Advanced Functional Materials

Cover image for Vol. 22 Issue 1

January 11, 2012

Volume 22, Issue 1

Pages 1–224

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    1. Liquid Crystals: Mesomorphic Organization and Thermochromic Luminescence of Dicyanodistyrylbenzene-Based Phasmidic Molecular Disks: Uniaxially Aligned Hexagonal Columnar Liquid Crystals at Room Temperature with Enhanced Fluorescence Emission and Semiconductivity (Adv. Funct. Mater. 1/2012) (page 1)

      Seong-Jun Yoon, Jong H. Kim, Kil Suk Kim, Jong Won Chung, Benoît Heinrich, Fabrice Mathevet, Pyosang Kim, Bertrand Donnio, André-Jean Attias, Dongho Kim and Soo Young Park

      Version of Record online: 2 JAN 2012 | DOI: 10.1002/adfm.201290004

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      (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(3,4,5-tris(dodecyloxy)phenyl)acrylonitrile) (GDCS) molecules self-assemble into supramolecular disks consisting of a pair of molecules in a side-by-side dis-position assisted by secondary bonding interactions of the lateral polar cyano group, which, in turn, constitute the hexagonal columnar LC structure. As demonstrated on page 61 by Dongho Kim, Soo Young Park, and co-workers, uniaxially aligned liquid crystal (LC) and crystalline GDCS microwires with enhanced fluorescence and semiconductivity are successfully fabricated by using a micromolding in capillaries (MIMIC) process.

  2. Inside Front Cover

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    1. Biomedical Applications: Controlling The Mobility Of Oligonucleotides In The Nanochannels Of Mesoporous Silica (Adv. Funct. Mater. 1/2012) (page 2)

      Timo Lebold, Axel Schlossbauer, Katrin Schneider, Lothar Schermelleh, Heinrich Leonhardt, Thomas Bein and Christoph Bräuchle

      Version of Record online: 2 JAN 2012 | DOI: 10.1002/adfm.201290005

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      Mesoporous silica particles represent a novel, highly versatile class of drug-delivery systems. On page 106, Thomas Bein, Christoph Bräuchle, and co-workers utilize these materials as a host for the incorporation of short oligonucleotides as model gene therapeutics. The diffusion of a labelled oligo-nucleotide through a nanometer-sized silica pore is shown. Organic functionalization of the silica pore system offers a means to control oligonucleotide mobility and stability.

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

      Version of Record online: 2 JAN 2012 | DOI: 10.1002/adfm.201290006

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  5. Editorial

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  6. Feature Article

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    1. Shape-Controlled Synthesis of Polyhedral Nanocrystals and Their Facet-Dependent Properties (pages 14–24)

      Michael H. Huang and Po-Heng Lin

      Version of Record online: 23 SEP 2011 | DOI: 10.1002/adfm.201101784

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      Crystal Morphology Control: In this Article, the syntheses of Au, Cu2O, and Ag2O nanocrystals with shape evolution are described. As an example, the images show submicrometer-sized Cu2O crystals with cubic, truncated cubic, cuboctahedral, truncated octahedral, octahedral, and hexapod structures that can be synthesized systematically. These crystals with sharp faces are ideal for the examination of their facet-dependent properties.

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    1. Inverse-Woodpile Photonic Band Gap Crystals with a Cubic Diamond-like Structure Made from Single-Crystalline Silicon (pages 25–31)

      J. M. van den Broek, L. A. Woldering, R. W. Tjerkstra, F. B. Segerink, I. D. Setija and W. L. Vos

      Version of Record online: 28 SEP 2011 | DOI: 10.1002/adfm.201101101

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      Three-dimensional silicon photonic band gap crystals with a diamond-like symmetry are fabricated by complementary metal oxide–semiconductor compatible methods. These “inverse woodpiles” consist of two perpendicular sets of pores etched consecutively after careful alignment. The crystals are analyzed in detail regarding pore depth, radius, tapering, shape, and alignment. Optical reflectivity demonstrates that the crystals are of high quality.

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    1. Organic Single Crystalline Lasers: Distributed Feedback Lasers Based on Thiophene/Phenylene Co-Oligomer Single Crystals (Adv. Funct. Mater. 1/2012) (page 32)

      Hong-Hua Fang, Ran Ding, Shi-Yang Lu, Jie Yang, Xu-Lin Zhang, Rui Yang, Jing Feng, Qi-Dai Chen, Jun-Feng Song and Hong-Bo Sun

      Version of Record online: 2 JAN 2012 | DOI: 10.1002/adfm.201290002

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      On page 33, Jing Feng, Hong-Bo Sun, and co-workers report the use of an interference ablation method to fabricate an organic single-crystalline distributed feedback laser. Organic single crystals are difficult to treat using traditional fabrication methods because of their fragility and sensitivity to organic solvents and this method resolves these difficulties. The method may be applied to fabricate high-quality organic devices based on the single-crystalline materials.

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    1. Distributed Feedback Lasers Based on Thiophene/Phenylene Co-Oligomer Single Crystals (pages 33–38)

      Hong-Hua Fang, Ran Ding, Shi-Yang Lu, Jie Yang, Xu-Lin Zhang, Rui Yang, Jing Feng, Qi-Dai Chen, Jun-Feng Song and Hong-Bo Sun

      Version of Record online: 6 OCT 2011 | DOI: 10.1002/adfm.201101467

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      Distributed feedback lasing is produced from high-mobility organic thin-film single crystals. High-quality 1D distributed feedback resonators are constructed in BP2T single-crystalline thin film materials by an extremely simple method – laser interference ablation. This method does not involve chemical solution and avoids the need for good-quality end facets of crystals.

    2. Active Enzyme Nanocoatings Affect Settlement of Balanus amphitrite Barnacle Cyprids (pages 39–47)

      Mariana Tasso, Sheelagh L. Conlan, Anthony S. Clare and Carsten Werner

      Version of Record online: 19 OCT 2011 | DOI: 10.1002/adfm.201101173

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      The efficacy of covalently immobilized Subtilisin A on the exploratory behavior, settlement and adhesion of the major marine fouling pest Balanus amphitrite is systematically tested. The coating is suggested as the first step towards the development of a nontoxic, clear anti-fouling and fouling-release coating that could have uses within both medical fields and the marine industry.

    3. Versatile α,ω-Disubstituted Tetrathienoacene Semiconductors for High Performance Organic Thin-Film Transistors (pages 48–60)

      Jangdae Youn, Peng-Yi Huang, Yu-Wen Huang, Ming-Chou Chen, Yu-Jou Lin, Hui Huang, Rocio Ponce Ortiz, Charlotte Stern, Ming-Che Chung, Chieh-Yuan Feng, Liang-Hsiang Chen, Antonio Facchetti and Tobin J. Marks

      Version of Record online: 8 NOV 2011 | DOI: 10.1002/adfm.201101053

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      Perfluorophenyl-functionalized tetrathienothiophene (DFP-TTA) exhibits n- channel transport with a mobility as high as 0.30 cm2 V−1 s−1 and an on-off ratio of 1.8 × 107. The large TTA core size and good solid state packing in combination with optimum film growth conditions enhance electron transport in DFP-TTA thin-film transistors.

    4. Mesomorphic Organization and Thermochromic Luminescence of Dicyanodistyrylbenzene-Based Phasmidic Molecular Disks: Uniaxially Aligned Hexagonal Columnar Liquid Crystals at Room Temperature with Enhanced Fluorescence Emission and Semiconductivity (pages 61–69)

      Seong-Jun Yoon, Jong H. Kim, Kil Suk Kim, Jong Won Chung, Benoît Heinrich, Fabrice Mathevet, Pyosang Kim, Bertrand Donnio, André-Jean Attias, Dongho Kim and Soo Young Park

      Version of Record online: 18 OCT 2011 | DOI: 10.1002/adfm.201101818

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      A new dicyanodistyrylbenzene-based liquid-crystalline material [(2Z,2'Z)-2,2’-(1,4-phenylene)bis(3-(3,4,5-tris(dodecyloxy)phenyl)acrylonitrile) (GDCS)] shows intense green/yellow fluorescence in liquid/solid crystal state. The aggregation-induced enhanced emission and two-color luminescence behaviors are promoted by intra- and intermolecular actions, which are caused by the dipolar cyanostilbene unit. The aligned microwires of GDCS are fabricated by micromolding in capillaries for enhanced electrical conductivity.

    5. Effects of Moisture on the Switching Characteristics of Oxide-Based, Gapless-Type Atomic Switches (pages 70–77)

      Tohru Tsuruoka, Kazuya Terabe, Tsuyoshi Hasegawa, Ilia Valov, Rainer Waser and Masakazu Aono

      Version of Record online: 14 OCT 2011 | DOI: 10.1002/adfm.201101846

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      The role of moisture in the switching characteristics of oxide-based, gapless-type atomic switches is clarified. A certain amount of residual water exists in the oxide layer, forming a hydrogen-bond network at grain boundaries. Its stability has an impact on the ionization of Cu at the anode interfaces and the migration of Cu ions in the oxide layer, which plays a major role in determining the operation – important findings for the microscopic understanding of the switching behavior of oxide-based atomic switches.

    6. Encapsulation of Perchlorate Salts within Metal Oxides for Application as Nanoenergetic Oxidizers (pages 78–85)

      Chunwei Wu, Kyle Sullivan, Snehaunshu Chowdhury, Guoqiang Jian, Lei Zhou and Michael R. Zachariah

      Version of Record online: 7 NOV 2011 | DOI: 10.1002/adfm.201100479

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      High-oxygen-content strong oxidizers are encapsulated within mild oxidizer particles. This approach enables the use of hygroscopic materials by stabilizing them within a matrix. When mixed with nanoaluminum these formulations illicit a very violent reaction, which significantly outperform the single metal oxide system in both pressurization rate and peak pressure.

    7. Merocyanine/C60 Planar Heterojunction Solar Cells: Effect of Dye Orientation on Exciton Dissociation and Solar Cell Performance (pages 86–96)

      Antti Ojala, Andreas Petersen, Andreas Fuchs, Robert Lovrincic, Carl Pölking, Jens Trollmann, Jaehyung Hwang, Christian Lennartz, Helmut Reichelt, Hans Wolfgang Höffken, Annemarie Pucci, Peter Erk, Thomas Kirchartz and Frank Würthner

      Version of Record online: 31 OCT 2011 | DOI: 10.1002/adfm.201101697

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      Substrate heating and post-annealing techniques are used to control the orientation of dye molecules in thermally vacuum-deposited planar heterojunction merocyanine/C60 solar cells. Favorable molecular orientation at the heterointerface substantially improves the exciton dissociation efficiency resulting in up to 100% improvement of the fill factor.

    8. Solution-Processed Ambipolar Field-Effect Transistor Based on Diketopyrrolopyrrole Functionalized with Benzothiadiazole (pages 97–105)

      Yuan Zhang, Chunki Kim, Jason Lin and Thuc-Quyen Nguyen

      Version of Record online: 21 OCT 2011 | DOI: 10.1002/adfm.201101820

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      An inverter is fabricated from solution-processed small molecules containing a diketopyrrolopyrrole core (BTDPP2)using a simple thermally evaporated electrode pattern. The device architecture is composed of two BTDPP2 ambipolar transistors connected in parallel. The inverter displays gain values exceeding 25 when operated under both p-type and n-type regimes.

    9. Controlling The Mobility Of Oligonucleotides In The Nanochannels Of Mesoporous Silica (pages 106–112)

      Timo Lebold, Axel Schlossbauer, Katrin Schneider, Lothar Schermelleh, Heinrich Leonhardt, Thomas Bein and Christoph Bräuchle

      Version of Record online: 24 OCT 2011 | DOI: 10.1002/adfm.201101365

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      Template-free SBA-15 type mesoporous silica particles are loaded with siRNA and dsDNA. The particles’ uptake capability is controlled by an organic surface functionalization and the dynamics of the intact oligonucleotides inside the functionalized nanochannels determined. The study demonstrates the potential of mesoporous silica as an alternative means for gene delivery. Such alternatives are urgently needed since the delivery of oligonucleotides to their target sites still represents a major hurdle in the application of gene therapy.

    10. CO2-Laser-Induced Growth of Epitaxial Graphene on 6H-SiC(0001) (pages 113–120)

      Spyros N. Yannopoulos, Angeliki Siokou, Nektarios K. Nasikas, Vassilios Dracopoulos, Fotini Ravani and George N. Papatheodorou

      Version of Record online: 4 NOV 2011 | DOI: 10.1002/adfm.201101413

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      A novel method for the fast, one-step growth of large-area, homogeneous, high-quality epitaxial graphene on SiC(0001) is presented. An infrared CO2 laser (10.6 μm) is used as the heating source enabling in situ patterning. A number of experimental techniques, such as scanning electron microscopy, X-ray photoelectron spectroscopy, depth profiling methods, and Raman spectroscopy, is employed to present an in-depth analysis of the quantitative and qualitative features of the EG grown by the current method.

    11. Formation of Embryoid Bodies with Controlled Sizes and Maintained Pluripotency in Three-Dimensional Inverse Opal Scaffolds (pages 121–129)

      Yu Zhang and Younan Xia

      Version of Record online: 22 NOV 2011 | DOI: 10.1002/adfm.201101690

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      Uniform embryoid bodies (EBs) with controlled sizes were formed in the pores of an alginate inverse opal scaffold and then recovered after disintegration of the scaffold. The EBs maintained their viability and undifferentiated state, and they were able to differentiate into specific lineages upon stimulation.

  10. Frontispiece

    1. Top of page
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    1. Drug Delivery: Harnessing Interfacial Phenomena to Program the Release Properties of Hollow Microcapsules (Adv. Funct. Mater. 1/2012) (page 130)

      Myung Han Lee, Kolin C. Hribar, Teresa Brugarolas, Neha P. Kamat, Jason A. Burdick and Daeyeon Lee

      Version of Record online: 2 JAN 2012 | DOI: 10.1002/adfm.201290001

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      The generation of near-infrared-sensitive microcapsules with programmable release properties is reported by Daeyeon Lee and co-workers on page 131. Poly(DL-lactic-co-glycolic) acid (PLGA) microcapsules are generated using monodisperse water-in-oil-inwater double emulsions as templates. The composition of the oil phase of double emulsions and that of PLGA determine the morphology and, in turn, the release properties of microcapsules. These microcapsules enable the release of hydrophobic and hydrophilic agents in a programmed sequence.

  11. Full Papers

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    1. Harnessing Interfacial Phenomena to Program the Release Properties of Hollow Microcapsules (pages 131–138)

      Myung Han Lee, Kolin C. Hribar, Teresa Brugarolas, Neha P. Kamat, Jason A. Burdick and Daeyeon Lee

      Version of Record online: 12 OCT 2011 | DOI: 10.1002/adfm.201101303

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      Near infrared (NIR)-sensitive PLGA microcapsules with programmed release properties are generated by controlling the capsule morphology. The figures illustrate the effect of PLGA microcapsule morphology on their NIR responsiveness.

    2. Low-Power-Photon Up-Conversion in Dual-Dye-Loaded Polymer Nanoparticles (pages 139–143)

      Angelo Monguzzi, Michel Frigoli, Chantal Larpent, Riccardo Tubino and Francesco Meinardi

      Version of Record online: 14 OCT 2011 | DOI: 10.1002/adfm.201101709

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      Sensitized triplet–triplet annihilation in multicomponent organic systems in solution allows efficient up-conversion at the solar-irradiance power density, but loses efficiency in the solid state. Here, it is demonstrated that this limitation can be avoided by incorporating suitable dyes into polymer nanoparticles, which can be used for drop-cast films or as dopants for solid matrices.

    3. Charge-Carrier Balance and Color Purity in Polyfluorene Polymer Blends for Blue Light-Emitting Diodes (pages 144–150)

      Li-Ping Lu, Dinesh Kabra, Kerr Johnson and Richard H. Friend

      Version of Record online: 25 OCT 2011 | DOI: 10.1002/adfm.201101892

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      Charge-carrier balance and color purity is achieved in an arylated polyfluorene-based blue-emitting light-emitting diode (LED) by use of a macromolecular additive (TFB). This additive provides excellent control over current density while keeping the optical properties of emissive materials intact. Luminance efficiency of up to 5.9 cd A−1 along with a pure blue emission is achieved in the blend instead of 1.2 cd A−1 in the homopolymer-based LED.

    4. Stoichiometry Controlled, Single-Crystalline Bi2Te3 Nanowires for Transport in the Basal Plane (pages 151–156)

      Nicola Peranio, Eva Leister, William Töllner, Oliver Eibl and Kornelius Nielsch

      Version of Record online: 14 OCT 2011 | DOI: 10.1002/adfm.201101273

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      Stoichiometric, single-crystalline Bi2Te3 nanowires with diameters of 50–80 nm are grown by potential-pulsed electrochemical deposition in a nanostructured Al2O3 matrix. X-ray diffraction, electron diffraction, and high-accuracy energy-dispersive X-ray spectroscopy unambiguously prove that, for the first time, single-crystalline, stoichiometric Bi2Te3 nanowires are grown that allow transport in the basal plane without being affected by grain boundaries.

    5. Charge Transport in a Highly Phosphorescent Iridium(III) Complex-Cored Dendrimer with Double Dendrons (pages 157–165)

      Salvatore Gambino, Shih-Chun Lo, Zehua Liu, Paul L. Burn and Ifor D. W. Samuel

      Version of Record online: 19 OCT 2011 | DOI: 10.1002/adfm.201101727

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      High phosphorescence efficiency can be combined with non-dispersive charge transport in doubly dendronized iridium(III) complex-cored dendrimers for organic light-emitting diodes. The double dendrons give the macromolecule a more spherical shape, reducing energetic disorder in the film and hence improving charge transport, as well as increasing photoluminescence quantum yield.

    6. Mesoporous Anatase Titania Hollow Nanostructures though Silica-Protected Calcination (pages 166–174)

      Ji Bong Joo, Qiao Zhang, Ilkeun Lee, Michael Dahl, Francisco Zaera and Yadong Yin

      Version of Record online: 19 OCT 2011 | DOI: 10.1002/adfm.201101927

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      A new silica-protected calcination process has been developed for the synthesis of mesoporous hollow spheres of small-grain-size anatase TiO2 with controllable crystallinity, high surface area, and excellent dispersity in water. The mesoporous TiO2 shells show significantly enhanced photocatalytic activity towards degradation of organic molecules.

    7. Mechanistic Considerations of Bending-Strain Effects within Organic Semiconductors on Polymer Dielectrics (pages 175–183)

      Anatoliy N. Sokolov, Yadong Cao, Olasupo B. Johnson and Zhenan Bao

      Version of Record online: 21 OCT 2011 | DOI: 10.1002/adfm.201101418

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      To produce flexible organic electronics, understanding the effects of strain on the device performance is critical. A comprehensive study of seven polymer dielectrics with two organic semiconductors is presented. The novel influence of both dielectric and organic semiconductor structure is described.

    8. Magnetic Memory Effect of Nanocomposites (pages 184–191)

      M. Y. Razzaq, M. Behl and A. Lendlein

      Version of Record online: 25 OCT 2011 | DOI: 10.1002/adfm.201101590

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      Magnetic memory materials can remember a magnetic field strength Hdef, at which they were deformed recently. In cyclic, magneto-mechanical tests, a linear correlation was found between Hdef and the magnetic field strength Hsw, at which the magnetic memory effect occurred. This correlation impressively demonstrates excellent magnetic memory properties.

    9. Sub-Picosecond Processes of Ferroelectric Domain Switching from Field and Temperature Experiments (pages 192–199)

      An Quan Jiang, Hyun Ju Lee, Cheol Seong Hwang and James F. Scott

      Version of Record online: 8 NOV 2011 | DOI: 10.1002/adfm.201101521

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      Field dependence of domain-switching speeds is estimated over five orders of magnitude at temperatures of 5.4–280 K from domain-switching current transients in Pb(Zr0.4Ti0.6)O3 thin films. By using Merz's equation and nucleation-rate limited models, an ultimate domain-switching current density of 1.4 × 108 A cm−1 and nucleation time of 0.47 ps at the highest field of 0.20 MV cm−1 are extracted.

    10. Highly Efficient Organic THz Generator Pumped at Near-Infrared: Quinolinium Single Crystals (pages 200–209)

      Pil-Joo Kim, Jae-Hyeok Jeong, Mojca Jazbinsek, Soo-Bong Choi, In-Hyung Baek, Jong-Taek Kim, Fabian Rotermund, Hoseop Yun, Yoon Sup Lee, Peter Günter and O-Pil Kwon

      Version of Record online: 24 OCT 2011 | DOI: 10.1002/adfm.201101458

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      Highly efficient ionic electro-optic quinolinium single crystals with a high order parameter and a large macroscopic optical nonlinearity, exhibit more than three times higher THz generation efficiency than benchmark organic phenolic polyene crystals and almost one order of magnitude higher than inorganic standard ZnTe crystals pumped by near-infrared Ti:sapphire femtosecond laser pulses at 836 nm.

    11. Novel Approach for Alternating Current (AC)-Driven Organic Light-Emitting Devices (pages 210–217)

      Ajay Perumal, Markus Fröbel, Sandeep Gorantla, Thomas Gemming, Björn Lüssem, Jürgen Eckert and Karl Leo

      Version of Record online: 7 NOV 2011 | DOI: 10.1002/adfm.201100747

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      A novel approach for alternating current (AC)-driven organic light-emitting devices is reported, which uses the concept of molecular doping in organic semiconductors. Doped charge-transport layers are used for generation of charge carriers within the device. Bright luminance of up to 1000 cdm−2 is observed under AC bias. The luminance observed is attributed to charge-carrier generation and recombination within the device without injection of charge carriers through external electrodes.

    12. Arrays of Cone-Shaped ZnO Nanorods Decorated with Ag Nanoparticles as 3D Surface-Enhanced Raman Scattering Substrates for Rapid Detection of Trace Polychlorinated Biphenyls (pages 218–224)

      Haibin Tang, Guowen Meng, Qing Huang, Zhuo Zhang, Zhulin Huang and Chuhong Zhu

      Version of Record online: 2 DEC 2011 | DOI: 10.1002/adfm.201102274

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      Small Ag nanoparticles and large Ag spheres are simultaneously sputtered uniformly onto the side surface and the top ends of cone-shaped ZnO-nanorods fabricated by ZnO-seeds-induced electrodeposition, respectively. The as-prepared 3D hybrid surface-enhanced Raman spectroscopy substrate manifests high detection sensitivity to rhodamine and a detection limit as low as 10−11 M to polychlorinated biphenyl 77—one of the highly toxic persistent organic pollutants.

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