Two- and three-dimensional Au nanoparticle/CoTMPyP self-assembled nanotructured materials: Film structure, tunable electrocatalytic activity, and plasmonic properties

Two- and three-dimensional Au nanoparticle/[tetrakis(N-methylpyridyl)porphyrinato]cobalt (CoTMPyP) nanostructured materials were prepared by "bottom-up" self-assembly. The electrocatalytic and plasmonic properties of the Au nanoparticle/CoTMPyP self-assembled nanostructured materials (abbreviated as Au/CoTMPyP SANMs) are tunable by controlled self-assembly of the An nanoparticles and CoTMPyP on indium tin oxide (ITO) electrode. The electrocatalytic activity of the Au/CoTMPyP SANMs can be tuned in two ways. One way is that citrate-stabilized An nanoparticles are positioned first on ITO surface with tunable number density, and then positively charged CoTMPyP ions are planted selectively on these gold sites. The other way is that An nanoparticles and CoTMPyP are deposited by virtue of layer-by-layer assembly, which can also tune the amount of the as-deposited electrocatalysts. FE-SEM studies showed that three-dimensional SANMs grow in the lateral expansion mode, and thermal annealing resulted in both surface diffusion of nanoparticles and atomic rearrangement to generate larger gold nanostructures with predominant (I 11) facets.

Preparation of hybrid thin film modified carbon nanotubes on glassy carbon electrode and its electrocatalysis for oxygen reduction

A hybrid thin film containing Pt nanoparticles and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) modified multi-walled carbon nanotubes (MWNTs) on a glassy carbon (GC) electrode surface was fabricated. This hybrid film electrode exhibited remarkable electrocatalytic activity for oxygen reduction and high stability with promising applications in fuel cells.

Nanocomposite multilayer film of preyssler-type polyoxometalates with fine tunable electrocatalytic activities

Through layer-by-layer (LBL) assembly technique, iron oxide (Fe3O4) nanoparticles coated by poly (diallyldimethylammonium chloride) (PDDA) and Preyssler-type polyoxometalates (NH4)(14)NaP5W30O110.31H(2)O (P5W30) were alternately deposited on quartz and ITO substrates, and 4-aminobenzoic acid modified glassy carbon electrodes. Thus-prepared multilayer films were characterized by UV-visible spectroscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry. It was proved that the multilayer films are uniform and stable. And the electrocatalytic activities of the multilayer films can be fine-tuned by adjusting the assembly conditions in the LBL assembly process, such as the pH of the assembly solution. The multilayer films fabricated from P5W30 solutions dissolved in 0.1 M H2SO4 exhibit high electrocatalytic response and sensitivity toward the reduction of two substrates of important analytical interests, HNO2 and IO3- whereas the films assembled with P5W30 solutions dissolved in 1.0 M H2SO4 show remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). Furthermore, the electrocatalytic properties of the HER of the latter film can be obtained from the former film upon exposure to 1.0 M H2SO4 for several hours.

Conductive property of multiwall carbon nanotubes-PEO-salt nanocomposite film

By adding a small amount of multiwall carbon nanotubes (MWNTs) to polyethylene oxide (PEO) and a salt system, a new type of nanocomposite film was constructed. At ambient temperature, the conductivity of the PEO-salt-0.5 wt % MWNTs was nearly three orders of magnitude higher than that of the PEO-salt system. The conductive property of the nanocomposite film was characterized by ac impedance and the differential scanning calorimetry technique.

The electrocatalytic oxidation of ascorbic acid on polyaniline film synthesized in the presence of camphorsulfonic acid

Polyaniline-camphorsulfonic acid (PAN-CSA) composite film on platinum electrode surface has been synthesized via the electrochemical polymerization of aniline in the presence of camphorsulfonic acid (CSA). It was found that the doping of polyaniline (PAN) with CSA extends the electroactivity of PAN in neutral and even in alkaline media. The PAN-CSA composite film coated platinum electrodes are shown to be good electrocatalytic surfaces for the oxidation of ascorbic acid (AA) in phosphate buffer solution (PBS) of pH 7.0. The anodic peak potential of AA shifts from 0.63 V at the bare platinum electrode to 0.34 V at the PAN-CSA composite modified platinum electrode with a greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5-50 mM using cyclic voltammetry. The kinetics of the catalytic reaction are investigated using rotating disk electrode voltammetry and chronoamperometry. The results are explained using the theory of electrocatalytic reactions at chemically modified electrodes. The PAN-CSA composite on the electrode surface shows good reproducibility and stability.

Fabrication and characterization of DNA/QPVP-Os redox-active multilayer film

Calf thymus DNA was immobilized on functionalized glassy carbon, gold and quartz substrates, respectively, by the layer-by-layer (LBL) assembly method with a polycation QPVP-Os, a quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) as counterions. UV-visible absorption and surface plasmon resonance spectroscopy (SPR) showed that the resulting film was uniform with the average thickness 3.4 nm for one bilayer. Cyclic voltammetry (CV) showed that the total surface coverage of the polycations increases as each QPVP-Os/DNA bilayer added to the electrode surface, but the surface formal potential of Os-centered redox reaction shifts negatively, which is mainly attributed to the intercalation of redox-active complex to DNA chain. The electron transfer kinetics of electroactive QPVP-Os in the multilayer film was investigated by electrochemical impedance experiment for the first time. The permeability of Fe(CN)(6)(3-) in the solution into the multilayer film depends on the number of bilayers in the film. It is worth noting that when the multilayer film is up to 4 bilayers, the CV curves of the multilayer films display the typical characteristic of a microelectrode array.

Morphology development of ultrathin symmetric diblock copolymer film via solvent vapor treatment

We have followed the time development of the microdomain structure in symmetric diblock copolymer poly(styrene-b-methyl methacrylate), P(S-b-MMA), ultrathin films via PMMA-selective solvent vapor treatment by atomic force microscopy (AFM). After preparation on a substrate preferentially attracting the PMMA block, PS forms a continuous layer at a film's free surface. With subsequent solvent vapor treatment, the film gradually shows a well-ordered hexagonally packed nanocylinders structure. It is shown that only when the film thickness is less than the 1/2L(0) (lamellar repeat spacing), and exposed to PMMA block selective solvent for an appropriate time, can the well-ordered hexagonally packed nanocylinders form. On an extended solvent vapor treatment, a mixed morphology containing nanocylinders and stripes appears, followed by the striped morphologies. When the annealing time is long enough, the film comes back to the flat surface again, however, with PMMA instead of PS dominating the free surface.

Pattern formation in a confined polymer film induced by a temperature gradient

We have studied a morphological instability of a double layer comprising the polymer film and air gap confined between the two plates set to different temperatures. The temperature gradient across the double layer causes the breakup of the polymer film into well-defined columnar, striped or spiral structures spanning the two plates. The pattern formation mechanisms have been discussed. The formed patterns can be transferred to produce PDMS stamp, a key element of soft lithography for future microfabrication.

Tunable ordered droplets induced by convection in phase-separating P2VP/PS blend film

Ordered hexagonal droplets patterns in phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/PVP) formed due to the convection effect by solvent evaporation. The influences of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to PVP on the PVP-rich domains pattern formation and distributions were investigated by atomic force microscope (AFM). Only in an appropriate range of molecular weight of PS, can the ordered pattern form. Too low or too high molecular weight of PS led no ordered pattern due to the viscosity effects. The increase of solvent evaporation rate decreased the mean radius of the PVP-rich domains and the intervals between the centers of the domains due to the enhancement of the viscosity on the top layer of the fluid film. The increase of the weight ratio of PS to PVP decreased mean radius of the PVP-rich domains whereas the intervals between the centers of droplets remained constant. Therefore, the size and the distributions of ordered patterns can be tuned by the polymer molecular weight, the weight ratio of the two components and the solvent evaporation rate.

Ordered pattern formation from dewetting of polymer thin film with surface disturbance by capillary force lithography

The dewetting process of thin polystyrene (PS) film with built-in ordered disturbance by capillary force lithography (CFL) has. been investigated in situ by AFM. Two different phenomena are observed depending on the excess surface energy (DeltaF(gamma)) of the system. When DeltaF(gamma) is less than a certain critical value (i.e., the disturbance amplitude is under a critical value), the PS film would be flattened and become stable finally by heating above T-g. While, if the size of the disturbance amplitude is larger than the critical value, ordered PS liquid droplets form by further dewetting. The pattern formation mechanisms and influencing factors have been discussed in detail.

Ordered droplet formation by thin polymer film dewetting on a stripe-patterned substrate

The dewetting process of thin polystyrene (PS) film on flat and stripe-patterned substrates is presented. Different dewetting processes were observed when the thin PS films annealed at above the glass transition temperature on these different kinds of substrates. The final dewetting on the flat substrate led to formation of polygonal liquid droplets, while on the stripe-patterned substrate, the droplets were observed to align at the centers of the stripes. A possible explanation for the dewetting process on the stripe-patterned substrate is proposed.

Annealing effects on the surface morphologies of thin PS/PMMA blend films with different film thickness

The surface morphology evolution of three thin polystyrene (PS)/polymethyl methacrylate (PMMA) blend films (<70 nm) on SiOx substrates upon annealing were investigated by atomic force microscopy (AFM) and some interesting phenomena were observed. All the spin-coated PS/PMMA blend films were not in thermodynamic equilibrium. For the 67.1 and the 27.2 nm PS/PMMA blend films, owing to the low mobility of the PMMA-rich phase layer at substrate surfaces and interfacial stabilization caused by long-range van der Waals forces of the substrates, the long-lived metastable surface morphologies (the foam-like and the bicontinuous morphologies) were first observed. For the two-dimensional ultrathin PS/PMMA blend film (16.3 nm), the discrete domains of the PS-rich phases upon the PMMA-rich phase layer formed and the secondary phase separation occurred after a longer annealing time.

Fabrication and luminescent properties of rare earths-doped Gd-2(WO4)(3) thin film phosphors by Pechini sol-gel process

Rare earth ions (Eu3+ and Dy3+)-doped Gd-2(WO4)(3) phosphor films were prepared by a Pechini sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting powders and films. The results of XRD indicate that the films begin to crystallize at 600degreesC and the crystallinity increases with the elevation of annealing temperatures. The film is uniform and crack-free, WO(4)(2-)mainly consists of closely packed fine particles with an average grain size of 80 nm. Owing to an energy transfer from 4 groups, the rare earth ions show their characteristic emissions in crystalline Gd-2(WO4)(3) phosphor films, i.e., D-5(J) -F-7(J), (J = 0, 1, 2, 3; J' = 0 1, 2, 3, 4, not in all cases) transitions for Eu3+ and F-4(9/2)-H-6(J) (J = 13/2, 15/2) transitions for D Y3+, with the hypersensitive transitions D-5(0)-F-7(2) (Eu3+) and F-4(9/2) - H-6(13/2) (Dy3+) being the most prominent groups, respectively.

Organic thin-film transistors having inorganic/organic double gate insulators

Bottom-contact organic thin-film transistors (BC OTFTs) based on inorganic/organic double gate insulators were demonstrated. The double gate insulators consisted of tantalum pentoxide (Ta2O5) with high dielectric constant (kappa) as the first gate insulator and octadecyltrichlorosilane (OTS) with low kappa as the second gate insulator. The devices have carrier mobilities larger than 10(-2) cm(2)/V s, on/off current ratio greater than 10(5), and the threshold voltage of -14 V, which is threefold larger field-effect mobility and an order of magnitude larger on/off current ratio than the OTFTs with a Ta2O5 gate insulator. The leakage current was decreased from 2.4x10(-6) to 7.4x10(-8) A due to the introduction of the OTS second dielectric layer. The results demonstrated that using inorganic/organic double insulator as the gate dielectric layer is an effective method to fabricate OTFTs with improved electric characteristics.