Advanced Materials

Cover image for Vol. 17 Issue 1

January, 2005

Volume 17, Issue 1

Pages 3–130

    1. Cover Picture: Nanostructured Electrodes and the Low-Temperature Performance of Li-Ion Batteries (Adv. Mater. 1/2005)

      C. R. Sides and C. R. Martin

      Article first published online: 18 JAN 2005 | DOI: 10.1002/adma.200590003

      Template-synthesized V2O5 nanostructured electrodes (see Figure and cover) are used as tools for fundamental investigations into the poor low-temperature performance of Li-ion batteries. The electrodes consisted of nanofibers of V2O5, and by controlling the dimensions of the nanofibers it has been determined that the rate-limiting factor at low temperatures is the concentration polarization of the Li ion in the electrode material.

    2. Inside Front Cover: An Ultraviolet Organic Thin-Film Solid-State Laser for Biomarker Applications (Adv. Mater. 1/2005)

      D. Schneider, T. Rabe, T. Riedl, T. Dobbertin, M. Kröger, E. Becker, H.-H. Johannes, W. Kowalsky, T. Weimann, J. Wang, P. Hinze, A. Gerhard, P. Stössel and H. Vestweber

      Article first published online: 18 JAN 2005 | DOI: 10.1002/adma.200590004

      A thin-film, organic solid-state laser operating in the ultraviolet wavelength region is fabricated using a novel spiro-linked material as an active organic layer in an optically pumped distributed feedback (DFB) structure. The laser could be tuned between 377.7 nm and 395 nm by varying the grating period of the substrate and was utilized as the excitation source for solutions containing biomarker fluorescent dyes (see Figure and inside cover).

    3. Contents: Adv. Mater. 1/2005 (pages 3–11)

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200590002

    4. Guide for Authors Adv. Mater. 1/2005 (pages 14–15)

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200590001

    5. Covalent Surface Chemistry of Single-Walled Carbon Nanotubes (pages 17–29)

      S. Banerjee, T. Hemraj-Benny and S. S. Wong

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200401340

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      Single-walled carbon nanotubes are now considered chemical reagents in their own right. Understanding the reactivity of carbon nanotubes will lead to manipulation of their unique properties in a predictable manner. In this review, reactions leading to functionalization of carbon nanotubes at their ends, at defect sites, and along their sidewalls are discussed with the goal of creating functional nanomaterials with possible device applications and of generating nanoscale hierarchical architectures and assemblies.

    6. An Ultraviolet Organic Thin-Film Solid-State Laser for Biomarker Applications (pages 31–34)

      D. Schneider, T. Rabe, T. Riedl, T. Dobbertin, M. Kröger, E. Becker, H.-H. Johannes, W. Kowalsky, T. Weimann, J. Wang, P. Hinze, A. Gerhard, P. Stössel and H. Vestweber

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400570

      Thumbnail image of graphical abstract

      A thin-film, organic solid-state laser operating in the ultraviolet wavelength region is fabricated using a novel spiro-linked material as an active organic layer in an optically pumped distributed feedback (DFB) structure. The laser could be tuned between 377.7 nm and 395 nm by varying the grating period of the substrate and was utilized as the excitation source for solutions containing biomarker fluorescent dyes (see Figure and inside cover).

    7. Bright White Organic Light-Emitting Devices from a Single Active Molecular Material (pages 34–39)

      M. Mazzeo, V. Vitale, F. Della Sala, M. Anni, G. Barbarella, L. Favaretto, G. Sotgiu, R. Cingolani and G. Gigli

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400670

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      Bright, balanced white-light electroluminescence has been achieved from a single active oligothiophene compound. White light is created by the superposition of a broad blue–green-light emission originating from the single molecule and a red-shifted narrow peak due to dimer formation. These results open the way to the fabrication of novel, low-cost white-light-emitting devices with a single molecular material as the active compound.

    8. Photolithographic Patterning of Ring-Opening Metathesis Catalysts on Silicon (pages 39–42)

      R. F. Harris, M. J. Ricci, R. A. Farrer, J. Praino, S. J. Miller, B. E. A. Saleh, M. C. Teich and J. T. Fourkas

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400311

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      Ruthenium-based metathesis catalysts have been successfully covalently bound to a thermal oxide layer on a Si(100) wafer. Selective inactivation of the catalyst is achieved via exposure to UV light using standard photolithographic techniques. Subsequent exposure of the wafer to a suitable monomer results in the formation of a patterned polymeric film that is covalently attached to the oxide layer (see Figure).

    9. Three-Dimensionally Oriented Aggregation of a Few Hundred Nanoparticles into Monocrystalline Architectures (pages 42–47)

      Z. Zhang, H. Sun, X. Shao, D. Li, H. Yu and M. Han

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400401

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      Three-dimensional nanoarchitectures (see Figure) are formed by the oriented aggregation of CuO nanoparticles. One-dimensional orientation in the early stages of aggregation (in the [001] plane) of CuO nanoparticles is followed by formation of single-crystalline nanostructures consisting of hundreds of oriented nanoparticles.

    10. Large-Scale Design of Cubic Ia3d Mesoporous Silica Monoliths with High Order, Controlled Pores, and Hydrothermal Stability (pages 47–53)

      S. A. El-Safty, T. Hanaoka and F. Mizukami

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200401317

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      Gyroidal cubic Ia3d silica monoliths (see Figure) with controlled pores of 8–10 nm diameter, thick-walled framework up to 17 nm, and highly uniform mesoporosity have been fabricated using a simple strategy. Such structural features are likely to expand the industrial applications of these monoliths.

    11. Weakly Ferromagnetic Ordered Mesoporous Co3O4 Synthesized by Nanocasting from Vinyl-Functionalized Cubic Ia3d Mesoporous Silica (pages 53–56)

      Y. Wang, C.-M. Yang, W. Schmidt, B. Spliethoff, E. Bill and F. Schüth

      Article first published online: 22 NOV 2004 | DOI: 10.1002/adma.200400777

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      Ordered, mesoporous cobalt oxide was synthesized via a nanocasting pathway from organically modified large-pore Ia3d silica. A replica structure could be obtained, which shows weak magnetic ordering at low temperatures due to the small size of the individual Co3O4 domains forming the mesostructure.

    12. Orientation-Controlled Growth of Single-Crystal Silicon-Nanowire Arrays (pages 56–61)

      S. Ge, K. Jiang, X. Lu, Y. Chen, R. Wang and S. Fan

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400474

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      Silicon nanowire arrays on silicon substrates can be synthesized with precise orientation depending on the crystal orientation of the substrate using a vapor–liquid–solid epitaxial growth mechanism. The projections of the as-grown arrays form rectangular networks on silicon (100) substrates (see Figure), parallel straight lines on silicon (110) substrates, and triangular networks on silicon (111) substrates.

    13. Anatase and Rutile TiO2 Macrocellular Foams: Air–Liquid Foaming Sol–Gel Process Towards Controlling Cell Sizes, Morphologies, and Topologies (pages 62–66)

      F. Carn, A. Colin, M.-F. Achard, H. Deleuze, C. Sanchez and R. Backov

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200401080

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      Titania foams (see Figure) can be produced using a non-static air–liquid foaming sol–gel process where nitrogen is bubbled through a mixture of a surfactant and a sol–gel precursor. Either anatase or rutile phase mesoporous titania foams are produced upon thermal treatment. Macroscopic cell morphologies can be tuned by changing the air-to-liquid-foam ratios and the size of the nitrogen bubbles, while wall topologies can be varied by changing surfactant.

    14. A Hybrid Planar–Mixed Molecular Heterojunction Photovoltaic Cell (pages 66–71)

      J. Xue, B. P. Rand, S. Uchida and S. R. Forrest

      Article first published online: 25 NOV 2004 | DOI: 10.1002/adma.200400617

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      An organic hybrid planar-mixed molecular heterojunction photovoltaic cell, whose photoactive region consists of a mixed layer of donor and acceptor molecules sandwiched between homogeneous donor and acceptor layers, is demonstrated. A power conversion efficiency of (5.0 ± 0.3) % under 1 sun AM1.5G solar illumination is achieved. The cell exhibits a low resistance to charge transport and a high exciton-diffusion efficiency.

    15. Template Synthesis of Sc@C82(I) Nanowires and Nanotubes at Room Temperature (pages 71–73)

      C.-J. Li, Y.-G. Guo, B.-S. Li, C.-R. Wang, L.-J. Wan and C.-L. Bai

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400155

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      Metallofullerene-based nanowire and nanotube arrays are fabricated for the first time using a technique that allows the diameter, length, and morphology of the non-crystalline Sc@C82 nanostructures to be controlled by adjusting the experimental conditions. The Figure shows the geometrical structure of Sc@C82.

    16. Synthesis of SiC Ceramics by the Carbothermal Reduction of Mineralized Wood with Silica (pages 73–77)

      Y. Shin, C. Wang and G. J. Exarhos

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400371

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      Ordered wood cellular structures are used for the synthesis of hierarchical SiC via mineralization with silica followed by carbothermal reduction in argon.

    17. Graphite Nanoplatelet Reinforcement of Electrospun Polyacrylonitrile Nanofibers (pages 77–80)

      J. J. Mack, L. M. Viculis, A. Ali, R. Luoh, G. Yang, H. T. Hahn, F. K. Ko and R. B. Kaner

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400133

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      Thin graphite nanoplatelets synthesized by an intercalation/exfoliation process are incorporated into a polymer fiber matrix by an electrospinning process, creating ultrafine nanocomposite fibrils (see Figure). Uniform nanofibers of average diameter 300 nm show a modest increase in thermal stability with increasing weight percentage of graphite nanoplatelets. The mechanical properties of the fibrils are examined, and the normalized Young's modulus is found to increase two-fold upon addition of 4 wt.-% graphite nanoplatelets.

    18. Coordination Compound Molecular Sieve Membranes (pages 80–84)

      J. Won, J. S. Seo, J. H. Kim, H. S. Kim, Y. S. Kang, S.-J. Kim, Y. Kim and J. Jegal

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400447

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      Highly selective molecular sieve composite membranes have been prepared using dispersions of porous coordination compounds confined within amorphous glassy polysulfone. This new approach is a promising method for fabricating organic molecular sieve composite membranes with tailor-made structures and pore sizes. The organic molecular sieves exhibit enhanced selectivity for H2 over CH4 (approximately 200 at 5 wt.-% loading).

    19. Toughness of Spider Silk at High and Low Temperatures (pages 84–88)

      Y. Yang, X. Chen, Z. Shao, P. Zhou, D. Porter, D. P. Knight and F. Vollrath

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400344

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      The toughness of the major ampullate silk of spiders is shown to increase at low temperatures, unlike synthetic fibers. This temperature dependence of the mechanical properties of spider silk, together with other remarkable properties, demonstrates the potential usefulness of such a super-fiber in harsh environments. The Figure shows a single fiber of Nephila edulis spider silk fractured in liquid nitrogen.

    20. Effects of Carbon Nanotubes on Grain Boundary Sliding in Zirconia Polycrystals (pages 88–91)

      M. Daraktchiev, B. Van de Moortèle, R. Schaller, E. Couteau and L. Forró

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400598

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      Introducing carbon nanotubes into zirconia is shown to drastically reduce grain boundary sliding and consequently mechanical loss at high temperatures. The nanotubes are observed at the grain boundaries by high-resolution transmission electron microscopy (see Figure) and are related to the reduction of superplastic flow through the boundaries, which should improve creep resistance.

    21. Near-Infrared-Electroluminescent Light-Emitting Planar Optical Sources Based on Gallium Nitride Doped with Rare Earths (pages 91–96)

      J. H. Kim and P. H. Holloway

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200306402

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      Strong near-infrared (NIR) electroluminescent emission at wavelengths used in telecommunication optical fibers was produced from rare-earth-doped GaN semiconductors in thin-metal-film/semiconductor/insulator/metal structures (see Figure). Strong near-infrared emission at wavelengths of 800 nm, 1082 nm, and 1550 nm has been demonstrated at room temperature with the trivalent thulium-, neodymium-, or erbium-doped GaN devices, respectively.

    22. Large Electro-optic Kerr Effect in Polymer-Stabilized Liquid-Crystalline Blue Phases (pages 96–98)

      Y. Hisakado, H. Kikuchi, T. Nagamura and T. Kajiyama

      Article first published online: 20 OCT 2004 | DOI: 10.1002/adma.200400639

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      A polymer-stabilized liquid-crystal blue phase with a Kerr constant 170 times larger than that of nitrobenzene is shown to be capable of microsecond electro-optical switching over a wide temperature range in flat Kerr cells, without need for additional surface processing to generate alignment. The Figure shows a polarizing optical micrograph, under crossed polarizers, of an in-plane switched Kerr cell containing the polymer-stabilized blue phase.

    23. Three-Dimensionally Ordered Mesoporous Molecular-Sieve Films as Solid Superacid Photocatalysts (pages 99–102)

      X. Wang, J. C. Yu, Y. Hou and X. Fu

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400884

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      Mesoporous solid superacid molecular sieve films have been prepared (see Figure) and used as photocatalysts. The new class of superacid possesses large surface area, uniform pore size, and accessible 3D mesoporous architecture. These are attractive properties for catalytic or photocatalytic applications.

    24. Synthesis and Crystallization of Monodisperse Spherical Colloids of Amorphous Selenium (pages 102–106)

      U. Jeong and Y. Xia

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400498

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      Monodisperse amorphous-selenium spherical colloids (see Figure) have been synthesized in large quantities by reducing selenious acid with hydrazine in ethylene glycol. The diameters of these colloids could be controlled in the range of 90–420 nm by adjusting the molar ratio between selenious acid and hydrazine. The as-obtained colloids could be readily crystallized into long-range-ordered three-dimensional lattices with well-defined Bragg-diffraction peaks.

    25. Layered Double Hydroxide Surface Modified with (3-aminopropyl)triethoxysilane by Covalent Bonding (pages 106–109)

      A.-Y. Park, H. Kwon, A. J. Woo and S.-J. Kim

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400135

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      Interlayer surfaces of layered double hydroxide (LDH) have been functionalized with amine moieties by condensation between the hydroxyl groups and (3-aminopropyl)triethoxysilane (APS) molecules via the covalent oxane bonds M-O-Si (M=Zn and Cr) (see Figure). Since the galleries of the modified LDHs have a hydrophobic field, various functional molecules such as enzymes, catalysts, and organic molecules can be incorporated between the LDH layers.

    26. Growth and Field Emission of Hierarchical Single-Crystalline Wurtzite AlN Nanoarchitectures (pages 110–114)

      L.-W. Yin, Y. Bando, Y.-C. Zhu, M.-S. Li, Y.-B. Li and D. Golberg

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400504

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      Hierarchical single-crystalline AlN nanocombs were self-assembled through a chemical-vapor transport and condensation process. The wurtzite AlN nanoarchitectures are composed of core stems along the <0001> direction and comb-like nanotips growing perpendicularly out from both sides of the stems along the <01�10> direction (see Figure). Low-threshold field emission could be obtained from the nanostructures, with potential applications in field-emission displays and microvacuum tubes for microwave amplifiers.

    27. Diameter-Controlled Synthesis of Silicon Nanowires Using Nanoporous Alumina Membranes (pages 114–117)

      T. E. Bogart, S. Dey, K.-K. Lew, S. E. Mohney and J. M. Redwing

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400373

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      The use of nanoporous alumina membranes to control the diameter of silicon nanowires synthesized by vapor–liquid–solid growth is demonstrated. An increase in nanowire diameter was observed when the nanowires grew out from the top surface of the membrane (see Figure). The diameter increase was attributed to a change in the shape of the Au–Si liquid alloy when the nanowires emerged from the membrane surface.

    28. Thermogelling Multiblock Poloxamer Aqueous Solutions with Closed-Loop Sol–Gel–Sol Transitions on Increasing pH (pages 118–120)

      J. M. Suh, S. J. Bae and B. Jeong

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400905

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      A closed-loop sol–gel–sol transition is reported for aqueous solutions of a multiblock polyoxamer. The combination of ionizable carboxylic acid groups and water-soluble poly(ethylene glycol) units balance each other to form a gel phase between pH 4 and 6 (see Figure).

    29. A Novel Route to Three-Dimensionally Ordered Macroporous Polymers by Electron Irradiation of Polymer Colloids (pages 120–125)

      S. O. Cho, H. Y. Jun and S. K. Ahn

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400376

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      A novel method for synthesizing ordered macroporous polymers is presented. Simply irradiating an electron beam onto colloidal polymer crystals generates regularly ordered macroporous polymers. No post-treatment is required for the formation of porous polymers. In addition, arbitrarily shaped two- and three-dimensional macroporous polymers of tunable pore sizes are fabricated via the electron-irradiation method.

    30. Nanostructured Electrodes and the Low-Temperature Performance of Li-Ion Batteries (pages 125–128)

      C. R. Sides and C. R. Martin

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200400517

      Thumbnail image of graphical abstract

      Template-synthesized V2O5 nanostructured electrodes (see Figure and cover) are used as tools for fundamental investigations into the poor low-temperature performance of Li-ion batteries. The electrodes consisted of nanofibers of V2O5, and by controlling the dimensions of the nanofibers it has been determined that the rate-limiting factor at low temperatures is the concentration polarization of the Li ion in the electrode material.

    31. Author Index and Subject Index Adv. Mater. 1/2005 (pages 129–130)

      Article first published online: 13 JAN 2005 | DOI: 10.1002/adma.200590000

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