Advanced Functional Materials

Cover image for Vol. 21 Issue 13

July 8, 2011

Volume 21, Issue 13

Pages 2385–2598

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    1. Lithium-Ion Batteries: Epitaxial Growth of Branched α-Fe2O3/SnO2 Nano-Heterostructures with Improved Lithium-Ion Battery Performance (Adv. Funct. Mater. 13/2011) (page 2385)

      Weiwei Zhou, Chuanwei Cheng, Jinping Liu, Yee Yan Tay, Jian Jiang, Xingtao Jia, Jixuan Zhang, Hao Gong, Huey Hoon Hng, Ting Yu and Hong Jin Fan

      Article first published online: 1 JUL 2011 | DOI: 10.1002/adfm.201190048

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      Unique branched α-Fe2O3/SnO2 nano-heterostructures with six-fold symmetry are presented by Ting Yu, Hong Jin Fan, and co-workers on page 2439. When used as anode material for lithium-ion batteries, the composite demonstrates superior performance to either of the individual components. The improvement is ascribed to a synergetic effect between the two oxides and the unique feature of the branched structure, which provides an increased specific surface areas.

  2. Inside Front Cover

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    1. Thermoresponsive Capsules: Hybrid Capsules via Self-Assembly of Thermoresponsive and Interfacially Active Bionanoparticle–Polymer Conjugates (Adv. Funct. Mater. 13/2011) (page 2386)

      Nathalie C. Mougin, Patrick van Rijn, Hyunji Park, Axel H. E. Müller and Alexander Böker

      Article first published online: 1 JUL 2011 | DOI: 10.1002/adfm.201190049

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      The image shows a soft capsule prepared from a newly developed protein-polymer hybrid conjugate. On page 2470, Alexander Böker and co-workers report the formation of functional thin layers that are stabilized by cross-linking and allow for the production of very stable soft-matter capsules. In addition to the control gained by the defined structure of proteins, the authors use a thermoresponsive protein (ferriting) that allows for several possible release mechanisms and for the formation of thin responsive layers. Such systems may find application in controlled release processes, for example, drug delivery. (Cover design: P. van Rijn)

  3. Back Cover

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    1. Chemically Controlled Miniature Devices: Microchemomechanical Systems (Adv. Funct. Mater. 13/2011)

      Jatinder S. Randhawa, Kate E. Laflin, Natasha Seelam and David H. Gracias

      Article first published online: 1 JUL 2011 | DOI: 10.1002/adfm.201190053

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      A new class of miniature micromechanical devices that do not utilize electricity but respond to different chemical environments are reviewed by David H. Gracias and coworkers on page 2395. The wireless device shown in the image, for example, opens/closes in response to surface oxidation and reduction. The intellectual motivation to pursue chemically stimulated devices is their wide occurrence in nature. From a practical standpoint, since chemicals can readily diffuse and produce changes over large distances, this approach is especially attractive for very small wireless and autonomous devices. (Image credit: A. Zarafshar and J. Randhawa)

  4. Contents

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    1. Contents: (Adv. Funct. Mater. 13/2011) (pages 2387–2394)

      Article first published online: 1 JUL 2011 | DOI: 10.1002/adfm.201190050

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    1. Microchemomechanical Systems (pages 2395–2410)

      Jatinder S. Randhawa, Kate E. Laflin, Natasha Seelam and David H. Gracias

      Article first published online: 7 JUN 2011 | DOI: 10.1002/adfm.201100482

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      Multilayer lithographic methods are used to integrate chemomechanical thin-film actuators as hinges within larger rigid structures, to fabricate devices analogous to microelectromechanical systems (MEMS). Microchemomechanical systems (MCMS) are a class of integrated, miniaturized devices that are actuated on exposure to specific chemical environments. The MCMS approach is especially attractive in enabling wireless and autonomous devices at small size scales. The image shows a microgripper closing spontaneously around an object, in response to chemical stimuli.

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    1. LITHIUM-ION BATTERIES: Strain Anisotropies and Self-Limiting Capacities in Single-Crystalline 3D Silicon Microstructures: Models for High Energy Density Lithium-Ion Battery Anodes (Adv. Funct. Mater. 13/2011) (page 2411)

      Jason L. Goldman, Brandon R. Long, Andrew A. Gewirth and Ralph G. Nuzzo

      Article first published online: 1 JUL 2011 | DOI: 10.1002/adfm.201190051

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      This false-colored SEM image shows a model high-energy- density lithium-ion battery anode that consists of an array of 3D hierarchically patterned single-crystalline silicon microstructures. Ralph G. Nuzzo and co-workers utilize these model anodes to demonstrate the crystallographic anisotropy of strain evolution on electrochemical intercalation of lithium atoms and self-strain-limited charging of a lithium-ion battery anode.

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    1. Strain Anisotropies and Self-Limiting Capacities in Single-Crystalline 3D Silicon Microstructures: Models for High Energy Density Lithium-Ion Battery Anodes (pages 2412–2422)

      Jason L. Goldman, Brandon R. Long, Andrew A. Gewirth and Ralph G. Nuzzo

      Article first published online: 12 APR 2011 | DOI: 10.1002/adfm.201002487

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      Model single-crystalline silicon systems are used to examine the anisotropies in the evolution of strain during electrochemical lithium intercalation. Quasi 1D, 2D, and 3D design rules passively exploit these anisotropies in order to limit strain on the anode during charge/discharge cycling. Strain-limited charge capacities ranging from 677 mAhg−1 to 2833 mAhg−1 were achieved.

    2. Tunable Low-Field Magnetoresistance in (La0.7Sr0.3MnO3)0.5:(ZnO)0.5 Self-Assembled Vertically Aligned Nanocomposite Thin Films (pages 2423–2429)

      Aiping Chen, Zhenxing Bi, Chen-Fong Tsai, JoonHwan Lee, Qing Su, Xinghang Zhang, Quanxi Jia, Judith L. MacManus-Driscoll and Haiyan Wang

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201002746

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      Self-assembled (La0.7Sr0.3MnO3)0.5:(ZnO)0.5 vertically aligned nanocomposite (VAN) thin films are epitaxially grown on SrTiO3 (001) substrates by pulsed laser deposition (PLD). The unique VAN system with a vertical ferromagnetic–insulating–ferromagnetic struc­­ture exhibits tunable and enhanced low-field magnetoresistance that is associated with the tunable vertical phase boundaries.

    3. Fe3O4 Nanoparticles Confined in Mesocellular Carbon Foam for High Performance Anode Materials for Lithium-Ion Batteries (pages 2430–2438)

      Eunae Kang, Yoon Seok Jung, Andrew S. Cavanagh, Gi-Heon Kim, Steven M. George, Anne C. Dillon, Jin Kon Kim and Jinwoo Lee

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201002576

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      Fe3O4 nanocrystals confined in mesocellular carbon foam (MSU-F-C) exhibit capacities larger than 1000 mA h g−1 at 0.1 A g−1 with excellent cycling performance and rate capability as an anode material for lithium-ion batteries. The combined effect of nanosized Fe3O4, extra pore volume to accommodate volume expansion of Fe3O4, and large three dimensional interconnected mesoporous carbon pores with excellent electronic connectivity accounts for the excellent performance.

    4. Epitaxial Growth of Branched α-Fe2O3/SnO2 Nano-Heterostructures with Improved Lithium-Ion Battery Performance (pages 2439–2445)

      Weiwei Zhou, Chuanwei Cheng, Jinping Liu, Yee Yan Tay, Jian Jiang, Xingtao Jia, Jixuan Zhang, Hao Gong, Huey Hoon Hng, Ting Yu and Hong Jin Fan

      Article first published online: 25 MAR 2011 | DOI: 10.1002/adfm.201100088

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      A unique six-fold-symmetry branched α-Fe2O3/SnO2 nano-heterostructure composed of SnO2 nanowire stems and α-Fe2O3 nanorod branches are prepared by combining a vapour transport deposition and a facile hydrothermal method. As a lithium-ion battery material, the composite exhibits low initial irreversible loss and high reversible capacity in comparison to both single components.

    5. Template-Confined Dewetting Process to Surface Nanopatterns: Fabrication, Structural Tunability, and Structure-Related Properties (pages 2446–2455)

      Shikuan Yang, Feng Xu, Stefan Ostendorp, Gerhard Wilde, Huaping Zhao and Yong Lei

      Article first published online: 2 MAY 2011 | DOI: 10.1002/adfm.201002387

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      Surface nanopatterns are prepared using a template-confined dewetting process with multiple structural controllabilities. Importantly, the size and the composition of the building units in the patterns can be pre-calculated and accurately designed. The features are highly dependent on the annealing parameters. The optical properties can be tailored through structural manipulations of the surface nanopatterns.

    6. Amino Acid Pairing for De Novo Design of Self-Assembling Peptides and Their Drug Delivery Potential (pages 2456–2464)

      Shan-Yu Fung, Hong Yang, Parisa Sadatmousavi, Yuebiao Sheng, Tewodros Mamo, Reyhaneh Nazarian and P. Chen

      Article first published online: 2 MAY 2011 | DOI: 10.1002/adfm.201002497

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      A de novo design principle of amino acid pairing (AAP) to generate new classes of self-assembling peptides is proposed. The AAP assembly utilizes hydrogen bonding, and ionic and hydrophobic interactions among amino acid pairs to form stable nanostructures. Using these three strategies, a short novel self-assembling peptide is constructed. It can form stable nanofibers and shows a potential in stabilizing and delivering the hydrophobic anticancer model drug ellipticine in aqueous solution.

    7. An Electrolyte-Free Fuel Cell Constructed from One Homogenous Layer with Mixed Conductivity (pages 2465–2469)

      Bin Zhu, Rizwan Raza, Ghazanfar Abbas and Manish Singh

      Article first published online: 5 MAY 2011 | DOI: 10.1002/adfm.201002471

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      A break through for fuel-cell research based on new principles. Fuel cells are traditionally based on a three-layer configuration; anode, electrolyte, and cathode, and this leads to a complex structure, not least since the three layers have to be chemically stable and mutually compatible. A new electrolyte-free, single-layer fuel cell represents a radically new approach to fuel-cell research and design. This approach will lead to simpler construction and improved cost-efficiency, and open up new opportunities for fuel cells.

    8. Hybrid Capsules via Self-Assembly of Thermoresponsive and Interfacially Active Bionanoparticle–Polymer Conjugates (pages 2470–2476)

      Nathalie C. Mougin, Patrick van Rijn, Hyunji Park, Axel H. E. Müller and Alexander Böker

      Article first published online: 28 MAR 2011 | DOI: 10.1002/adfm.201002315

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      Modified horse spleen ferritin conjugated with thermoresponsive cross-linkable polymers displays a strong preference for polar/apolar interfaces and is used to form Pickering emulsions. Due to the self-assembly of these protein–polymer conjugates at interfaces, they are close enough to each other to become covalently cross-linked upon UV-irradiation. This stabilization results in the formation of self-assembled soft matter capsules.

    9. Kinetic Monte Carlo Simulations of Anisotropic Lithium Intercalation into LixFePO4 Electrode Nanocrystals (pages 2477–2487)

      Céline Hin

      Article first published online: 10 MAY 2011 | DOI: 10.1002/adfm.201002049

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      The kinetic anisotropy of lithium ion adsorption and lithium absorption for LixFePO4 olivine nanocrystals is simulated and reported. The kinetics depend on the electrolyte/LixFePO4 interface orientation with respect to the far-field ionic flux. As a consequence of these kinetics and a Li miscibility gap in LixFePO4, the morphology of the two-phase evolution also depends on particle geometry and orientation.

    10. Pegylated Composite Nanoparticles Containing Upconverting Phosphors and meso-Tetraphenyl porphine (TPP) for Photodynamic Therapy (pages 2488–2495)

      Jingning Shan, Stephanie J. Budijono, Guohong Hu, Nan Yao, Yibin Kang, Yiguang Ju and Robert K. Prud'homme

      Article first published online: 5 MAY 2011 | DOI: 10.1002/adfm.201002516

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      A kinetically driven self-assembly process successfully produces poly(ethylene glycol)-stabilized composite nanoparticles, which simultaneously encapsulate upconverting phosphors and photosensitizers within the cores. These nanoparticles are capable of producing cytotoxic singlet oxygen upon near-infrared excitation and have potential applications in improved photodynamic cancer therapy, deep tissue imaging and biomarker identification.

  8. Frontispiece

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    1. MULTICOLOR LUMINESCENCE: Heterogeneous Transparent Ultrathin Films with Tunable-Color Luminescence Based on the Assembly of Photoactive Organic Molecules and Layered Double Hydroxides (Adv. Funct. Mater. 13/2011) (page 2496)

      Dongpeng Yan, Jun Lu, Min Wei, Shenghui Qin, Li Chen, Shitong Zhang, David G. Evans and Xue Duan

      Article first published online: 1 JUL 2011 | DOI: 10.1002/adfm.201190052

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      Microscopically, the ordered assembly of the hexagonal layered double hydroxide (LDH) nanosheets and different photoactive molecules can construct ultrathin films with tunable multiple-color (R/G/B and white) luminescence. Examples are presented by Jun Lu, Min Wei, and co-workers. This is similar to, in a macroscopic scenario, the variable-color light emitting from the magical “Watercube” (National Swimming Center in Beijing, China).

  9. Full Papers

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    1. Heterogeneous Transparent Ultrathin Films with Tunable-Color Luminescence Based on the Assembly of Photoactive Organic Molecules and Layered Double Hydroxides (pages 2497–2505)

      Dongpeng Yan, Jun Lu, Min Wei, Shenghui Qin, Li Chen, Shitong Zhang, David G. Evans and Xue Duan

      Article first published online: 4 MAY 2011 | DOI: 10.1002/adfm.201002446

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      Heterogeneous two- (blue/green, blue/orange, red/blue, red/green) and three-color (blue/red/green) light-emitting ultrathin films have been fabricated using different photofunctional molecules and Mg-Al-layered double hydroxide nanosheets as building blocks.

    2. Copper-Based Nanostructured Coatings on Natural Cellulose: Nanocomposites Exhibiting Rapid and Efficient Inhibition of a Multi-Drug Resistant Wound Pathogen, A. baumannii, and Mammalian Cell Biocompatibility In Vitro (pages 2506–2514)

      Nathaniel C. Cady, Jason L. Behnke and Aaron D. Strickland

      Article first published online: 24 MAY 2011 | DOI: 10.1002/adfm.201100123

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      Nanostructured copper coatings on natural cellulose (woven cotton substrate; left) are produced using a layer-by-layer electrostatic self-assembly process. The resulting copper nanoparticle-coated cotton fiber composites exhibit extremely efficient antimicrobial activity against a multi-drug resistant bacterial pathogen through a putative contact-killing mechanism at the nanostructured cotton interface. The substrates exhibit an 8-log reduction in bacterial growth in as little as ten minutes. These unique materials also show mammalian cell biocompatibility as indicated in the confocal fluorescence microscopy image showing healthy mouse fibroblast cells growing in the presence of nanostructured copper-coated cotton substrates after 48 hours.

    3. Array of Single-Walled Carbon Nanotube Intrajunction Devices Fabricated via Type Conversion by Partial Coating with β-Nicotinamide Adenine Dinucleotide (pages 2515–2521)

      Jangyeol Yoon, Jaehyun Park, Junsung Kim, Gyu Tae Kim and Jeong Sook Ha

      Article first published online: 2 MAY 2011 | DOI: 10.1002/adfm.201100265

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      Intratube p–n junctions made of well-aligned pristine and nicotinamide adenine dinucleotide (NADH)-coated single-walled carbon nanotubes (SWCNTs) exhibit gate-dependent rectifying characteristics with low contact resistance and an ideality factor of approximately two. This work shows the easy fabrication of SWCNT intratube p–n-junction devices via growth of well-aligned SWCNTs and type-conversion with NADH coating, which will be widely used as a building block of future nanoelectronic circuits.

    4. Critical Role of Triplet Exciton Interface Trap States in Bilayer Films of NPB and Ir(piq)3 (pages 2522–2526)

      Vygintas Jankus, Chris Winscom and Andrew P. Monkman

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201002262

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      Investigations into triplet transfer in bilayer organic films of NPB and Ir(piq)3 are reported. Experiments and modeling show that transfer between layers having different triplet energy is not always governed by a simple exothermic process. It is proposed that triplets from the donor NPB are trapped at the interface sites and are not always transferred into the bulk states of Ir(piq)3.

    5. Carbon Fiber–Bismaleimide Composites Filled with Nickel-Coated Single-Walled Carbon Nanotubes for Lightning-Strike Protection (pages 2527–2533)

      Divya K. Chakravarthi, Valery N. Khabashesku, Ranji Vaidyanathan, Jeanette Blaine, Shridhar Yarlagadda, David Roseman, Qiang Zeng and Enrique V. Barrera

      Article first published online: 29 APR 2011 | DOI: 10.1002/adfm.201002442

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      Lightning-strike protection: Coating SWNTs with nickel makes them promising candidates for lightning-strike applications. Carbon fiber–bismaleimide composites filled with Ni-SWNTs (A) show enhanced resistance to lightning-strike damage as compared to their baseline counterparts (B) with no Ni-SWNTs. By coating the purified SWNTs with nickel, improved dispersion and surface coverage were obtained which enhanced the electrical conductivity of the composites.

    6. Porous Supramolecularly Templated Optical Resonators Built in 1D Photonic Crystals (pages 2534–2540)

      Nuria Hidalgo, Mauricio E. Calvo, Martín G. Bellino, Galo J. A. A. Soler-Illia and Hernán Míguez

      Article first published online: 5 MAY 2011 | DOI: 10.1002/adfm.201002486

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      Controlled porosity: Photonic multilayers that presents controlled porosity only at the middle-layer level are herein introduced. The optical response of the ensemble shows strong sensitivity to the presence of vapors adsorbed or condensed within the void network, providing a potentially relevant material for gas detection.

    7. High Pseudocapacitance from Ultrathin V2O5 Films Electrodeposited on Self-Standing Carbon-Nanofiber Paper (pages 2541–2547)

      Arunabha Ghosh, Eun Ju Ra, Meihua Jin, Hae-Kyung Jeong, Tae Hyung Kim, Chandan Biswas and Young Hee Lee

      Article first published online: 9 MAY 2011 | DOI: 10.1002/adfm.201002603

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      An ultrathin film of V2O5 is electrodeposited on the surface of carbon nanofibers to obtain a high surface area with an improved electrode conductivity. This provides a high pseudocapacitance of 1308 F g−1 with respect to the effective contribution from the deposited oxide layer. The schematic shows the distribution of V2O5 throughout the nanofiber. The graph shows the dependence of the specific capacitance on the deposited amount of V2O5.

    8. Magnetic/Silica Nanocomposites as Dual-Mode Contrast Agents for Combined Magnetic Resonance Imaging and Ultrasonography (pages 2548–2555)

      Maria Ada Malvindi, Antonio Greco, Francesco Conversano, Albert Figuerola, Maurizio Corti, Marco Bonora, Alessandro Lascialfari, Houshang Amiri Doumari, Marco Moscardini, Roberto Cingolani, Giuseppe Gigli, Sergio Casciaro, Teresa Pellegrino and Andrea Ragusa

      Article first published online: 9 MAY 2011 | DOI: 10.1002/adfm.201100031

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      The synthesis of a range of hybrid nanocomposites based on a core of silica covered by an outer shell of superparamagnetic nanoparticles, either iron oxide or heterodimeric FePt-iron oxide nano­crystals, is presented. The nanocomposites show potential as contrast agents for dual-mode imaging purposes, combining magnetic resonance imaging and ultrasonography.

    9. Layer-by-Layer Growth of Multicomponent Colloidal Crystals Over Large Areas (pages 2556–2563)

      Gurvinder Singh, Saju Pillai, Ayyoob Arpanaei and Peter Kingshott

      Article first published online: 3 MAY 2011 | DOI: 10.1002/adfm.201002716

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      Evaporation driven layer-by-layer self-assembly of different sized colloidal particles yields a variety of well-ordered binary and ternary colloidal crystals depending on the size ratio and volume fraction of the small particles in the suspension. These complex crystals can be grown reproducibly to over a centimeter length scale.

    10. Sub-Micrometer Patterning of Amorphous- and β-Phase in a Crosslinkable Poly(9,9-dioctylfluorene): Dual-Wavelength Lasing from a Mixed-Morphology Device (pages 2564–2570)

      Alexander J. C. Kuehne, Markus Kaiser, Allan R. Mackintosh, Bodo H. Wallikewitz, Dirk Hertel, Richard A. Pethrick and Klaus Meerholz

      Article first published online: 11 MAY 2011 | DOI: 10.1002/adfm.201002553

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      Sub-wavelength patterning of a crosslinkable polyfluorene by electron beam lithography is presented. The previously induced morphology, namely amorphous or β-phase, is frozen-in during crosslinking. This enables subsequent processing of the patterns produced. A double layer DFB grating, resulting in a two-frequency laser in accordance with the two morphologies, is demonstrated.

    11. Influence of Ion Induced Local Coulomb Field and Polarity on Charge Generation and Efficiency in Poly(3-Hexylthiophene)-Based Solid-State Dye-Sensitized Solar Cells (pages 2571–2579)

      Agnese Abrusci, R. Sai Santosh Kumar, Mohammed Al-Hashimi, Martin Heeney, Annamaria Petrozza and Henry J. Snaith

      Article first published online: 10 MAY 2011 | DOI: 10.1002/adfm.201100048

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      The cascade of photophysical events that occurs within the operating device when ions are incorporated in the dye-sensitized solar cells is described. It is demonstrated that the ionic influence on the excited state energy is the primary reason for enhanced charge generation and devices performance.

    12. Time-of-Flight Studies of Electron-Collection Kinetics in Polymer:Fullerene Bulk-Heterojunction Solar Cells (pages 2580–2586)

      Anthony J. Morfa, Alexandre M. Nardes, Sean E. Shaheen, Nikos Kopidakis and Jao van de Lagemaat

      Article first published online: 11 MAY 2011 | DOI: 10.1002/adfm.201100432

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      Transient photoconductivity measurements Schottky solar cells of poly(3-hexylthiophene:[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) at several voltages demonstrate the dependence of charge collection on transit time. The applied bias is controlled, which tunes the depletion layer width, and thus the field-free region. The total charge collected versus the average transit time is then calculated. First-order charge kinetics are demonstrated.

      Corrected by:

      Correction: Correction: Time-of-Flight Studies of Electron-Collection Kinetics in Polymer:Fullerene Bulk-Heterojunction Solar Cells

      Vol. 21, Issue 22, 4210, Article first published online: 16 NOV 2011

    13. Ultrasmooth Gold Films via Pulsed Laser Deposition (pages 2587–2592)

      Doris K. T. Ng, Bipin S. Bhola, Reuben M. Bakker and Seng-Tiong Ho

      Article first published online: 17 MAY 2011 | DOI: 10.1002/adfm.201002303

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      A simple, one step technique for depositing ultrasmooth gold films using pulsed laser deposition is demonstrated. The smoothest films have a root-mean-square roughness of 0.17 nm (including the silicon substrate roughness of 0.11 nm). This is the best result reported so far for a single step deposition of gold and points towards low-loss gold films for surface plasmon applications.

    14. E-Field Control of Exchange Bias and Deterministic Magnetization Switching in AFM/FM/FE Multiferroic Heterostructures (pages 2593–2598)

      Ming Liu, Jing Lou, Shandong Li and Nian X. Sun

      Article first published online: 17 MAY 2011 | DOI: 10.1002/adfm.201002485

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      Electric field modulating exchange bias and near 180° dynamic magnetization switching at room temperature were demonstrated in novel AFM (antiferromagnetic)/FM(ferromagnetic)/FE(ferroelectric) multiferroic hetero­structures of FeMn/Ni80Fe20/FeGaB/PZN-PT. Through competition between E-field induced uniaxial anisotropy and unidirectional anisotropy, large E-field induced exchange bias field shift up to equation image and near 180° deterministic magnetization switching were achieved, which would pave a new way for magnetoelectric random access memories and other memory technologies.

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