Advanced Materials

Cover image for Vol. 26 Issue 20

May 28, 2014

Volume 26, Issue 20

Pages 3165–3354

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      Networks: Shifting Networks to Achieve Subgroup Symmetry Properties (Adv. Mater. 20/2014) (page 3165)

      Han-Yu Hsueh, Yi-Chun Ling, Hsiao-Fang Wang, Lung-Yu Chang Chien, Yu-Chueh Hung, Edwin L. Thomas and Rong-Ming Ho

      Version of Record online: 22 MAY 2014 | DOI: 10.1002/adma.201470130

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      A double gyroid structure made by the self-assembly of block copolymers is used as a model system for the demonstration of shifting networks to achieve single gyroid-like scattering properties. R.-M. Ho and co-workers demonstrate on page 3225 that free-standing single gyroid-like network materials can be fabricated to give nanophotonic properties, similar to the photonic properties of a butterfly wing structure.

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      Graphene: Water-Free Transfer Method for CVD-Grown Graphene and Its Application to Flexible Air-Stable Graphene Transistors (Adv. Mater. 20/2014) (page 3166)

      Hyun Ho Kim, Yoonyoung Chung, Eunho Lee, Seong Kyu Lee and Kilwon Cho

      Version of Record online: 22 MAY 2014 | DOI: 10.1002/adma.201470131

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      K. Cho and co-workers develop on page 3213 a water-free transfer method for placing chemical vapor depositiongrown graphene onto arbitrary substrates. Transferring graphene without water enables water-sensitive substrates to be used in graphene electronics. Using this method, high-performance flexible air-stable graphene transistors are fabricated. A polymeric bilayer (poly(methyl methacrylate)/polybutadiene) is used as supporting layer during the transfer process, which provides not only robust support but also effective passivation that protects graphene from undesirable charged impurities.

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      Graphene: Layer-Stacking Growth and Electrical Transport of Hierarchical Graphene Architectures (Adv. Mater. 20/2014) (page 3355)

      Birong Luo, Bingyan Chen, Lan Meng, Dechao Geng, Hongtao Liu, Jie Xu, Zhiyong Zhang, Hantang Zhang, Lianmao Peng, Lin He, Wenping Hu, Yunqi Liu and Gui Yu

      Version of Record online: 22 MAY 2014 | DOI: 10.1002/adma.201470135

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      A layered stacking growth route for the hierarchical assembly of graphene on a liquid copper catalyst by chemical vapor deposition is described by G. Yu and co-workers on page 3218. These hierarchical graphene architectures, displaying a snow-like morphology, reveal the non-equilibrium growth processes of multi-layer graphene and present electrical anisotropy. This work potentially offers impetus for the application of graphenebased electronics.

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      Oxygen Reduction: Nitrogen-Doped Holey Graphitic Carbon from 2D Covalent Organic Polymers for Oxygen Reduction (Adv. Mater. 20/2014) (page 3356)

      Zhonghua Xiang, Dapeng Cao, Ling Huang, Jianglan Shui, Min Wang and Liming Dai

      Version of Record online: 22 MAY 2014 | DOI: 10.1002/adma.201470136

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      L. Dai, D. Cao, and co-workers develop on page 3315 a new strategy to obtain N-doped holey graphitic carbon materials using covalent organic polymer precursors with controlled locations for the N-atoms. These N-doped holey graphene analogues are promising candidates for efficient energy conversion and storage, particularly as efficient metal-free electrocatalysts for oxygen reduction reaction in fuel cells.

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      Masthead: (Adv. Mater. 20/2014)

      Version of Record online: 22 MAY 2014 | DOI: 10.1002/adma.201470133

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  7. Reviews

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    1. Hollow-Structured Mesoporous Materials: Chemical Synthesis, Functionalization and Applications (pages 3176–3205)

      Yongsheng Li and Jianlin Shi

      Version of Record online: 31 MAR 2014 | DOI: 10.1002/adma.201305319

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      Hollow-structured mesoporous materials (HMMs), a type of mesoporous material with a unique morphology, present promising application prospects in the fields of storage, adsorption and separation, confined catalysis, controlled drug release, and simultaneous diagnosis and therapy of cancers, owing to the subtle combination of the hollow architecture with the mesoporous nanostructure.

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      Biomimetic Composites: Amyloid-Hydroxyapatite Bone Biomimetic Composites (Adv. Mater. 20/2014) (page 3206)

      Chaoxu Li, Anne-Kathrin Born, Thomas Schweizer, Marcy Zenobi-Wong, Marta Cerruti and Raffaele Mezzenga

      Version of Record online: 22 MAY 2014 | DOI: 10.1002/adma.201470134

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      On page 3207, R. Mezzenga and co-workers demonstrate a human trabecular bone-derived pre-osteoblast cell growing and anchoring by filopodia and lamellipodia on top of a biomimetic bone hybrid composite made of lysozyme amyloid fibrils and hydroxyapatite platelets. Such spreading and focal adhesion complexes suggest a direct, integrin-mediated connection of the cell cytoskeleton with the substrate.

  9. Communications

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    1. Amyloid-Hydroxyapatite Bone Biomimetic Composites (pages 3207–3212)

      Chaoxu Li, Anne-Kathrin Born, Thomas Schweizer, Marcy Zenobi-Wong, Marta Cerruti and Raffaele Mezzenga

      Version of Record online: 14 MAR 2014 | DOI: 10.1002/adma.201306198

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      A “bottom up” strategy is proposed to synthesize high aspect ratio hydroxyapatite (and brushite) platelets, and combine them with amyloid fibrils into layered hybrid nanocomposites. Their hierarchical structure, despite the differences from natural bone, confers to the nanocomposites a density and elastic modulus matching those of cancellous bone. Evidence of good adhesion and spreading of human trabecular bone-derived pre-osteoblasts cells on these nanocomposites is provided.

    2. Water-Free Transfer Method for CVD-Grown Graphene and Its Application to Flexible Air-Stable Graphene Transistors (pages 3213–3217)

      Hyun Ho Kim, Yoonyoung Chung, Eunho Lee, Seong Kyu Lee and Kilwon Cho

      Version of Record online: 14 MAR 2014 | DOI: 10.1002/adma.201305940

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      Transferring graphene without water enables water-sensitive substrates to be used in graphene electronics. A polymeric bilayer (PMMA/PBU) is coated on graphene as a supporting layer for the water-free transfer process and as an excellent passivation layer that enhances device operation.

    3. Layer-Stacking Growth and Electrical Transport of Hierarchical Graphene Architectures (pages 3218–3224)

      Birong Luo, Bingyan Chen, Lan Meng, Dechao Geng, Hongtao Liu, Jie Xu, Zhiyong Zhang, Hantang Zhang, Lianmao Peng, Lin He, Wenping Hu, Yunqi Liu and Gui Yu

      Version of Record online: 11 FEB 2014 | DOI: 10.1002/adma.201305627

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      Hierarchical graphene architectures (HGAs) that grow by stacking of layers are produced on a liquid copper surface using chemical vapor deposition. The stacking mode — for example hexagonal–hexagonal–hexagonal or hexagonal–snowflake–dendritic — can be simply controlled. Measurements of the electrical properties of HGAs indicate that hierarchical stacking of graphene may be a simple and effective way of tailoring their properties without degrading them.

    4. Shifting Networks to Achieve Subgroup Symmetry Properties (pages 3225–3229)

      Han-Yu Hsueh, Yi-Chun Ling, Hsiao-Fang Wang, Lung-Yu Chang Chien, Yu-Chueh Hung, Edwin L. Thomas and Rong-Ming Ho

      Version of Record online: 27 MAR 2014 | DOI: 10.1002/adma.201305618

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      A simple method for the preparation of nanomaterials with new functionality by physical displacement of a network phase is suggested, giving a change in space group symmetry and hence properties. A double gyroid structure made by the self-assembly of block copolymers is used as a model system for the demonstration of shifting networks to achieve single gyroid-like scattering properties. Free-standing single gyroid-like network materials can be fabricated to give nanophotonic properties, similar to the photonic properties of a butterfly wing structure.

    5. Bioinspired Carbon Nanotube Fuzzy Fiber Hair Sensor for Air-Flow Detection (pages 3230–3234)

      Matthew R. Maschmann, Gregory J. Ehlert, Benjamin T. Dickinson, David M. Phillips, Cody W. Ray, Greg W. Reich and Jeffery W. Baur

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/adma.201305285

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      Artificial hair sensors consisting of a piezoresistive carbon-nanotube-coated glass fiber embedded in a microcapillary are assembled and characterized. Individual sensors resemble a hair plug that may be integrated in a wide range of host materials. The sensors demonstrate an air-flow detection threshold of less than 1 m/s with a piezoresistive sensitivity of 1.3% per m/s air-flow change.

    6. The Compromises of Printing Organic Electronics: A Case Study of Gravure-Printed Light-Emitting Electrochemical Cells (pages 3235–3240)

      Gerardo Hernandez-Sosa, Serpil Tekoglu, Sebastian Stolz, Ralph Eckstein, Claudia Teusch, Jannik Trapp, Uli Lemmer, Manuel Hamburger and Norman Mechau

      Version of Record online: 26 FEB 2014 | DOI: 10.1002/adma.201305541

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      Light-emitting electrochemical cells (LECs) are fabricated by gravure printing. The compromise between device performance and printing quality is correlated to the ink formulation and the printing process. It is shown that the rheological properties of the ink formulations of LECs can be tailored without changing the chemical composition of the material blend.

    7. Graphene Nanoribbon Aerogels Unzipped from Carbon Nanotube Sponges (pages 3241–3247)

      Qingyu Peng, Yibin Li, Xiaodong He, Xuchun Gui, Yuanyuan Shang, Chunhui Wang, Chao Wang, Wenqi Zhao, Shanyi Du, Enzheng Shi, Peixu Li, Dehai Wu and Anyuan Cao

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/adma.201305274

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      Graphene nanoribbon aerogels are fabricated by directly unzipping multi-walled carbon nanotube sponges. These fascinating materials have potential applications as high performance nanocomposites and supercapacitor electrodes.

    8. Spatially Controlled Channel Entrances Functionalization of Zeolites L (pages 3248–3252)

      Nermin Seda Kehr, Bahar Ergün, Henning Lülf and Luisa De Cola

      Version of Record online: 8 FEB 2014 | DOI: 10.1002/adma.201305745

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      The spatially controlled channel entrances functionalization of disk shaped zeolite L crystals is described. Fluorescent dye or bioactive molecules are immobilized at one end of the channels of zeolite crystals and subsequently the other side of the crystals is derivatized with magnetic iron oxide nanoparticles. The asymmetrically functionalized crystals were used for the control of the movement of bacteria in solution.

    9. Developmentally-Inspired Shrink-Wrap Polymers for Mechanical Induction of Tissue Differentiation (pages 3253–3257)

      Basma Hashmi, Lauren D. Zarzar, Tadanori Mammoto, Akiko Mammoto, Amanda Jiang, Joanna Aizenberg and Donald E. Ingber

      Version of Record online: 18 FEB 2014 | DOI: 10.1002/adma.201304995

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      A biologically inspired thermoresponsive polymer has been developed that mechanically induces tooth differentiation in vitro and in vivo by promoting mesenchymal cell compaction as seen in each pore of the scaffold. This normally occurs during the physiological mesenchymal condensation response that triggers tooth formation in the embryo.

    10. Metal–Organic Frameworks as Cathode Materials for Li–O2 Batteries (pages 3258–3262)

      Doufeng Wu, Ziyang Guo, Xinbo Yin, Qingqing Pang, Binbin Tu, Lijuan Zhang, Yong-Gang Wang and Qiaowei Li

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/adma.201305492

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      Metal–organic frameworks (MOFs) with open metal sites enrich the population of O2 in the pores significantly and assist the Li–O2 reaction when employed as a cell electrode material. A primary capacity of 9420 mA h g−1 is achieved in a cell with Mn-MOF-74; more than four times higher than the value obtained in a cell without an MOF.

    11. Ambipolar MoTe2 Transistors and Their Applications in Logic Circuits (pages 3263–3269)

      Yen-Fu Lin, Yong Xu, Sheng-Tsung Wang, Song-Lin Li, Mahito Yamamoto, Alex Aparecido-Ferreira, Wenwu Li, Huabin Sun, Shu Nakaharai, Wen-Bin Jian, Keiji Ueno and Kazuhito Tsukagoshi

      Version of Record online: 1 APR 2014 | DOI: 10.1002/adma.201305845

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      We report ambipolar charge transport in α-molybdenum ditelluride (MoTe2) flakes, whereby the temperature dependence of the electrical characteristics was systematically analyzed. The ambipolarity of the charge transport originated from the formation of Schottky barriers at the metal/MoTe2 contacts. The Schottky barrier heights as well as the current on/off ratio could be modified by modulating the electrostatic fields of the back-gate voltage (V bg) and drain-source voltage (V ds). Using these ambipolar MoTe2 transistors we fabricated complementary inverters and amplifiers, demonstrating their feasibility for future digital and analog circuit applications.

    12. Photonic Crystal Microcapsules for Label-free Multiplex Detection (pages 3270–3274)

      Baofen Ye, Haibo Ding, Yao Cheng, Hongcheng Gu, Yuanjin Zhao, Zhuoying Xie and Zhongze Gu

      Version of Record online: 18 FEB 2014 | DOI: 10.1002/adma.201305035

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      A novel suspension array, which possesses the joint advantages of photonic crystal encoded technology, bioresponsive hydrogels, and photonic crystal sensors with capability of full multiplexing label-free detection is developed.

    13. Tunable, Ultralow-Power Switching in Memristive Devices Enabled by a Heterogeneous Graphene–Oxide Interface (pages 3275–3281)

      Min Qian, Yiming Pan, Fengyuan Liu, Miao Wang, Haoliang Shen, Daowei He, Baigeng Wang, Yi Shi, Feng Miao and Xinran Wang

      Version of Record online: 13 FEB 2014 | DOI: 10.1002/adma.201306028

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      Memristive devices based on vertical heterostructures of graphene and TiOx show a significant power reduction that is up to ∼103 times smaller than that of conventional structures. This power reduction arises as a result of a tunneling barrier at the interface. The barrier is tunable, opening up the possibility of engineering several key memory characteristics.

    14. (Gold Nanorod Core)/(Polyaniline Shell) Plasmonic Switches with Large Plasmon Shifts and Modulation Depths (pages 3282–3289)

      Nina Jiang, Lei Shao and Jianfang Wang

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/adma.201305905

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      (Gold nanorod core)/(polyaniline shell) nanostructures are prepared for functioning as active plasmonic switches. The single core/shell nanostructures exhibit a remarkable switching performance, with the modulation depth and scattering peak shift reaching 10 dB and 100 nm, respectively. The nanostructures are also deposited on substrates to form macroscale monolayers with remarkable ensemble plasmonic switching performances.

    15. Periosteum-Mimetic Structures Made from Freestanding Microgrooved Nanosheets (pages 3290–3296)

      Xuetao Shi, Toshinori Fujie, Akihiro Saito, Shinji Takeoka, Ying Hou, Yiwei Shu, Mingwei Chen, Hongkai Wu and Ali Khademhosseini

      Version of Record online: 11 MAR 2014 | DOI: 10.1002/adma.201305804

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      A “sticker-like” PLGA nanosheet with microgrooved patterns is developed through a facile combination of spin coating and micropatterning techniques. The resulting microgrooved PLGA nanosheets can be physically adhered on flat or porous surfaces with excellent stability in aqueous environments and can harness the spatial arrangements of cells, which make it a promising candidate for generating biomimic periosteum for bone regenerative applications.

    16. Nitrogen-Doped Graphene Oxide Quantum Dots as Photocatalysts for Overall Water-Splitting under Visible Light Illumination (pages 3297–3303)

      Te-Fu Yeh, Chiao-Yi Teng, Shean-Jen Chen and Hsisheng Teng

      Version of Record online: 22 FEB 2014 | DOI: 10.1002/adma.201305299

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      Nitrogen-doped graphene oxide quantum dots exhibit both p- and n-type conductivities and catalyze overall water-splitting under visible-light irradiation. The quantum dots contain p-n type photochemical diodes, in which the carbon sp2 clusters serve as the interfacial junction. The active sites for H2 and O2 evolution are the p- and n-domains, respectively, and the reaction mimics biological photosynthesis.

    17. Polymer Solar Cells with Diketopyrrolopyrrole Conjugated Polymers as the Electron Donor and Electron Acceptor (pages 3304–3309)

      Weiwei Li, W. S. Christian Roelofs, Mathieu Turbiez, Martijn M. Wienk and René A. J. Janssen

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/adma.201305910

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      A new class of diketopyrrolopyrrole conjugated acceptor polymer incorporating thiazoles with low-lying energy levels, high electron mobility, and broad absorption to the near infrared region provides a power conversion efficiency of 2.9% in solar cells with a second diketopyrrolo­pyrrole polymer as the donor.

    18. Rapid Coating of Surfaces with Functionalized Nanoparticles for Regulation of Cell Behavior (pages 3310–3314)

      Rui Tang, Daniel F. Moyano, Chandramouleeswaran Subramani, Bo Yan, Eunhee Jeoung, Gülen Yesilbag Tonga, Bradley Duncan, Yi-Cheun Yeh, Ziwen Jiang, Chaekyu Kim and Vincent M. Rotello

      Version of Record online: 21 FEB 2014 | DOI: 10.1002/adma.201306030

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      A robust monolayer of nanoparticles is formed via dip-coating of cell culture plates. These surfaces provide cell type-specific modulation of growth behavior without the uptake of nanoparticles.

    19. Nitrogen-Doped Holey Graphitic Carbon from 2D Covalent Organic Polymers for Oxygen Reduction (pages 3315–3320)

      Zhonghua Xiang, Dapeng Cao, Ling Huang, Jianglan Shui, Min Wang and Liming Dai

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/adma.201306328

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      Using covalent organic polymer pre­cursors, we have developed a new strategy for location control of N-dopant heteroatoms in the graphitic porous carbon, which otherwise is impossible to achieve with conventional N-doping techniques. The electrocatalytic activities of the N-doped holey graphene analogues are well correlated to the N-locations, showing possibility for tailoring the structure and property of N-doped carbon nanomaterials.

    20. Inverted Colloidal Quantum Dot Solar Cells (pages 3321–3327)

      Gi-Hwan Kim, Bright Walker, Hak-Beom Kim, Jin Young Kim, Edward H. Sargent, Jongnam Park and Jin Young Kim

      Version of Record online: 22 FEB 2014 | DOI: 10.1002/adma.201305583

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      An inverted architecture of quantum dot solar cells is demonstrated by introducing a novel ZnO method on top of the PbS CQD film. Improvements in device characteristics stem from constructive optical interference from the ZnO layer that enhances absorption in the PbS CQD layer. Outstanding diode characteristics arising from a superior PbS/ZnO junction provide a further electronic advantage.

    21. Ultraflexible, Freestanding Nanomembranes Based on Poly(ethylene glycol) (pages 3328–3332)

      Nikolaus Meyerbröker and Michael Zharnikov

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/adma.201305480

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      Extremely elastic and highly stable nanomembranes of variable thickness (5–350 nm) made completely of poly(ethylene glycol) are prepared by a simple procedure. The membranes exhibit distinct biorepulsive and hydrogel properties. They offer new possibilities for applications such as supports in transmission electron microscopy, matrices for inorganic nanoparticles, and pressure-sensitive elements for sensors.

    22. Mechanically Robust, Electrically Conductive and Stimuli-Responsive Binary Network Hydrogels Enabled by Superelastic Graphene Aerogels (pages 3333–3337)

      Ling Qiu, Diyan Liu, Yufei Wang, Chi Cheng, Kun Zhou, Jie Ding, Van-Tan Truong and Dan Li

      Version of Record online: 14 MAR 2014 | DOI: 10.1002/adma.201305359

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      The architecture of the nanofiller phase in polymer nanocomposites matters! Polymer hydrogels that can combine stimuli-responsiveness with excellent electrically conductivity and mechanical strength can be fabricated by incorporation of the polymer into an ultralight and superelastic graphene aerogel to form a binary network.

    23. Flexible and Binder-Free Organic Cathode for High-Performance Lithium-Ion Batteries (pages 3338–3343)

      Haiping Wu, Stephen A. Shevlin, Qinghai Meng, Wei Guo, Yuena Meng, Kun Lu, Zhixiang Wei and Zhengxiao Guo

      Version of Record online: 11 MAR 2014 | DOI: 10.1002/adma.201305452

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      Fabrication of a flexible organic ­electrode by growing polyimide nanoflakes on single-wall carbon nanotube films is presented. The flexible electrode exhibits high capacity and outstanding rate ­capability. This electrode is promising for the application in high-power flexible ­lithium-Ion batteries.

    24. All Spraying Processes for the Fabrication of Robust, Self-Healing, Superhydrophobic Coatings (pages 3344–3348)

      Yang Li, Shanshan Chen, Mengchun Wu and Junqi Sun

      Version of Record online: 31 MAR 2014 | DOI: 10.1002/adma.201306136

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      The spraying method is developed for the fabrication of mechanically robust and self-healing superhydrophobic coatings, which comprise highly porous and rough polyelectrolyte coatings preserved with low-surface-energy healing agents. These coatings can repetitively and autonomically restore superhydrophobicity in humid environments. After depletion of healing agents, superhydrophobic coatings with dual healing agents can regain their self-healing ability by re-spraying fluoroalkylsilane.

    25. Strong Photocurrent Enhancements in Highly Efficient Flexible Organic Solar Cells by Adopting a Microcavity Configuration (pages 3349–3354)

      Kung-Shih Chen, Hin-Lap Yip, José-Francisco Salinas, Yun-Xiang Xu, Chu-Chen Chueh and Alex K.-Y. Jen

      Version of Record online: 11 MAR 2014 | DOI: 10.1002/adma.201306323

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      Organic solar cells often show inefficient light harvesting due to a short absorption path length limited by the low charge mobility of organic semiconductors. We demonstrate a flexible organic solar cell in a microcavity configuration using a TeO2/Ag semitransparent electrode to confine the optical field within the device with significant performance improvements and reaching a power conversion efficiency of 8.56%.

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