Synthesis of ordered Al nanowire arrays

Ordered Al nanowire arrays with the same nanowire density but the diameters decrease radially embedded in one piece of anodic alumina membranes were successfully fabricated by two-step synthesis: electrodeposition of Zn and replacement in AlCl₃ solution. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected-area electron diffraction techniques were used to characterize the Al nanowires obtained. SEM and TEM images taken from the different areas of Al nanowire arrays show that we can control the growth of aligned Al nanowires with different diameters in a single process at the same time. The investigation results not only have potential applications in photoelectric devices but also open up a new method for fabricating nano-scale materials.     

Electrochemical synthesis of ordered alumina nanowire arrays

Ordered Al₂O₃ nanowire arrays embedded in the nanochannels of anodic alumina membranes (AAMs) were synthesized by electrodepostion at room temperature. Our synthetic route yielded large quantities of Al₂O₃ nanowires of uniform size and shape that are ~40 μm long with diameters of 70 nm. The Al₂O₃ nanowire structures were characterized by scanning and transmission electron microscopies, high-resolution transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. Electronic Publication     

Orthogonal gas sensor arrays by chemoresistive material design

Gas sensor arrays often lack discrimination power to different analytes and robustness to interferants, limiting their success outside of research laboratories. This is primarily due to the widely sensitive (thus weakly-selective) nature of the constituent sensors. Here, the effect of orthogonality on array accuracy and precision by selective sensor design is investigated. Therefore, arrays of (2–5) selective and non-selective sensors are formed by systematically altering array size and composition. Their performance is evaluated with 60 random combinations of ammonia, acetone and ethanol at ppb to low ppm concentrations. Best analyte predictions with high coefficients of determination (R²) of 0.96 for ammonia, 0.99 for acetone and 0.88 for ethanol are obtained with an array featuring high degree of orthogonality. This is achieved by using distinctly selective sensors (Si:MoO₃ for ammonia and Si:WO₃ for acetone together with Si:SnO₂) that improve discrimination power and stability of the regression coefficients. On the other hand, arrays with collinear sensors (Pd:SnO₂, Pt:SnO₂ and Si:SnO₂) hardly improve gas predictions having R² of 0.01, 0.86 and 0.28 for ammonia, acetone and ethanol, respectively. Sometimes they even exhibited lower coefficient of determination than single sensors as a Si:MoO₃ sensor alone predicts ammonia better with a R² of 0.68.

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Graphical abstract Conventional arrays (red) with weakly-selective sensors span a significantly smaller volume in the analyte space than arrays containing distinctly-selective sensors (orthogonal array, green). Orthogonal arrays feature better accuracy and precision than conventional arrays in mixtures of ammonia, acetone and ethanol.

     

Template ordered open-grid arrays of paired endohedral fullerenes

Developing useful molecular systems, such as planar networks for novel molecular electronics, requires the ability to control the way molecules assemble at surfaces. Here we report how an oxide crystal surface can be used as a template to controllably order endohedral fullerenes, Er3N@C80, into two-dimensional (2D) open-grid arrays. The crystal surface is made of highly ordered oxide nanostructures which self-assemble on the surface of SrTiO3(001). This method of molecular ordering can be applied to other fullerenes and has the potential to provide a basis for developing a wide range of molecular architectures.     

Self-assembly of highly ordered Peptide amphiphile metalloporphyrin arrays

Long fibers assembled from peptide amphiphiles capable of binding the metalloporphyrin zinc protoporphyrin IX ((PPIX)Zn) have been synthesized. Rational peptide design was employed to generate a peptide, c16-AHL(3)K(3)-CO(2)H, capable of forming a β-sheet structure that propagates into larger fibrous structures. A porphyrin-binding site, a single histidine, was engineered into the peptide sequence in order to bind (PPIX)Zn to provide photophysical functionality. The resulting system indicates control from the molecular level to the macromolecular level with a high order of porphyrin organization. UV/visible and circular dichroism spectroscopies were employed to detail molecular organization, whereas electron microscopy and atomic force microscopy aided in macromolecular characterization. Preliminary picosecond transient absorption data are also reported. Reduced hemin, (PPIX)Fe(II), was also employed to highlight the material's versatility and tunability.     

High density copper nanowire arrays deposition inside ordered titania pores by electrodeposition

Large area and free-standing TiO₂ films was prepared by ultrasonic splitting and a chemical etching step was used to open the closed bottom end of TiO₂ films and yields a high aspect-ratio anodic titanium oxide membrane open at both ends. Ordered Cu nanowire structures were fabricated by a simple electroplating method inside high aspect-ratio anodic titanium oxide membrane. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and the X-ray diffraction (XRD) were employed to characterize the resulting samples. Detailed results and the possible mechanism are presented.     

Transferable ordered ni hollow sphere arrays induced by electrodeposition on colloidal monolayer

We report an electrochemical synthesis of two-dimensionally ordered porous Ni arrays based on polystyrene sphere (PS) colloidal monolayer. The morphology can be controlled from bowl-like to hollow sphere-like structure by changing deposition time under a constant current. Importantly, such ordered Ni arrays on a conducting substrate can be transferred integrally to any other desired substrates, especially onto an insulting substrate or curved surface. The magnetic measurements of the two-dimensional hollow sphere array show the coercivity values of 104 Oe for the applied field parallel to the film, and 87 Oe for the applied field perpendicular to the film, which is larger than those of bulk Ni and hollow Ni submicrometer-sized spheres. The formation of hollow sphere arrays is attributed to preferential nucleation on the interstitial sites between PS in the colloidal monolayer and substrate, and growth along PSs' surface. The transferability of the arrays originates from partial contact between the Ni hollow spheres and substrate. Such novel Ni ordered nanostructured arrays with transferability and high magnetic properties should be useful in applications such as data storage, catalysis, and magnetics.     

Surface-enhanced Raman scattering from ordered Ag nanocluster arrays

We have examined the effect of ordered silver nanocluster substrates on the surface-enhanced Raman spectrum of rhodamine 6G (R6G). Triangular shaped silver nanocluster arrays with order on the approximately 100 mum range were prepared using nanosphere lithography. Direct comparisons of R6G surface-enhanced Raman spectroscopy (SERS) signals between ordered nanocluster regions and amorphous Ag regions prepared under identical deposition conditions provide strong evidence of an electromagnetic field enhancement attributed to the unique nanocluster morphology. We have obtained order of magnitude enhancement factors for both 200 and 90 nm Ag nanocluster SERS substrates relative to Ag films.     

Formation of ordered arrays of oriented polyaniline nanoparticle nanorods

We report the preparation of ordered polyaniline (PANI) nanorod arrays in an aqueous medium. The oriented PANI nanorods (80-400 nm in diameter and 8-15 mum in length) were synthesized in the presence of hydrophilic Allura Red AC (ARAC) as the structure-directing agent and ammonium persulfate as an oxidant in HCl solution. The morphologies of the oriented PANI nanoparticle nanorods were confirmed by scanning electron microscopy (SEM) and transmission electron microscopy images, and the effect of reaction conditions on the morphology of PANI nanostructures was also studied. On the basis of the result obtained from small-angle X-ray scattering, we propose that rodlike micelle arrays of ARAC-aniline are responsible for directing the formation of oriented PANI nanoparticle nanorods. SEM images and the data analysis of static and dynamic light scattering give supportive evidence to the formation of the PANI nanoparticle nanorods by an elongation process. The chemical and electronic structures of the PANI nanorods were also studied by Fourier transform IR and UV-vis spectrometries, respectively.     

Size-dependent orientation growth of large-area ordered Ni nanowire arrays

Large-area ordered Ni nanowire arrays with different diameters have been fabricated by the direct current electrodeposition into the holes of porous anodic alumina membrane. The crystal structure and micrograph of nanowire arrays are characterized by X-ray diffraction, field-emission scanning electron microscopy and high-resolution transmission electron microscopy. The results indicate that the growth orientation of Ni nanowires turns from [110] to [111] direction with increasing diameters of nanowires. The mechanism of the growth was discussed in terms of interface energy minimum principle. The size-dependent orientation of Ni nanowire arrays has the important significance for the design and control of nanostructures.     

Self-assembly of 10-microm-sized objects into ordered three-dimensional arrays

This paper describes the self-assembly of small objects--polyhedral metal plates with largest dimensions of 10 to 30 microm--into highly ordered, three-dimensional arrays. The plates were fabricated using photolithography and electrodeposition techniques, and the faces of the plates were functionalized to be hydrophobic or hydrophilic using self-assembled monolayers (SAMs). Self-assembly occurs in water through capillary interactions between thin films of a hydrophobic liquid (a liquid prepolymer adhesive) coated onto the hydrophobic faces of the plates; coalescence of the adhesive films reduces the interfacial free energy of the system and drives self-assembly. By altering the size and surface-patterning of the plates, the external morphologies of the aggregates were varied. Curing the adhesive furnished mechanically stable aggregates that were characterized by scanning electron microscopy (SEM). For assemblies formed by plates partially composed of a sacrificial material, a subsequent etching step furnished fully open, three-dimensional microstructures. This work validates the use of capillary interactions for three-dimensional mesoscale self-assembly in the 10-microm-size regime and opens new avenues for the fabrication of complex, three-dimensional microscructures.     

Self-assembled two-dimensional ordered arrays of tripod-type molecules on graphite

Tripod-type molecules with long alkyl chains, 1,1,1-tris(4-alkoxyphenyl)ethanes with octadecyloxy or docosyloxy chains, self-assemble into two-dimensional crystallites on drop-casting onto the surface of highly oriented pyrolytic graphite. In the two-dimensional crystalline domain, the molecules are organized in a mortise-and-tenon motif, as revealed by scanning tunneling microscopy. The time evolution of the crystallite formation has been followed by the dynamic force mode atomic force microscopy. The tripods may be used as a basis for the extension of a two-dimensional order into three-dimensional molecular architectures.     

Electrochemical characterization of ordered arrays of metallo-porphyrins in aqueous solution

Metallated meso-tetrakis(N-methyl-4-pyridyl)porphyrin (MTMPyP) and 5,11,17,23-tetrasulfonato-25,26,27,28-tetrakis-(hydroxylcarbonylmethoxy)-calix[4]arene (C(4)TsTc) were used as key components for building up discrete supramolecular entities starting from the formation of the template species MTMPyP:C(4)TsTc (1?:?4, M = Cu, Zn). The stepwise addition of further amount of porphyrin allows the facile non-covalent synthesis of discrete supramolecular entities (2?:?4 and 3?:?4) which can be built up just by programming the right stoichiometric addition of the proper porphyrin. The redox potentials of these supramolecular complexes in aqueous media, as well as those of the parent metalloporphyrins, have been characterized by using square wave voltammetry technique. The use of the simulation procedure leads us to establish the electrochemical steps involved in the redox processes for each supramolecular species, evidencing multistep electron reductions which were not experimentally resolved clearly because of their closeness. The most striking result is that the electrochemistry of each of these supramolecular complexes is different from that of the parent components. This "anomalous" behavior can be explained only considering each of these supramolecular complexes as a unique entity, in which such an internal electronic communication might occur. The formation of the 1?:?4 supramolecular complex produces a negative shift as to the metallated porphyrin redox potentials of about 30 mV. In the case of 2?:?4 and 3?:?4 species, the redox potentials progressively shifts towards more positive values by about 10-15 mV for each complexation step.     

Growth and photoelectrochemical properties of ordered CuInS2 nanorod arrays

CuInS(2) nanorod array structures are synthesized via a template-free and non-vacuum route for the first time. The obtained CuInS(2) thin films show promising conversion efficiency in a two-electrode photoelectrochemical cell.     

Magnetic field induced assembly of highly ordered two-dimensional particle arrays

Suspended magnetic beads are exposed to an external homogeneous magnetic field which rotates around the axis perpendicular to the field direction. Because of dipolar interactions, magnetic beads assemble in highly ordered two-dimensional hexagonal arrays perpendicular to the rotation axis. By continuous provision of the particle concentration, the growth modes of two-dimensional particle clusters and monolayers are observed. The structure of the resulting assembled objects is analyzed for different field frequencies and particle concentrations. We identify dynamic processes which enhance stability and reduce lattice distortions and, thus, allow for the application of these particle agglomerations as dynamic components in lab-on-a-chip technologies.     

The molecularly controlled synthesis of ordered bi-dimensional C60 arrays

Much of the research effort concerning the nanoscopic properties of clays has focused on its mechanical applications, for example, as nanofillers for polymer reinforcement. To broaden the horizon of what is possible by exploiting the richness of clays in nanoscience, herein we report a bottom-up approach for the production of hybrid materials in which clays act as the structure-directing interface and reaction media. This new method, which combines self-assembly with the Langmuir-Schaefer technique, uses the clay nanosheets as a template for the grafting of C(60) into a bi-dimensional array, and allows for perfect layer-by-layer growth with control at the molecular level. In contrast to the more-common growth of C(60) arrays through nanopatterning, our approach can be performed under atmospheric conditions, can be upscaled to areas of tenths of cm(2), and can be applied to almost any hydrophobic substrate. Herein, we report a detailed study of this approach by using temperature-dependent X-ray diffraction, spectroscopic measurements, and STM.     

Tailoring ordered taper-nanopore arrays by combined nanosphere self-assembling, imprinting, anodizing and etching

We report a simple and effective method for tailoring ordered three-dimensional alumina taper-nanopore arrays, dispensing with any unavailable and expensive top-down equipment.     

Conductive polymers as a new type of thermoelectric material

Thermoelectric properties were investigated for the films of electrically conductive doped polyanilines. The thermoelectric performance, evaluated by thermoelectric figure-of-merit (ZT = T (S² σ) / κ), of various protonic acid-doped polyaniline bulk films was found to depend on the electrical conductivity σ of the film. Thus, the higher the electrical conductivity, the higher the figure-of-merit is, because the thermal conductivity κ of polyaniline films does not depend on the electrical conductivity. Among the conductive bulk films of polyaniline, the highest figure-of-merit (ZT = 1 × 10⁻⁴) was observed for (±)-10-camphorsulfonic acid (CSA)-doped polyaniline in an emeraldine form (σ - 188 S cm⁻¹) at room temperature. The multilayered film, composed of electrically insulating emeraldine base layers and electrically conducting CSA-doped emeraldine salt layers, exhibited 6 times higher ZT at 300 K than that of a bulk film of CAS-doped polyaniline, showing the highest ZT value of 1.1 × 10⁻² at 423 K. Stretching of the CAS-doped polyaniline film also increased the figure-of-merit of doped polyaniline films along the direction of the stretching.