Advanced Functional Materials

Cover image for Vol. 22 Issue 23

December 5, 2012

Volume 22, Issue 23

Pages 4845–5059

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    1. Optical Waveguides: Polymorphism-Dependent Emission for Di(p-methoxylphenyl)dibenzofulvene and Analogues: Optical Waveguide/Amplified Spontaneous Emission Behaviors (Adv. Funct. Mater. 23/2012) (page 4845)

      Xinggui Gu, Jingjing Yao, Guanxin Zhang, Yongli Yan, Chuang Zhang, Qian Peng, Qing Liao, Yishi Wu, Zhenzhen Xu, Yongsheng Zhao, Hongbing Fu and Deqing Zhang

      Article first published online: 3 DEC 2012 | DOI: 10.1002/adfm.201290140

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      The solid state emission of di(p-methoxylphenyl) dibenzofulvene and analogues is polymorphism dependent. The crystalline forms are strongly emissive, whereas the amorphous solid is weakly fluorescent. As reported by Guanxin Zhang, Dequing Zhang, and co-workers on page 4862, organic crystalline microrods based on the same molecular entity exhibit strong blue and yellow-green emission, outstanding optical waveguide behavior, and amplified spontaneous emission.

  2. Inside Front Cover

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    1. Hierarchical Structures: Ice-Templated Scaffolds with Microridged Pores Direct DRG Neurite Growth (Adv. Funct. Mater. 23/2012) (page 4846)

      Benjamin W. Riblett, Nicola L. Francis, Margaret A. Wheatley and Ulrike G. K. Wegst

      Article first published online: 3 DEC 2012 | DOI: 10.1002/adfm.201290142

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      Hierarchically structured scaffolds are generated by controlled freeze casting of an aqueous biopolymer solution. As reported by Ulrike G. K. Wegst and coworkers on page 4920, under specific freezing conditions, the scaffolds exhibit a highly regular and aligned lamellar architecture. These ridges run parallel to the pore axis and are seen to act as secondary guidance features to align the neuritis of dorsal root ganglia, which is imaged by fluorescent microscopy.

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    1. Stimuli-Responsive Materials: Light-Controlled Reversible Manipulation of Microgel Particle Size Using Azobenzene-Containing Surfactant (Adv. Funct. Mater. 23/2012) (page 5064)

      Yuriy Zakrevskyy, Marcel Richter, Svitlana Zakrevska, Nino Lomadze, Regine von Klitzing and Svetlana Santer

      Article first published online: 3 DEC 2012 | DOI: 10.1002/adfm.201290143

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      As reported by Yuriy Zakrevskyy and co-workers on page 5000, all-optical reversible control of the swelling/contraction transition of a microgel is realized using an azobenzene-containing surfactant. The azobenzene unit is switched between the more hydrophobic trans (blue light) and the more hydrophilic cis (UV light) state, which alters the surfactant's affinity to the microgel. The trans-surfactant binds to the gel triggering its contraction and the cissurfactant unbinds leading to microgel swelling.

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    1. Masthead: (Adv. Funct. Mater. 23/2012)

      Article first published online: 3 DEC 2012 | DOI: 10.1002/adfm.201290144

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    1. Contents: (Adv. Funct. Mater. 23/2012) (pages 4847–4854)

      Article first published online: 3 DEC 2012 | DOI: 10.1002/adfm.201290138

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    1. You have free access to this content
      Correction: A Phosphorescent Nanoparticle-Based Probe for Sensing and Imaging of (Intra)Cellular Oxygen in Multiple Detection Modalities (page 4854)

      Alina V. Kondrashina, Ruslan I. Dmitriev, Sergey M. Borisov, Ingo Klimant, Ian O'Brien, Yvonne M. Nolan, Alexander V. Zhdanov and Dmitri B. Papkovsky*

      Article first published online: 3 DEC 2012 | DOI: 10.1002/adfm.201290141

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    1. Distinct Molecular Motions in a Switchable Chromophore Dielectric 4-N,N-Dimethylamino-4′-N′-methylstilbazolium Trifluoromethanesulfonate (pages 4855–4861)

      Zhihua Sun, Junhua Luo, Tianliang Chen, Lina Li, Ren-Gen Xiong, Ming-Liang Tong and Maochun Hong

      Article first published online: 26 JUL 2012 | DOI: 10.1002/adfm.201201770

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      A new organic chromophore dielectric, 4-N,N-dimethylamino-4′-N′- methylstilbazolium trifluoromethanesulfonate, which undergoes a reversible phase transition with striking dielectric anomalies, is synthesized as a molecular rotator. Two very distinct molecular motions are observed, namely the “earth rotation” of partial units and the “earth revolution” of the whole molecule. Above its critical point, the anionic moiety exhibits an unprecedented 51.2° orientational motion.

    2. Polymorphism-Dependent Emission for Di(p-methoxylphenyl)dibenzofulvene and Analogues: Optical Waveguide/Amplified Spontaneous Emission Behaviors (pages 4862–4872)

      Xinggui Gu, Jingjing Yao, Guanxin Zhang, Yongli Yan, Chuang Zhang, Qian Peng, Qing Liao, Yishi Wu, Zhenzhen Xu, Yongsheng Zhao, Hongbing Fu and Deqing Zhang

      Article first published online: 27 JUL 2012 | DOI: 10.1002/adfm.201201482

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      Di(p-methoxylphenyl)dibenzofulvene and its analogues are investigated. Two crystalline forms of di(p-methoxylphenyl)dibenzofulvene are strongly blue- and yellow-green-emissive, whereas the amorphous solid is weakly fluorescent with orange emission. The results also manifest that the solid-state emission of diphenyldibenzofulvene can be tuned by varying the length of the alkoxyl chains. Moreover, their microrods exhibit outstanding optical waveguide and amplified spontaneous emission behaviors.

    3. Functional Coating of Porous Silica Microparticles with Native Biomembranes towards Portable Flow-Through Biochemical Microreactors (pages 4873–4878)

      Murat Tutus, Stefan Kaufmann, Ingrid M. Weiss and Motomu Tanaka

      Article first published online: 13 JUL 2012 | DOI: 10.1002/adfm.201200570

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      Deposition of native sarcoplasmic reticulum membranes on porous silica microparticles enables one to confine a large amount (1.1 m2) of transmembrane Ca2+-ATPase on a portable flow-through biochemical microreactor that can be operated in a robust and stable manner.

    4. You have full text access to this OnlineOpen article
      Hydrogel-Forming Microneedle Arrays for Enhanced Transdermal Drug Delivery (pages 4879–4890)

      Ryan F. Donnelly, Thakur Raghu Raj Singh, Martin J. Garland, Katarzyna Migalska, Rita Majithiya, Cian M. McCrudden, Prashant Laxman Kole, Tuan Mazlelaa Tuan Mahmood, Helen O. McCarthy and A. David Woolfson

      Article first published online: 9 JUL 2012 | DOI: 10.1002/adfm.201200864

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      Microneedle arrays prepared from crosslinked polymers, which contain no drug themselves, are described. They rapidly take up skin interstitial fluid upon skin insertion to form continuous, unblockable, hydrogel conduits from attached patch-type drug reservoirs to the dermal microcirculation. This technology has the potential to further enhance the capabilities of microneedle strategies for transdermal drug delivery, while bypassing current difficulties.

    5. Vesicular Structures Self-Assembled from Oligonucleotide-Polymer Hybrids: Mechanical Prevention of Bacterial Colonization Upon their Surface Tethering Through Hybridization (pages 4891–4898)

      Nicolas Cottenye, Karine Anselme, Lydie Ploux and Corinne Vebert-Nardin

      Article first published online: 20 JUL 2012 | DOI: 10.1002/adfm.201200988

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      Oligonucleotide-polymer hybrids form vesicular structures that can be immobilized onto surfaces through hybridization. This type of soft coating is able to prevent bacterial adhesion and colonization without an antimicrobial agent. This interesting property is due to the mechanical properties of the coating and is attributed to the dissipative properties of the vesicle-based coating.

  8. Frontispiece

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    1. Metallic Nanoparticles: Tuning the Porosity of Bimetallic Nanostructures by a Soft Templating Approach (Adv. Funct. Mater. 23/2012) (page 4899)

      Anaïs Lehoux, Laurence Ramos, Patricia Beaunier, Daniel Bahena Uribe, Philippe Dieudonné, Fabrice Audonnet, Arnaud Etcheberry, Miguel José-Yacaman and Hynd Remita

      Article first published online: 3 DEC 2012 | DOI: 10.1002/adfm.201290139

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      Hexagonal mesophases composed of oil-swollen surfactant-stabilized tubes arranged on a lattice in water and doped with metallic salts are used as soft templates for the synthesis of porous bimetallic nanostructures of controlled porosity and composition. As reported by Hynd Remita and co-workers on page 4900, the pore size can be varied from 10 to 55 nm and control over such a large range the porosity of nanomaterials is a premiere. Image courtesy of Eve Ranvier.

  9. Full Papers

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    1. Tuning the Porosity of Bimetallic Nanostructures by a Soft Templating Approach (pages 4900–4908)

      Anaïs Lehoux, Laurence Ramos, Patricia Beaunier, Daniel Bahena Uribe, Philippe Dieudonné, Fabrice Audonnet, Arnaud Etcheberry, Miguel José-Yacaman and Hynd Remita

      Article first published online: 30 JUL 2012 | DOI: 10.1002/adfm.201200666

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      Hexagonal mesophases composed of oil-swollen surfactant-stabilized tubes arranged on a lattice in water and doped with metallic salts are used as soft templates for the synthesis of porous bimetallic nanostructures of controlled porosity and composition. The pore size can be varied from 10 to 55 nm. Control over such a large range of porosity range of nanomaterials is reported for the first time.

    2. Printed and Electrochemically Gated, High-Mobility, Inorganic Oxide Nanoparticle FETs and Their Suitability for High-Frequency Applications (pages 4909–4919)

      Subho Dasgupta, Ganna Stoesser, Nina Schweikert, Ramona Hahn, Simone Dehm, Robert Kruk and Horst Hahn

      Article first published online: 20 JUL 2012 | DOI: 10.1002/adfm.201200951

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      Ink-jet-printed and electrochemically gated, high-mobility field-effect transistors based on inorganic-oxide nanoparticles are presented. The speed of electrochemical gating is experimentally assessed with equivalent circuits involving blocking electrodes. Effective capacitance is calculated considering the double-layer capacitance and the electrolyte resistance. The electrolyte polarization is found to be fast enough to ensure that the maximum attainable speed of the long-channel, printed transistors is limited by the printing resolution.

    3. Ice-Templated Scaffolds with Microridged Pores Direct DRG Neurite Growth (pages 4920–4923)

      Benjamin W. Riblett, Nicola L. Francis, Margaret A. Wheatley and Ulrike G. K. Wegst

      Article first published online: 27 JUL 2012 | DOI: 10.1002/adfm.201201323

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      Hierarchically structured scaffolds are generated by controlled freeze casting of an aqueous biopolymer solution. Under specific freezing conditions, the scaffolds exhibit a highly regular and aligned lamellar architecture. These ridges run parallel to the pore axis and are seen to act as secondary guidance features to align the neurites.

    4. Enhancing the Cellular Delivery of Nanoparticles Using Lipo-Oligoarginine Peptides (pages 4924–4930)

      Jae Sam Lee and Ching-Hsuan Tung

      Article first published online: 27 JUL 2012 | DOI: 10.1002/adfm.201201345

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      Gold nanoparticles (AuNPs) are functionalized by conjugating a hydrophobic fatty acid moiety and hydrophilic oligoarginine cell penetrating peptide on their surface to enhance cellular uptake and intracellular localization into cells. AMLPs (AuNPs conjugated with a myristoyl acid and an oligoarginine group) are effectively delivered into intracellular compartments of a cell without detectable cellular toxicity.

    5. A Phosphorescent Nanoparticle-Based Probe for Sensing and Imaging of (Intra)Cellular Oxygen in Multiple Detection Modalities (pages 4931–4939)

      Alina V. Kondrashina, Ruslan I. Dmitriev, Sergey M. Borisov, Ingo Klimant, Ian O'Brien, Yvonne M. Nolan, Alexander V. Zhdanov and Dmitri B. Papkovsky

      Article first published online: 20 JUL 2012 | DOI: 10.1002/adfm.201201387

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      A new cell-penetrating nanoparticle-based O2 probe based on Pt(II)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)-porphyrin (PtTFPP) and poly(9,9-dioctylfluorene) (PFO) antennae dye is described. The probe allows for the sensing and imaging of molecular oxygen in different detection modalities including ratiometric intensity and lifetime-based imaging under one- and two-photon excitation.

    6. CdTe Quantum Dots/Layered Double Hydroxide Ultrathin Films with Multicolor Light Emission via Layer-by-Layer Assembly (pages 4940–4948)

      Ruizheng Liang, Simin Xu, Dongpeng Yan, Wenying Shi, Rui Tian, Hong Yan, Min Wei, David G. Evans and Xue Duan

      Article first published online: 20 JUL 2012 | DOI: 10.1002/adfm.201201367

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      The fabrication of finely tunable multicolor-light-emitting ultrathin films (UTFs) with 2D architecture based on CdTe QDs and MgAl-layered double hydroxide nanosheets via the layer-by-layer deposition technique is reported. The UTFs, which have significantly enhanced luminescence efficiency and stability, can be potentially applied in multicolor optical and optoelectronic devices.

    7. LaPO4 Mineral Liquid Crystalline Suspensions with Outstanding Colloidal Stability for Electro-Optical Applications (pages 4949–4956)

      Jongwook Kim, Alexis de la Cotte, Rodolphe Deloncle, Samuel Archambeau, Claudine Biver, Jean-Paul Cano, Khalid Lahlil, Jean-Pierre Boilot, Eric Grelet and Thierry Gacoin

      Article first published online: 23 JUL 2012 | DOI: 10.1002/adfm.201200825

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      A new type of mineral liquid crystal system composed of LaPO4 particles with tuned long rod-like morphology self-organizes into different mesophases. An electro-optical experiment shows a very efficient alignment of the nanorod suspension exhibiting large birefringence under a weak electric field. This result, combined with the high intrinsic transparency and athermal behavior, opens the way towards a new class of self-assembling materials for electro-optical applications.

    8. The Ferroelectric Field Effect within an Integrated Core/Shell Nanowire (pages 4957–4961)

      Stephen S. Nonnenmann, Mohammad A. Islam, Brian R. Beatty, Eric M. Gallo, Terrence McGuckin and Jonathan E. Spanier

      Article first published online: 25 JUL 2012 | DOI: 10.1002/adfm.201200865

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      The ferroelectric field effect is demonstrated within individual semiconductor silicon-core, ferroelectric PbZr0.52Ti0.48O3 (PZT)-shell nanowires. The observed effect on the measured source–drain current approaches four orders of magnitude, despite a ferroelectric layer/semiconducting channel ratio nearly three orders smaller than that of conventional planar ferroelectric field-effect transistors (FeFETs).

    9. Continuous Control of Charge Transport in Bi-Deficient BiFeO3 Films Through Local Ferroelectric Switching (pages 4962–4968)

      Tae Heon Kim, Byung Chul Jeon, Taeyoon Min, Sang Mo Yang, Daesu Lee, Yong Su Kim, Seung-Hyub Baek, Wittawat Saenrang, Chang-Beom Eom, Tae Kwon Song, Jong-Gul Yoon and Tae Won Noh

      Article first published online: 25 JUL 2012 | DOI: 10.1002/adfm.201201490

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      Continuous control of charge transport and polarization hysteresis in Bi-deficient BiFeO3 films through local ferroelectric switching is demonstrated. Application of a dc voltage stress to Bi1-δFeO3 capacitors causes local polarization switching. In the switched domain regions, holes are injected at the film/bottom electrode interface, leading to reverse diode behavior. The injected holes are trapped near tail-to-tail domain walls, inducing a pinning effect with shrinkage of the polarization hysteresis loop.

    10. Microstructure and Texture of Polycrystalline CVD-ZnS Analyzed via EBSD (pages 4969–4974)

      Tilman Zscheckel, Wolfgang Wisniewski and Christian Rüssel

      Article first published online: 25 JUL 2012 | DOI: 10.1002/adfm.201103131

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      Industrially produced chemical vapor deposition (CVD)-ZnS is analyzed using electron backscatter diffraction (EBSD) and X-ray diffraction (XRD). Wurtzite is detected within the first layer of deposition. The following 1000 μm of crystal growth occur in the form of large, heavily twinned grains. A sharp grain-size transition to grains <50 μm in length is observed. Local textures are described as well as twinning and grain fragmentation in the form of continuous orientation change.

    11. pH-Responsive Peptide Mimic Shell Cross-Linked Magnetic Nanocarriers for Combination Therapy (pages 4975–4984)

      Kanhu C. Barick, Sarika Singh, Neena V. Jadhav, Dhirendra Bahadur, Badri N. Pandey and Puthusserickal A. Hassan

      Article first published online: 3 JUL 2012 | DOI: 10.1002/adfm.201201140

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      The design and development of water dispersible, pH responsive peptide mimic shell cross-linked magnetic nanocarriers with functionalized exteriors (amine and carboxyl) for conjugation of drugs is reported. Specifically, the high loading affinity of nanocarriers for an anticancer drug (doxorubicin), their sustained release profiles, magnetic-field-induced heating, low toxicity, and good cellular internalization make them suitable for combination therapy involving hyperthermia and chemotherapy.

    12. Designing Bio-Inspired Adhesives for Shear Loading: From Simple Structures to Complex Patterns (pages 4985–4992)

      Michael D. Bartlett, Andrew B. Croll and Alfred J. Crosby

      Article first published online: 23 JUL 2012 | DOI: 10.1002/adfm.201201344

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      Design criteria for bio-inspired adhesives under shear loading is presented. Force capacity predictions of common geometric control parameters such as thickness, aspect ratio, and contact area are experimentally confirmed. This understanding is extended to over 25 simple and complex adhesive patterns. The force capacity of the various attachment features is described with a simple scaling parameter.

    13. Oxide Sandwiched Metal Thin-Film Electrodes for Long-Term Stable Organic Solar Cells (pages 4993–4999)

      Sylvio Schubert, Martin Hermenau, Jan Meiss, Lars Müller-Meskamp and Karl Leo

      Article first published online: 25 JUL 2012 | DOI: 10.1002/adfm.201201592

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      A stable semitransparent thin silver top contact for organic solar cells is fabricated by sandwiching it between thermally evaporated MoO3 layers. By using a MoO3 interlayer, the morphology of the Ag electrode is improved, leading to better charge collection. The sandwich increases the electrode transmittance, photocurrent generation, and lifetime. With this, more efficient solar cells with lifetimes of 4500 h are achieved.

    14. Light-Controlled Reversible Manipulation of Microgel Particle Size Using Azobenzene-Containing Surfactant (pages 5000–5009)

      Yuriy Zakrevskyy, Marcel Richter, Svitlana Zakrevska, Nino Lomadze, Regine von Klitzing and Svetlana Santer

      Article first published online: 9 JUL 2012 | DOI: 10.1002/adfm.201200617

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      Remote reversible control of swelling/contraction transition of a microgel is realized using azobenzene-containing surfactant. The azobenzene unit is switched between more hydrophilic cis (UV light) and more hydrophobic trans (blue light) state, which alters the surfactant's affinity to the microgel. The trans-surfactant binds to the gel, triggering its contraction, and the cis-surfactant unbinds, leading to microgel swelling.

    15. Pore Filling of Spiro-OMeTAD in Solid-State Dye-Sensitized Solar Cells Determined Via Optical Reflectometry (pages 5010–5019)

      Pablo Docampo, Andrew Hey, Stefan Guldin, Robert Gunning, Ullrich Steiner and Henry J. Snaith

      Article first published online: 23 JUL 2012 | DOI: 10.1002/adfm.201201223

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      A facile and accurate optical method for determining the pore-filling fraction of organic hole-transporters into mesoporous TiO2 photoanodes is described. Using this technique it is determined that maximum pore-filling fractions of up to 80% are achievable, and the long-held belief that pore-filling is the limiting factor to fabricate efficient thick (over 5 μm) devices, which is necessary to achieve optimum photovoltaic performance with standard dyes, is challenged.

    16. Electrically Induced Disassembly of Electroactive Multilayer Films Fabricated from Water Soluble Polythiophenes (pages 5020–5027)

      Damia Mawad, Paul J. Molino, Sanjeev Gambhir, Julie M. Locke, David L. Officer and Gordon G. Wallace

      Article first published online: 23 JUL 2012 | DOI: 10.1002/adfm.201200999

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      Induced controlled dissolution of electroactive multilayer films constructed using water soluble polythiophenes can be achieved in response to applied potentials. For the first time, the disassembly of conducting-polymer-based multilayers is demonstrated to be induced by the application of potential, opening the way for new architectural designs for bionic devices.

    17. Wide Range Control of Microstructure and Mechanical Properties of Carbon Nanotube Forests: A Comparison Between Fixed and Floating Catalyst CVD Techniques (pages 5028–5037)

      Onnik Yaglioglu, Anyuan Cao, A. John Hart, Rod Martens and A. H. Slocum

      Article first published online: 26 JUL 2012 | DOI: 10.1002/adfm.201200852

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      Wide range stiffness tuning of carbon nanotube (CNT) forests over three orders of magnitude is presented by directly modifying the diameter and packing density of CNTs through the modulation of chemical vapor deposition (CVD) parameters. Fixed catalyst and floating catalyst CVD techniques exhibit significantly different deformation mechanisms and the open-cell foam model predicts the stiffness ratio within one type of CVD method very well.

    18. Ultrahigh Specific Capacitances for Supercapacitors Achieved by Nickel Cobaltite/Carbon Aerogel Composites (pages 5038–5043)

      Hsing-Chi Chien, Wei-Yun Cheng, Yong-Hui Wang and Shih-Yuan Lu

      Article first published online: 25 JUL 2012 | DOI: 10.1002/adfm.201201176

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      An outstanding supercapacitor electrode material, NiCo2O4/carbon aerogel composite, is developed that exhibits an ultrahigh specific capacitance. The success is made possible by the fuller utilization of NiCo2O4, enabled by using highly conductive mesoporous carbon aerogels as the hosting matrix and the successful creation of an ultrathin NiCo2O4 nanostructure on the backbone of the matrix through a two-step wet chemistry process.

    19. Probing Individual Layers in Functional Oxide Multilayers by Wavelength-Dependent Raman Scattering (pages 5044–5049)

      Jens Kreisel, Mads C. Weber, Nico Dix, Florencio Sánchez, Pamela. A. Thomas and Josep Fontcuberta

      Article first published online: 26 JUL 2012 | DOI: 10.1002/adfm.201201272

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      The integration of functional oxides on silicon requires the use of complex heterostructures where the structure and properties strongly depend on the strain state. A Raman study of a multilayer BaTiO3/LaNiO3/CeO2/YSZ thin-film structure on silicon is reported, demonstrating that wavelength-dependent Raman scattering is well adapted for the investigation of strain and structural changes in complex heterostructures or even nanocomposites.

    20. Vapor Phase Growth of Functional Pentacene Films at Atmospheric Pressure (pages 5050–5059)

      Cédric Rolin, Karolien Vasseur, Björn Niesen, Myriam Willegems, Robert Müller, Sören Steudel, Jan Genoe and Paul Heremans

      Article first published online: 27 JUL 2012 | DOI: 10.1002/adfm.201200896

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      The effect of carrier gas pressure on the growth of pentacene by organic vapor phase deposition is explored. At high pressures (>100 mbar), gas phase nucleation is observed, which results in rough layers. An optimized process window is defined to grow smooth pentacene thin films at atmospheric pressure. State-of-the-art transistors and circuits based on these films are demonstrated.

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