Advanced Materials

Cover image for Vol. 24 Issue 48

December 18, 2012

Volume 24, Issue 48

Pages 6387–6541

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
    1. Nonlinear Optics: High-Contrast Photoswitching of Nonlinear Optical Response in Crosslinked Ferroelectric Liquid-Crystalline Polymers (Adv. Mater. 48/2012) (page 6387)

      Arri Priimagi, Keiji Ogawa, Matti Virkki, Jun-ichi Mamiya, Martti Kauranen and Atsushi Shishido

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/adma.201290306

      Thumbnail image of graphical abstract

      Azobenzene-containing crosslinked ferroelectric liquid-crystalline polymers offer unique opportunities for reversible, high-contrast switching of a second-order nonlinear optical response in the solid state. Atsushi Shishido and co-workers show on p. 6410 that this is achieved by reversibly controlling non-centrosymmetric chromophore alignment through two-photon isomerization of azobenzene molecules.

  2. Inside Front Cover

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
    1. New Catalysis Concept: Enhanced Catalytic Activity of Self-Assembled-Monolayer-Capped Gold Nanoparticles (Adv. Mater. 48/2012) (page 6388)

      Tomoya Taguchi, Katsuhiro Isozaki and Kazushi Miki

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/adma.201290307

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      An unprecedented substrate-selective catalytic enhancement effect of an alkanethiol-self-assembled monolayer (SAM) on Au nanoparticles (AuNPs) is reported on p. 6462 by Tomoya Taguchi, Katsuhiro Isozaki, and Kazushi Miki. This new catalyst system based on weak intermolecular interactions provides a brand new concept for artificial metalloenzyme-type enhanced catalysis.

  3. Back Cover

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
    1. Chiroptical Spherulites: Circularly Polarized Blue Luminescent Spherulites Consisting of Hierarchically Assembled Ionic Conjugated Polymers with a Helically π-Stacked Structure (Adv. Mater. 48/2012) (page 6546)

      Kazuyoshi Watanabe, Hiroshi Iida and Kazuo Akagi

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/adma.201290308

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      On p. 6451 Kazuo Akagi and co-workers demonstrate that cationic π-conjugated polymers form an interchain helically π-stacked assembly with anionic chiral compounds that is stabilized by both electrostatic and π–π interactions. The assembly hierarchically self-organizes into a spherulite with a circularly polarized blue luminescence. The back cover shows the characteristic optical image, “Maltese Cross pattern” with extinction rings, and the hierarchical structures for the spherulite.

  4. Masthead

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
    1. Masthead: (Adv. Mater. 48/2012)

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/adma.201290309

  5. Contents

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
  6. Progress Report

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
    1. Powering up the Future: Radical Polymers for Battery Applications (pages 6397–6409)

      Tobias Janoschka, Martin D. Hager and Ulrich S. Schubert

      Version of Record online: 9 NOV 2012 | DOI: 10.1002/adma.201203119

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      For over a hundred years, rechargeable batteries have facilitated the evolution from a mains-operated to a mobile society. During this process, our society's dependency on limited resources such as lithium, cobalt, and rare earth metals grew steadily. With the recent development of electroactive nitroxide-radical-bearing polymers, a new and seminal class of electrode material is evolving quickly.

  7. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
    1. High-Contrast Photoswitching of Nonlinear Optical Response in Crosslinked Ferroelectric Liquid-Crystalline Polymers (pages 6410–6415)

      Arri Priimagi, Keiji Ogawa, Matti Virkki, Jun-ichi Mamiya, Martti Kauranen and Atsushi Shishido

      Version of Record online: 2 OCT 2012 | DOI: 10.1002/adma.201203369

      Thumbnail image of graphical abstract

      A conceptually novel materials design, based on crosslinked ferroelectric liquid-crystalline polymers, is demonstrated for efficient switching of a second-order nonlinear optical (NLO) response in the solid state. By controlling the molecular alignment of the NLO moieties through two-photon isomerization of azobenzene molecules, reversible isothermal photocontrol of second-harmonic generation is achieved with contrast of up to 20.

    2. Functionalized CdSe/ZnS QDs for the Detection of Nitroaromatic or RDX Explosives (pages 6416–6421)

      Ronit Freeman, Tali Finder, Lily Bahshi, Ron Gill and Itamar Willner

      Version of Record online: 25 SEP 2012 | DOI: 10.1002/adma.201202793

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      Chemically modified CdSe/ZnS quantum dots (QDs) are used as fluorescent probes for the analysis of explosives, and specifically, the detection of trinitrotoluene (TNT) or trinitrotriazine (RDX). The QDs are functionalized with electron-donating ligands that bind nitro-containing explosives, exhibiting electron-acceptor properties, to the QD surface, via supramolecular donor–acceptor interactions leading to the quenching of the luminescence of the QDs.

  8. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
    1. Nanoengineering: Atomic Layer Engineering of Perovskite Oxides for Chemically Sharp Heterointerfaces (Adv. Mater. 48/2012) (page 6422)

      Woo Seok Choi, Christopher M. Rouleau, Sung Seok A. Seo, Zhenlin Luo, Hua Zhou, Timothy T. Fister, Jeffrey A. Eastman, Paul H. Fuoss, Dillon D. Fong, Jonathan Z. Tischler, Gyula Eres, Matthew F. Chisholm and Ho Nyung Lee

      Version of Record online: 12 DEC 2012 | DOI: 10.1002/adma.201290305

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      Pulsed laser deposition (PLD) is a widely used growth technique for epitaxy of a wide range of oxide thin films and heterostructures. While the highly energetic PLD process is beneficial for epitaxy, it can deteriorate the interface's structure and chemical abruptness when grown under high vacuum. On page 6423, Ho Nyung Lee and co-workers provide a route to a chemically sharp oxide hetero-interface by atomic layer growth control during pulsed laser epitaxy.

  9. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Progress Report
    8. Communications
    9. Frontispiece
    10. Communications
    1. Atomic Layer Engineering of Perovskite Oxides for Chemically Sharp Heterointerfaces (pages 6423–6428)

      Woo Seok Choi, Christopher M. Rouleau, Sung Seok A. Seo, Zhenlin Luo, Hua Zhou, Timothy T. Fister, Jeffrey A. Eastman, Paul H. Fuoss, Dillon D. Fong, Jonathan Z. Tischler, Gyula Eres, Matthew F. Chisholm and Ho Nyung Lee

      Version of Record online: 4 OCT 2012 | DOI: 10.1002/adma.201202691

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      Atomic layer engineering enables fabrication of a chemically sharp oxide heterointerface. The interface formation and strain evolution during the initial growth of LaAlO3/SrTiO3 heterostructures by pulsed laser deposition are investigated in search of a means for controlling the atomic-sharpness of the interface. This study shows that inserting a monolayer of LaAlO3 grown at high oxygen pressure dramatically enhances interface abruptness.

    2. Unveiling Self-Assembled Monolayers' Potential for Molecular Spintronics: Spin Transport at High Voltage (pages 6429–6432)

      Marta Galbiati, Clément Barraud, Sergio Tatay, Karim Bouzehouane, Cyrile Deranlot, Eric Jacquet, Albert Fert, Pierre Seneor, Richard Mattana and Frédéric Petroff

      Version of Record online: 11 OCT 2012 | DOI: 10.1002/adma.201203136

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      Molecular magnetic tunnel junctions using self-assembled monolayers (SAMs) as tunnel barriers show stable and efficient spin transport properties. Large tunnel magnetoresistance with a flat bias voltage dependence of the magnetoresistance is observed in La2/3Sr1/3MnO3/dodecylphosphonic acid SAM/Co nanocontacts. This opens the door to spintronic tailoring though SAM engineering and could also lead to new venues for spin injection in organic devices.

    3. Coordination Polymer Coated Mesoporous Silica Nanoparticles for pH-Responsive Drug Release (pages 6433–6437)

      Lei Xing, Haoquan Zheng, Yuanyuan Cao and Shunai Che

      Version of Record online: 24 SEP 2012 | DOI: 10.1002/adma.201201742

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      Coordination polymer coated mesoporous silica nanoparticles for drug delivery are successfully synthesized. The system ensures that drugs are stored in the mesopores under a physiological environment. Upon H+ stimulus in the endosomal and lysosomal compartments, the drugs are released into the intracellular organelles of cancer cells, effectively killing the cells.

    4. Full Color Tunable Photonic Crystal from Crystalline Colloidal Arrays with an Engineered Photonic Stop-Band (pages 6438–6444)

      Moon Gyu Han, Chang Gyun Shin, Seog-Jin Jeon, HongShik Shim, Chul-Joon Heo, Haishun Jin, Jung Woo Kim and SangYoon Lee

      Version of Record online: 9 OCT 2012 | DOI: 10.1002/adma.201203211

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      An electrically tunable photonic crystal is developed utilizing crystalline colloidal arrays of high refractive index particles. Through modulation of the refractive index of the particle, and the applied electric field, both the bandwidth and position of the photonic bandgap could be tuned. Full color modulation with high optical quality is achieved, which paves a way to develop a novel reflective display.

    5. Initiated Chemical Vapor Deposition-Based Method for Patterning Polymer and Metal Microstructures on Curved Substrates (pages 6445–6450)

      Christy D. Petruczok and Karen K. Gleason

      Version of Record online: 26 SEP 2012 | DOI: 10.1002/adma.201201975

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      A simple, efficient, and scalable method for patterning microstructures on curved substrates is demonstrated. Initiated chemical vapor deposition is used to synthesize a thin film that crosslinks upon UV exposure. Polymeric features are defined on glass rods with high curvature and used as masks for metal patterning. Additionally, vapor-deposited polymer layers are selectively patterned to produce bifunctional surfaces.

    6. Circularly Polarized Blue Luminescent Spherulites Consisting of Hierarchically Assembled Ionic Conjugated Polymers with a Helically π-Stacked Structure (pages 6451–6456)

      Kazuyoshi Watanabe, Hiroshi Iida and Kazuo Akagi

      Version of Record online: 18 SEP 2012 | DOI: 10.1002/adma.201203155

      Thumbnail image of graphical abstract

      Cationic π-conjugated polymers form an interchain helically π-stacked assembly with anionic chiral compounds that is stabilized by both electrostatic and π−π interactions to hierarchically self-organize into a spherulite with a circularly polarized blue luminescence. To the best of our knowledge, this is the first example of a chiroptical spherulite that is hierarchically constructed from π-conjugated polymers.

    7. Influence of Alkyl Chain Branching Positions on the Hole Mobilities of Polymer Thin-Film Transistors (pages 6457–6461)

      Ting Lei, Jin-Hu Dou and Jian Pei

      Version of Record online: 24 SEP 2012 | DOI: 10.1002/adma.201202689

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      Four polymers that contain alkyl chains branched at different positions on the polymer backbone are prepared. A polymer with 4-decyltetradecyl chains gives an impressive mobility of 3.62 cm2 V−1 s−1. This may arise from tighter polymer packing as well as stacking conformation change of the polymer backbone induced by the branching of the alkyl chains.

    8. Enhanced Catalytic Activity of Self-Assembled-Monolayer-Capped Gold Nanoparticles (pages 6462–6467)

      Tomoya Taguchi, Katsuhiro Isozaki and Kazushi Miki

      Version of Record online: 12 SEP 2012 | DOI: 10.1002/adma.201202979

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      An unprecedented substrate-selective catalytic enhancement effect of an alkanethiol-self-assembled monolayer (SAM) on Au nanoparticles (AuNPs) is reported. In the supported 2D-array of AuNPs, the alkanethiol-SAM acts as a protein-like soft reaction space in which the substrate molecules are encapsulated through non-covalent intermolecular hydrophobic interactions, and thus catalytic reactions are accelerated at AuNP surfaces.

    9. Stretchable Spin Valves on Elastomer Membranes by Predetermined Periodic Fracture and Random Wrinkling (pages 6468–6472)

      Michael Melzer, Gungun Lin, Denys Makarov and Oliver G. Schmidt

      Version of Record online: 5 OCT 2012 | DOI: 10.1002/adma.201201898

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      The first highly stretchable and sensitive spin valve sensor on elastomeric membranes are demonstrated. The sensor elements exhibit stable GMR behavior up to tensile strains of 29% in in situ stretching experiments and show no fatigue over 500 loading cycles. This remarkable stretchability is achieved by a predetermined periodic fracture mechanism that creates a meander-like pattern upon stretching.

    10. Stimulated Resonance Raman Scattering and Laser Oscillation in Highly Emissive Distyrylbenzene-Based Molecular Crystals (pages 6473–6478)

      Shinto Varghese, Seong-Jun Yoon, Eva M. Calzado, Santiago Casado, Pedro G. Boj, María A. Díaz-García, Roland Resel, Roland Fischer, Begoña Milián-Medina, Reinhold Wannemacher, Soo Young Park and Johannes Gierschner

      Version of Record online: 12 OCT 2012 | DOI: 10.1002/adma.201202525

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      Three-in-one: A novel distyrylbenzene-based material forms J-type aggregates in single crystals with highly polarized and bright red emission, giving rise to optical gain narrowing, for which different mechanisms (amplified spontaneous emission, laser emission and stimulated resonance Raman scattering) are observed. These are correlated with the favorable intrinsic and macroscopic properties of the crystal, in particular to the orientation of the molecules to the crystal surface.

    11. Multicompartment Intracellular Self-Expanding Nanogel for Targeted Delivery of Drug Cocktail (pages 6479–6483)

      Remant Bahadur K. C. and Peisheng Xu

      Version of Record online: 24 SEP 2012 | DOI: 10.1002/adma.201202687

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      A nano cocktail, NCPD, fabricated from a pH and redox dual responsive polymer shows a multicompartment structure. The NCPD nanogel is stable in physiological environments while intracellular spontaneous swelling and fast releasing its payload. NCPD displays much stronger synergism than its free drug counterpart, which suggests that NCPD could greatly attenuate the side effects of drug cocktails while boosting synergistic anticancer effects.

    12. Antimicrobial and Antifouling Hydrogels Formed In Situ from Polycarbonate and Poly(ethylene glycol) via Michael Addition (pages 6484–6489)

      Shao Qiong Liu, Chuan Yang, Yuan Huang, Xin Ding, Yan Li, Wei Min Fan, James L. Hedrick and Yi-Yan Yang

      Version of Record online: 27 SEP 2012 | DOI: 10.1002/adma.201202225

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      A novel class of antimicrobial cationic polycarbonate/PEG hydrogels are designed and synthesized by Michael addition chemistry. These hydrogels demonstrate strong broad-spectrum antimicrobial activities against various clinically isolated multidrug-resistant microbes. Moreover, they exhibit nonfouling properties and prevent the substrate from microbial adhesion. These antimicrobial and antifouling gels are promising materials as catheter coatings and wound dressings to prevent infections.

    13. Active Control of Ferroelectric Switching Using Defect-Dipole Engineering (pages 6490–6495)

      Daesu Lee, Byung Chul Jeon, Seung Hyub Baek, Sang Mo Yang, Yeong Jae Shin, Tae Heon Kim, Yong Su Kim, Jong-Gul Yoon, Chang Beom Eom and Tae Won Noh

      Version of Record online: 1 OCT 2012 | DOI: 10.1002/adma.201203101

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      Active control of defect structures and associated polarization switching in a ferroelectric material is achieved without compromising its ferroelectric properties. Based on dipolar interaction between defect dipole and polarization, the unique functionality of the defect dipole to control ferroelectric switching is visualized. This approach can provide a foundation for novel ferroelectric applications, such as high-density multilevel data storage.

    14. All-Conjugated Triblock Polyelectrolytes (pages 6496–6501)

      Lei Ying, Peter Zalar, Samuel D. Collins, Zhao Chen, Alexander A. Mikhailovsky, Thuc-Quyen Nguyen and Guillermo C. Bazan

      Version of Record online: 2 OCT 2012 | DOI: 10.1002/adma.201202817

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      All-conjugated triblock polyfluorenes with well-defined molecular weights and low polydispersities are synthesized via chain-growth Suzuki-Miyaura polymerization. Ionization of pendant alkylbromide chains by pyridine affords amphiphilic triblock polyelectrolytes with neutral/charged/neutral or charged/neutral/charged segments. The immiscible blocks lead to aggregation in polar and nonpolar solvents, and to complex surface morphologies depending on the polarity of the substrate. These triblock polyelectrolytes can also be used as interfacial layers in polymer light-emitting diodes to facilitate electron injection from aluminum.

    15. Hydrogenated Li4Ti5O12 Nanowire Arrays for High Rate Lithium Ion Batteries (pages 6502–6506)

      Laifa Shen, Evan Uchaker, Xiaogang Zhang and Guozhong Cao

      Version of Record online: 5 OCT 2012 | DOI: 10.1002/adma.201203151

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      Self-supported Li4Ti5O12 nanowire arrays with high conductivity architectures are designed and fabricated for application in a Li-ion battery. The Li4Ti5O12 nanowire arrays grow directly on Ti foil by a facile solution-based method, further enhancing Li-ion storage properties by creating Ti3+ sites through hydrogenation. This configuration ensures that every Li4Ti5O12 nanowire participates in the fast electrochemical reaction, enabling remarkable rate performance and a long cycle life.

    16. Measuring Electrical Properties of Thin Film Fuel Cell Electrodes by In Situ Infrared Spectroscopy (pages 6507–6512)

      Jong Hoon Joo, Rotraut Merkle, Jung-Hwa Kim and Joachim Maier

      Version of Record online: 1 OCT 2012 | DOI: 10.1002/adma.201202934

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      The electrical conductivities of cathode films on a solid oxide fuel cell electrolyte can be determined quantitatively by in situ infrared spectroscopy over a wide range of temperatures and partial oxygen pressures. This method allows measurement of the electrical conductivity of an electrode film on the electrolyte excluding leakage current effects through the substrate.

    17. Bistable Large-Strain Actuation of Interpenetrating Polymer Networks (pages 6513–6519)

      Xiaofan Niu, Xinguo Yang, Paul Brochu, Hristiyan Stoyanov, Sungryul Yun, Zhibin Yu and Qibing Pei

      Version of Record online: 18 SEP 2012 | DOI: 10.1002/adma.201202876

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      The bistable electroactive polymer is a new smart material capable of large strain, rigid-to-rigid actuation. At the rubbery state of the polymer heated to above its glass transition, stable electrically-induced actuation is obtained at strains as large as 150%. Electromechanical instability can be effectively overcome by the formation of interpenetrating polymer networks. An application as a refreshable braille display is demonstrated.

    18. New Photorotor for the Induction of Anisotropy (pages 6520–6523)

      Regina Rosenhauer, Christian Kempe, Beate Sapich, Markus Klein, Eike Poetsch and Joachim Stumpe

      Version of Record online: 16 OCT 2012 | DOI: 10.1002/adma.201202234

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      A new class of photosensitive compounds generates optical anisotropy comparable to azobenzene systems upon irradiation with linearly polarized light, but, in contrast to these systems, the new photorotor system does not absorb in the visible range. High values of dichroism and birefringence are induced and in the case of LC polymers the light induced order can be amplified by self-organization.

    19. Integrated Synthesis of Poly(o-phenylenediamine)-Derived Carbon Materials for High Performance Supercapacitors (pages 6524–6529)

      Hui Zhu, Xiaolei Wang, Xuexia Liu and Xiurong Yang

      Version of Record online: 9 OCT 2012 | DOI: 10.1002/adma.201202461

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      Poly(o-phenylenediamine) (POPD)-derived functional carbon materials with excellent capacitive performance (see figure) are successfully synthesized by means of an integrated one-step process, in which FeCl3 not only oxidizes the polymerization of the organic monomers but also activates the carbonization. Furthermore, extensive research has proved that this strategy to discover novel carbons is useful not only for capacitors but also for other energy storage/conversion devices.

    20. Nd2Fe14B/FeCo Anisotropic Nanocomposite Films with a Large Maximum Energy Product (pages 6530–6535)

      Wei-Bin Cui, Yukiko K. Takahashi and Kazuhiro Hono

      Version of Record online: 26 OCT 2012 | DOI: 10.1002/adma.201202328

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      Anisotropic Nd2Fe14B/Fe67Co33 nanocomposite thin films are successfully fabricated. The multilayer composite films comprise Nd-rich shell-enveloped Nd2Fe14B grains and a Fe67Co33 phase. The strong (001) texture of the Nd2Fe14B grains and the presence of exchange-coupled Fe67Co33 lead to a high remanence and the presence of the Nd-rich shell gives rise to a high coercivity. The unique nanocomposite microstructure provides hints for developing rare-earth-lean high-performance magnets.

      Corrected by:

      Correction: Correction: Nd2Fe14B/FeCo Anisotropic Nanocomposite Films with a Large Maximum Energy Product

      Vol. 25, Issue 14, 1966, Version of Record online: 8 APR 2013

    21. Influence of D/A Ratio on Photovoltaic Performance of a Highly Efficient Polymer Solar Cell System (pages 6536–6541)

      Xia Guo, Maojie Zhang, Jiahui Tan, Shaoqing Zhang, Lijun Huo, Wenping Hu, Yongfang Li and Jianhui Hou

      Version of Record online: 9 OCT 2012 | DOI: 10.1002/adma.201202719

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      A new copolymer PIDTDTQx based on indacenodithiophene and quinoxaline is synthesized and characterized. The correlation between the D/A ratio, mobility, and photovoltaic properties, as well as morphology of the D/A blend based on a PIDTDTQx:PC70BM system is investigated. The power conversion efficiency of the polymer solar cells based on PIDTDTQx/PC70BM (1:4, w/w) reaches 7.51%.

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