sintering. These materials are potential candidates for the generation of ultrahigh-density magnetic recording media.

Two methods for modelling the propagation of terahertz radiation in a layered structure

Modelling the interaction of terahertz(THz) radiation with biological tissueposes many interesting problems. THzradiation is neither obviously described byan electric field distribution or anensemble of photons and biological tissueis an inhomogeneous medium with anelectronic permittivity that is bothspatially and frequency dependent making ita complex system to model.A three-layer system of parallel-sidedslabs has been used as the system throughwhich the passage of THz radiation has beensimulated. Two modelling approaches havebeen developed a thin film matrix model anda Monte Carlo model. The source data foreach of these methods, taken at the sametime as the data recorded to experimentallyverify them, was a THz spectrum that hadpassed though air only.Experimental verification of these twomodels was carried out using athree-layered in vitro phantom. Simulatedtransmission spectrum data was compared toexperimental transmission spectrum datafirst to determine and then to compare theaccuracy of the two methods. Goodagreement was found, with typical resultshaving a correlation coefficient of 0.90for the thin film matrix model and 0.78 forthe Monte Carlo model over the full THzspectrum. Further work is underway toimprove the models above 1 THz.

Structure variation and evolution in microphase-separated grafted diblock copolymer films

The phase behavior of grafted d-polystyrene-block-poly(methyl methacrylate) diblock copolymer films is examined, with particular focus on the effect of solvent and annealing time. It was observed that the films undergo a two-step transformation from an initially disordered state, through an ordered metastable state, to the final equilibrium configuration. It was also found that altering the solvent used to wash the films, or complete removal of the solvent prior to thermal annealing using supercritical CO2, could influence the structure of the films in the metastable state, though the final equilibrium state was unaffected. To aid in the understanding to these experimental results, a series of self-consistent field theory calculations were done on a model diblock copolymer brush containing solvent. Of the different models examined, those which contained a solvent selective for the grafted polymer block most accurately matched the observed experimental behavior. We hypothesize that the structure of the films in the metastable state results from solvent enrichment of the film near the film/substrate interface in the case of films washed with solvent or faster relaxation of the nongrafted block for supercritical CO2 treated (solvent free) films. The persistence of the metastable structures was attributed to the slow reorganization of the polymer chains in the absence of solvent.

Detection of nitroaromatic vapours with diketopyrrolopyrrole thin films: exploring the role of structural order and morphology on thin film properties and fluorescence quenching efficiency

Sensitive optical detection of nitroaromatic vapours with diketo-pyrrolopyrrole thin films is reported for the first time and the impact of thin film crystal structure and morphology on fluorescence quenching behaviour demonstrated.