Advanced Functional Materials

Cover image for Vol. 22 Issue 15

August 7, 2012

Volume 22, Issue 15

Pages 3097–3314

  1. Cover Picture

    1. Top of page
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    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Full Papers
    8. Frontispiece
    9. Full Papers
    1. Liquid Crystals: Reversible Fragmentation and Self-Assembling of Nematic Liquid Crystal Droplets on Functionalized Pyroelectric Substrates (Adv. Funct. Mater. 15/2012) (page 3097)

      Francesco Merola, Simonetta Grilli, Sara Coppola, Veronica Vespini, Sergio De Nicola, Pasquale Maddalena, Cosimo Carfagna and Pietro Ferraro

      Article first published online: 1 AUG 2012 | DOI: 10.1002/adfm.201290090

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      Pico-femtoliter nematic liquid crystal droplets are fragmented on a functionalized lithium niobate substrate covered with polydimethylsiloxane (PDMS) circular microstructures. On page 3267, Francesco Merola and co-workers report that the droplets move and assemble themselves outside or inside the structures, driven by electric field lines that are generated by the pyroelectric effect.

  2. Inside Front Cover

    1. Top of page
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    3. Inside Front Cover
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    5. Masthead
    6. Contents
    7. Full Papers
    8. Frontispiece
    9. Full Papers
    1. Thin Films: Growth of Transparent and Conductive Polycrystalline (0001)-ZnO Films on Glass Substrates Under Low-Temperature Hydrothermal Conditions (Adv. Funct. Mater. 15/2012) (page 3098)

      Matejka Podlogar, Jacob J. Richardson, Damjan Vengust, Nina Daneu, Zoran Samardžija, Slavko Bernik and Aleksander Rečnik

      Article first published online: 1 AUG 2012 | DOI: 10.1002/adfm.201290091

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      In a race to find alternatives for indium tin oxide (ITO) in flat panel display technology, new replacement materials are being extensively investigated. As reported by Aleksander Rečnik and co-workers on page 3136, the basic principles of crystal growth under geometrically constrained conditions can be exploited to manufacture highly transparent and conductive ZnO films on glass. The image was recorded using a JEOL JSM-7600F microscope by Matejka Podlogar and graphically designed by Aljaž Iveković.

  3. Back Cover

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    5. Masthead
    6. Contents
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    1. Optoelectronic Devices: CNTs in Optoelectronic Devices: New Structural and Photophysical Insights on Porphyrin-DWCNTs Hybrid Materials (Adv. Funct. Mater. 15/2012) (page 3315)

      Claudia Aurisicchio, Riccardo Marega, Valentina Corvaglia, John Mohanraj, Romain Delamare, Dana Alina Vlad, Cristian Kusko, Constantin Augustin Dutu, Andrea Minoia, Gaëlle Deshayes, Olivier Coulembier, Sorin Melinte, Philippe Dubois, Roberto Lazzaroni, Nicola Armaroli and Davide Bonifazi

      Article first published online: 1 AUG 2012 | DOI: 10.1002/adfm.201290092

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      On page 3209, Sorin Melinte, Philippe Dubois, Roberto Lazzaroni, Nicola Armaroli, and Davide Bonifazi, and co-workers present new insights into the structural and photophysical properties of porphyrin—double-walled carbon nanotube (DWCNT) hybrid materials. Contrary to previous observations in solution, the spectral features of porphyrin—nanotube derivatives recorded in the solid state show the presence J- and H-type aggregates that influence the performance of optoelectronic devices. A covalent porphyrin—nanotube hybrid promotes J-type, head-to-tale, aggregation whereas the non-covalent hybrid exhibits typical face-to-face H-type assembly.

  4. Masthead

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    1. Masthead: (Adv. Funct. Mater. 15/2012)

      Article first published online: 1 AUG 2012 | DOI: 10.1002/adfm.201290093

  5. Contents

    1. Top of page
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    3. Inside Front Cover
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    6. Contents
    7. Full Papers
    8. Frontispiece
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  6. Full Papers

    1. Top of page
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    1. Conjugated Polymer Based Nanoparticles as Dual-Modal Probes for Targeted In Vivo Fluorescence and Magnetic Resonance Imaging (pages 3107–3115)

      Kai Li, Dan Ding, Da Huo, Kan-Yi Pu, Ngo Nguyen Phuong Thao, Yong Hu, Zhi Li and Bin Liu

      Article first published online: 30 APR 2012 | DOI: 10.1002/adfm.201102234

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      Conjugated polymer based nanoparticles as fluorescent-magnetic probes with targeting ability to folate-receptor-overexpressed cancer cells is reported. In vivo far-red/near-infrared fluorescence and magnetic resonance imaging studies suggest that the conjugated polymer based dual-modal imaging probes hold great promise in advanced bioimaging applications.

    2. An Elastomeric Poly(Thiophene-EDOT) Composite with a Dynamically Variable Permeability Towards Organic and Water Vapors (pages 3116–3127)

      Brett D. Martin, Gusphyl A. Justin, Martin H. Moore, Jawad Naciri, Theresa Mazure, Brian J. Melde, Rhonda M. Stroud and Banahalli Ratna

      Article first published online: 24 APR 2012 | DOI: 10.1002/adfm.201102237

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      An interpenetrating polymer network (IPN) with molecular tethers can be reversibly switched between two conducting states by the application of a small voltage in the absence of standard liquid electrolyte. The switching causes the nanoporosity of the IPN to change, thus the IPN is able to adopt an “open” state and a “closed” state. The diffusivities of vapor molecules are strongly influenced by the changes in nanoporosity.

    3. Sonochemical Activation of Al/Ni Hydrogenation Catalyst (pages 3128–3135)

      Jana Dulle, Silke Nemeth, Ekaterina V. Skorb, Torsten Irrgang, Jürgen Senker, Rhett Kempe, Andreas Fery and Daria V. Andreeva

      Article first published online: 30 APR 2012 | DOI: 10.1002/adfm.201200437

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      Sonochemical activation of Al/Ni particles results in nanostructuring of initial Al/Ni alloy and the formation of an effective and reusable catalyst for the hydrogenation reactions. This catalyst can be stored and handled under ambient conditions, in comparison to traditional Raney Ni catalysts. The catalyst is fully characterized and catalytic experiments are carried out.

    4. Growth of Transparent and Conductive Polycrystalline (0001)-ZnO Films on Glass Substrates Under Low-Temperature Hydrothermal Conditions (pages 3136–3145)

      Matejka Podlogar, Jacob J. Richardson, Damjan Vengust, Nina Daneu, Zoran Samardžija, Slavko Bernik and Aleksander Rečnik

      Article first published online: 30 APR 2012 | DOI: 10.1002/adfm.201200214

      Thumbnail image of graphical abstract

      In a race to find alternatives to indium-tin-oxide (ITO) in flat panel display technology, replacement materials are extensively investigated. The basic principles of crystal growth under geometrically constrained conditions are exploited to manufacture highly transparent (82%) and conductive (100 Ω sq−1) ZnO films on inexpensive glass substrates.

    5. The Impact of Carrier Transport Confinement on the Energy Transfer Between InGaN/GaN Quantum-Well Nanorods and Colloidal Nanocrystals (pages 3146–3152)

      Bin Jiang, Chunfeng Zhang, Xiaoyong Wang, Min Joo Park, Joon Seop Kwak, Jian Xu, Huichao Zhang, Jiayu Zhang, Fei Xue and Min Xiao

      Article first published online: 3 MAY 2012 | DOI: 10.1002/adfm.201200351

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      Energy transfer between InGaN multiple-quantum-well (MQW) nanorods and semiconductor nanocrystals is studied for white light conversion in a proximal side-wall coupling configuration. The roles of bound excitons and free carriers are identified using temperature-dependent transient spectroscopy. An exceptional contribution of the carrier transport confinement effect to the energy transfer mechanisms is observed.

    6. Layer-Controlled and Wafer-Scale Synthesis of Uniform and High-Quality Graphene Films on a Polycrystalline Nickel Catalyst (pages 3153–3159)

      Youpin Gong, Xuemin Zhang, Guangtong Liu, Liqiong Wu, Xiumei Geng, Mingsheng Long, Xiaohui Cao, Yufen Guo, Weiwei Li, Jianbao Xu, Mengtao Sun, Li Lu and Liwei Liu

      Article first published online: 24 APR 2012 | DOI: 10.1002/adfm.201200388

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      The layer-controlled synthesis of uniform and high-quality graphene films is a challenging task. A novel and viable synthesis of layer-controlled high-quality graphene films on a wafer-scale Ni surface by the sequentially separated steps of gas carburization, hydrogen exposure, and segregation at ambient pressure is developed. The hydrogen exposure plays a critical role in promoting the preferential segregation through reducing carbon content in the Ni.

  7. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Full Papers
    8. Frontispiece
    9. Full Papers
    1. Microfabrication: Honeycomb Structures of Bulk Metallic Glasses (Adv. Funct. Mater. 15/2012) (page 3160)

      Baran Sarac, Jittisa Ketkaew, Dawn Olivia Popnoe and Jan Schroers

      Article first published online: 1 AUG 2012 | DOI: 10.1002/adfm.201290089

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      A combination of lithography and thermoplastic forming allows for the precise fabrication of honeycombs from bulk metallic glass and selective manipulation of its structure. As reported on page 3161 by Jan Schroers and co-workers, the deformation behavior of such honeycombs can be controlled through microstructural design, from brittle to ductile, by changing the length to thickness ratio of the ligaments.

  8. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Full Papers
    8. Frontispiece
    9. Full Papers
    1. Honeycomb Structures of Bulk Metallic Glasses (pages 3161–3169)

      Baran Sarac, Jittisa Ketkaew, Dawn Olivia Popnoe and Jan Schroers

      Article first published online: 23 APR 2012 | DOI: 10.1002/adfm.201200539

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      A combination of lithography and thermoplastic forming allows for the fabrication of honeycombs from bulk metallic glass (BMG) and for the selective manipulation of the structure. The characteristics of the honeycomb, such as ligament length over thickness, are varied and how changes in these characteristics affect properties under uniaxial in-plane compression testing is determined.

    2. Biomimetic Design of Protein Nanomaterials for Hydrophobic Molecular Transport (pages 3170–3180)

      Dongmei Ren, Mercè Dalmau, Arlo Randall, Matthew M. Shindel, Pierre Baldi and Szu-Wen Wang

      Article first published online: 23 APR 2012 | DOI: 10.1002/adfm.201200052

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      A biomimetic strategy that encapsulates organic molecules into a protein nanocapsule by engineering non-native hydrophobicity into the interior of the capsule is demonstrated. These complexes enable delivery of drug molecules to cancer cells. This novel approach may be broadly utilized to attach guest molecules non-covalently to other protein-based materials for molecular transport and has applications in bionanotechnology.

    3. Injectable and Biodegradable Nanohybrid Polymers with Simultaneously Enhanced Stiffness and Toughness for Bone Repair (pages 3181–3190)

      Lei Cai, Jihua Chen, Adam J. Rondinone and Shanfeng Wang

      Article first published online: 24 APR 2012 | DOI: 10.1002/adfm.201200457

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      Novel injectable and photo-crosslinkable poly(propylene fumarate) (PPF)-co-polyhedral oligomeric silsesquioxane (POSS) copolymers are synthesized to improve both stiffness and toughness and to promote biological performance of bone tissue engineering scaffolds. The mechanical properties with the non-monotonic dependence on weight compositions of POSS are correlated with mouse pre-osteoblastic MC3T3-E1 cell attachment, spreading, proliferation, differentiation, and gene expression.

    4. Synthesis and Biophysical Study of Disassembling Nanohybrid Bioconjugates with a Cubic Octasilsesquioxane Core (pages 3191–3201)

      Beatriz Trastoy, Daniel A. Bonsor, M. Eugenia Pérez-Ojeda, M. Luisa Jimeno, Alejandro Méndez-Ardoy, José Manuel García Fernández, Eric J. Sundberg and Jose Luis Chiara

      Article first published online: 24 APR 2012 | DOI: 10.1002/adfm.201200423

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      Polyhedral oligosilsesquioxanes (POSS)-based cubic glycoclusters (glyco-POSS) are readily obtained by “click” chemistry. These nanohybrid bioconjugates slowly disassemble under physiological conditions. The disassembling process offers an important advantage for POSS conjugates over other nanoparticle conjugates intended for in vivo applications in terms of the expected rapid clearance from the body and low toxicity of their organosilane fragments, thus preventing bioaccumulation and saturation of complementary receptors.

    5. Selective Enhancement of Photoluminescence in Filled Single-Walled Carbon Nanotubes (pages 3202–3208)

      Xianjie Liu, Hans Kuzmany, Paola Ayala, Matteo Calvaresi, Francesco Zerbetto and Thomas Pichler

      Article first published online: 23 APR 2012 | DOI: 10.1002/adfm.201200224

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      Organometallic compounds inside single-walled carbon nanotubes can drastically change their properties. Using biocompatible standardized suspensions of pristine, opened, and ferrocene-filled nanotubes, a selective enhancement of the photoluminescence and optical absorption up to a factor of three is observed. This is attributed to a local electron charge transfer from the encapsulated molecules.

    6. CNTs in Optoelectronic Devices: New Structural and Photophysical Insights on Porphyrin-DWCNTs Hybrid Materials (pages 3209–3222)

      Claudia Aurisicchio, Riccardo Marega, Valentina Corvaglia, John Mohanraj, Romain Delamare, Dana Alina Vlad, Cristian Kusko, Constantin Augustin Dutu, Andrea Minoia, Gaëlle Deshayes, Olivier Coulembier, Sorin Melinte, Philippe Dubois, Roberto Lazzaroni, Nicola Armaroli and Davide Bonifazi

      Article first published online: 3 MAY 2012 | DOI: 10.1002/adfm.201102632

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      The synthesis as well as the structural and photophysical properties of porphyrin-double-walled carbon nanotubes (DWCNTs) are comprehensively described. By means of absorption and emission spectroscopies, new insights into the electronic communication existing between CNTs and covalently linked porphyrin molecules are unravelled both in solution and in the solid state.

    7. Strained Interface Defects in Silicon Nanocrystals (pages 3223–3232)

      Benjamin G. Lee, Daniel Hiller, Jun-Wei Luo, Octavi E. Semonin, Matthew C. Beard, Margit Zacharias and Paul Stradins

      Article first published online: 30 APR 2012 | DOI: 10.1002/adfm.201200572

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      Interface defects in silicon nanocrystals strongly affect the photoluminescence (PL) efficiency and optical absorption. Passivation of the nanocrystals nearly eliminates dangling-bond defects, decreasing absorption below the quantum-confined bandgap and enhancing PL efficiency by an order of magnitude. Remaining, unpassivated, non-paramagnetic defects are revealed using photothermal deflection spectroscopy. Theoretical studies attribute these defects to distorted bonds at the nanocrystal surface: Si–Si and bridging Si–O–Si bonds.

    8. Heteroatom-Modulated Switching of Photocatalytic Hydrogen and Oxygen Evolution Preferences of Anatase TiO2 Microspheres (pages 3233–3238)

      Gang Liu, Jian Pan, Lichang Yin, John TS Irvine, Feng Li, Jun Tan, Philip Wormald and Hui-Ming Cheng

      Article first published online: 23 APR 2012 | DOI: 10.1002/adfm.201200414

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      By moving heteroatom boron from the core to the shell of an anatase TiO2 microsphere via thermal diffusion control, the photocatalysis reaction preferences towards hydrogen and oxygen evolution from water splitting can be sensitively switched.

    9. Ellipsoidal Polyaspartamide Polymersomes with Enhanced Cell-Targeting Ability (pages 3239–3246)

      Mei-Hsiu Lai, Jae Hyun Jeong, Ross J. DeVolder, Christopher Brockman, Charles Schroeder and Hyunjoon Kong

      Article first published online: 25 APR 2012 | DOI: 10.1002/adfm.201102664

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      Ellipsoidal polymersomes are made by self-assembly of polyaspartamide substituted with poly(ethylene glycol) (PEG) chains. Further modification of the ellipsoidal polymersomes with peptides containing an Arg-Gly-Asp(RGD) sequence leads to a significant increase in the rate of association with a substrate coated with αvβ3 integrins and also more binding with targeted cells in vitro than their spherical counterparts.

    10. Graphite Oxide as an Olefin Polymerization Carbocatalyst: Applications in Electrochemical Double Layer Capacitors (pages 3247–3253)

      Daniel R. Dreyer and Christopher W. Bielawski

      Article first published online: 27 APR 2012 | DOI: 10.1002/adfm.201103152

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      Graphite oxide (GO) is found to be an efficient heterogeneous catalyst for the polymerization of various olefinic monomers. For example, the polymerization of sodium 4-styrenesulfonate using GO affords composites of the corresponding polymer. After thermal treatment, the composites are fabricated into electrodes for use in electrochemical double layer capacitors. The devices display high specific capacitances and low cell resistances.

    11. Borax-Mediated Formation of Carbon Aerogels from Glucose (pages 3254–3260)

      Tim-Patrick Fellinger, Robin J. White, Maria-Magdalena Titirici and Markus Antonietti

      Article first published online: 23 APR 2012 | DOI: 10.1002/adfm.201102920

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      Hierarchically structured carbon aerogels with high surface areas are produced using only glucose as a carbon precursor. A simple, rapid, efficient, and sustainable hydrothermal approach is presented in which sodium borate (borax) is used as a novel catalyst and complex structure directing agent leading to nanostructured, carbonaceous monoliths that are structurally similar to the well-known sol-gel monoliths made of resorcinol and formaldehyde.

    12. Origin of Enhanced Hole Injection in Inverted Organic Devices with Electron Accepting Interlayer (pages 3261–3266)

      Cephas E. Small, Sai-Wing Tsang, Junji Kido, Shu Kong So and Franky So

      Article first published online: 24 APR 2012 | DOI: 10.1002/adfm.201200185

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      Hole injection is substantially enhanced using 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile (HAT-CN) as a hole-injection layer (HIL) with a top anode. The enhanced hole injection is achieved due to the strong electron accepting nature of the hole-transporting layer HAT-CN molecule and efficient doping at the surface of the hole-transporting layer (HTL). The more efficient top injection contact is due to the stronger doping effect of the HIL.

    13. Reversible Fragmentation and Self-Assembling of Nematic Liquid Crystal Droplets on Functionalized Pyroelectric Substrates (pages 3267–3272)

      Francesco Merola, Simonetta Grilli, Sara Coppola, Veronica Vespini, Sergio De Nicola, Pasquale Maddalena, Cosimo Carfagna and Pietro Ferraro

      Article first published online: 27 APR 2012 | DOI: 10.1002/adfm.201200323

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      The pyroelectric effect is able to drive a reversible fragmentation process in liquid crystal drops, starting from nanoliter drops and obtaining pico/femtoliter droplets. These small droplets are patterned according to the geometry of the substrate and aligned along the electric field lines. Applications such as spatial modulation of the wettability and dynamical optical elements able to switch from a diffuser (fragmentation) state to a microlens array (coalescence state) are foreseen.

    14. Electrochemically Triggered Selective Adsorption of Biotemplated Nanoparticles on Self-Assembled Organometallic Diblock Copolymer Thin Films (pages 3273–3278)

      Jean-Charles Eloi, Sarah E. Ward Jones, Veronika Poór, Mitsuhiro Okuda, Jessica Gwyther and Walther Schwarzacher

      Article first published online: 23 APR 2012 | DOI: 10.1002/adfm.201200210

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      The selective adsorption of the cage protein ferritin onto self-assembled diblock copolymer surfaces is reported. When desired, the adsorption is triggered in situ by changing the potential. Upon this potential change, the minority block, consisting of amorphous polyferrocenylsilane, becomes positively charged. Electrostatic forces are then responsible for the local adsorption of the globally negatively charged ferritin molecules.

    15. New Configuration of Solid-State Neutron Detector Made Possible with Solution-Based Semiconductor Processing (pages 3279–3283)

      Huiqiong Zhou, Nelson E. Coates, Gerardo Hernandez-Sosa and Daniel Moses

      Article first published online: 25 APR 2012 | DOI: 10.1002/adfm.201200097

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      An in situ semiconductor synthesis and film deposition facilitates a novel neutron detector configuration consisting of a host inorganic semiconductor matrix impregnated with a guest neutron sensitizing material. It consists of interpenetrating networks of the host semiconductor nanocrystals and sensitizing guest material that self-assemble during film formation. The detectors show high sensitivity to ionizing radiation and an ability to detecting thermal neutrons.

    16. Electrostatic Self-Assembly Conjugated Polyelectrolyte-Surfactant Complex as an Interlayer for High Performance Polymer Solar Cells (pages 3284–3289)

      Yi-Ming Chang, Rui Zhu, Eric Richard, Chun-Chao Chen, Gang Li and Yang Yang

      Article first published online: 25 APR 2012 | DOI: 10.1002/adfm.201200738

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      A simple method is demonstrated to improve the film-forming properties and air stability of a conjugated polyelectrolyte. Using this complex as a cathode interface layer, a high power conversion efficiency of 4% can be obtained in poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester (P3HT:PCBM) solar cells together with improved stability in air. Moreover, ≈20% performance enhancement can also be achieved when the complex is used to replace calcium metal for low bandgap polymer-based bulk heterojunction (BHJ) systems.

    17. A LiF Nanoparticle-Modified Graphene Electrode for High-Power and High-Energy Lithium Ion Batteries (pages 3290–3297)

      Zhong-Shuai Wu, Lili Xue, Wencai Ren, Feng Li, Lei Wen and Hui-Ming Cheng

      Article first published online: 24 APR 2012 | DOI: 10.1002/adfm.201200534

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      A surface modified strategy is proposed to synthesize LiF nanoparticle-modified graphene as an advanced electrode for high-power and high-energy lithium ion batteries. The crystalline LiF nanoparticles anchored on the graphene surface act as an effective electrode additive to suppress the electrolyte-decomposition reaction, affect the solid electrolyte interphase components, and reduce their thickness. The Li-storage performance is significantly improved at fast charge/discharge rates.

    18. Template-Assisted Synthesis of π-Conjugated Molecular Organic Nanowires in the Sub-100 nm Regime and Device Implications (pages 3298–3306)

      Kazi M. Alam, Abhay P. Singh, Ryan Starko-Bowes, Srikrishna C. Bodepudi and Sandipan Pramanik

      Article first published online: 18 APR 2012 | DOI: 10.1002/adfm.201102967

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      A novel fabrication process that allows growth of nanowires of π-conjugated small-molecular organics (e.g., rubrene, Alq3, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), and fullerene) in sub-100 nm diameter channels of nanoporous anodic alumina template is demonstrated. This process can be extended to synthesize more complex, radially and axially hetero-structured organic nanowires. Structural, compositional, and transport characterizations are performed, highlighting possible device implications.

    19. Highly Concentrated and Conductive Reduced Graphene Oxide Nanosheets by Monovalent Cation–π Interaction: Toward Printed Electronics (pages 3307–3314)

      Seung Yol Jeong, Sung Hun Kim, Joong Tark Han, Hee Jin Jeong, Soo Yeon Jeong and Geon-Woong Lee

      Article first published online: 30 APR 2012 | DOI: 10.1002/adfm.201200242

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      Highly concentrated and conductive reduced graphene oxide (RGO) nanosheets are prepared by introducing monovalent cation–π interactions between Na+ or K+ ions and six-membered sp2 carbons on graphene. Current–voltage characteristics demonstrate the interactions in terms of the presence of n-type doping effect due to the adsorption of cations with high electron mobility (39 cm2 V−1 s−1).

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