Tunable Crystallinity in Regioregular Poly(3‐Hexylthiophene) Thin Films and Its Impact on Field Effect Mobility

The properties of poly(alkylthiophenes) in solution are found to have a profound impact on the self assembly process and thus the microstructural and electrical properties of the resultant thin films. Ordered supramolecular precursors can be formed in regioregular poly(3‐hexylthiophene) (P3HT) solutions through the application of low intensity ultrasound. These precursors survive the casting process, resulting in a dramatic increase in the degree of crystallinity of the thin films obtained by spin coating. The crystallinity of the films is tunable, with a continuous evolution of mesoscale structures observed as a function of ultrasonic irradiation time. The photophysical properties of P3HT in solution as well in the solid state suggest that the application of ultrasound leads to a π stacking induced molecular aggregation resulting in field effect mobilities as high as 0.03 cm² V^?1 s^?1. A multiphase morphology, comprising short quasi‐ordered and larger, ordered nanofibrils embedded in a disordered amorphous phase is formed as a result of irradiation for at least 1 min. Two distinct regions of charge transport are identified, characterized by an initial sharp increase in the field effect mobility by two orders of magnitude due to an increase in crystallinity up to the percolation limit, followed by a gradual saturation where the mobility becomes independent of the thin film microstructure.     

The Effect of Ketone Defects on the Charge Transport and Charge Recombination in Polyfluorenes

The effect of on‐chain ketone defects on the charge transport of the polyfluorene derivative poly(9,9‐dioctylfluorene) (PFO) is investigated. Using MoO₃ as ohmic hole contact, the hole transport in a pristine PFO diode is observed to be limited by space‐charge, whereas fluorenone contaminated PFO (PFO‐F) is shown to be trap limited by the occurrence of an exponential trap distribution with a trap depth of 0.18 eV. The electron transport in PFO is also observed to be trap limited, but in order to describe the electron transport of PFO‐F, an additional trap level with a depth of 0.46 eV must be introduced. The obtained energy levels of the fluorenone trapping sites are in close agreement with cyclic voltammetry (CV) measurements reported in literature. As a result, the fluorenone defects are shown to simultaneously act as hole‐ and electron trap. Moreover, through ideality factor measurements, the green emission associated with these defects is observed to originate from trap‐assisted recombination.     

Solid‐State Electrode Materials with Ionic‐Liquid Properties for Energy Storage: the Lithium Solid‐State Ionic‐Liquid Concept.

Herein, the novel concept of a solid‐state electrode materials with ionic‐liquid (IL) properties is presented. These composite materials are a mixture of electroactive matter, an electronic conductor, a solid‐state ionic conductor and a polymeric binder. The approach of a solid‐state ionic conductor combines the high safety of an IL with the nanoconfinement of such a liquid in a mesoporous silica framework, an ionogel, thus leading to a solid with liquid‐like ionic properties. The same ionic conductor is also used as a solid‐state separator to evaluate the properties of our solid‐state electrode materials in all‐solid‐state batteries. Such a concept of a solid‐state electrode material contributes to addressing the challenge of energy storage, which is one of the major challenges of the 21^st century. The ionogel, along with its processability, allows a single‐step preparation of the assembly of the solid‐state electrode and solid‐electrolyte separator and can be applied without specific adaptation to present, thick electrodes prepared by the widespread tape‐casting technique. The filling of the electrode porosity by an ionogel is shown by elemental mapping using scanning electron microscopy, and is subsequently confirmed by electrochemical measurements. The ionogel approach is successfully applied without specific adaptation to two state‐of‐the‐art, positive electroactive materials developed for future‐generation lithium‐ion batteries, namely LiFePO₄ and LiNi_1/3Mn_1/3Co_1/3O₂.     

Solvent‐Induced Morphology in Polymer‐Based Systems for Organic Photovoltaics

Studies on the influence of four different solvents on the morphology and photovoltaic performance of bulk‐heterojunction films made of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) via spin‐coating for photovoltaic applications are reported. Solvent‐dependent PCBM cluster formation and P3HT crystallization during thermal annealing are investigated with optical microscopy and grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and are found to be insufficient to explain the differences in device performance. A combination of atomic force microscopy (AFM), X‐ray reflectivity (XRR), and grazing‐incidence small‐angle X‐ray scattering (GISAXS) investigations results in detailed knowledge of the inner film morphology of P3HT:PCBM films. Vertical and lateral phase separation occurs during spin‐coating and annealing, depending on the solvent used. The findings are summarized in schematics and compared with the IV characteristics. The main influence on the photovoltaic performance arises from the vertical material composition and the existence of lateral phase separation fitting to the exciton diffusion length. Absorption and photoluminescence measurements complement the structural analysis.     

Supramolecular Order of Solution‐Processed Perylenediimide Thin Films: High‐Performance Small‐Channel n‐Type Organic Transistors

N,N′‐1H,1H‐perfluorobutyl dicyanoperylenecarboxydiimide (PDIF‐CN₂), a soluble and air stable n‐type molecule, undergoes significant reorganization upon thermal annealing after solution deposition on several substrates with different surface energies. Interestingly, this system exhibits an exceptional edge‐on orientation regardless of the substrate chemistry. This preferential orientation is rationalized in terms of strong intermolecular interactions between the PDIF‐CN₂ molecules. The presence of a pronounced π–π stacking is confirmed by combining near‐edge X‐ray absorption fine structure spectroscopy (NEXAFS), dynamic scanning force microscopy (SFM) and surface energy measurements. The remarkable charge carrier mobility measured in field‐effect transistors, using both bottom‐ and top‐contact (bottom‐gate) configurations, underlines the importance of strong intermolecular interactions for the realization of high performing devices.     

Improving satellite services with cooperative communications

This paper proposes new transmission schemes for the delivery of satellite services. In the proposed scenarios, mobile terminals are allowed to forward the signal received from the satellite. This scheme provides spatial diversity just like MIMO transmission schemes. Moreover, the coverage area is extended because masked terminals have an additional opportunity to get the service from neighboring terminals. We use the paradigm of cooperative communications to compare the advantages and limitations of several scenarios in hybrid terrestrial/satellite systems. In particular, we study the following basic transmission scheme: in a first time slot, the satellite sends its signal and, in a second time slot, mobile terrestrial terminals are relaying the satellite signal. An analysis framework is proposed and applied to this cooperation scenario at the destination terminal. The framework is modeling the cooperation process and clearly separates the control part from the data user part. The paper outlines the importance of the control part by evaluating the relay selection policy on a basic hybrid satellite/ad hoc system. Copyright © 2011 John Wiley & Sons, Ltd.     

Highly Efficient Video Codec for Entertainment‐Quality

We present a novel video codec for supporting entertainment‐quality video. It has new coding tools such as an intra prediction with offset, integer sine transform, and enhanced block‐based adaptive loop filter. These tools are used adaptively in the processing of intra prediction, transform, and loop filtering. In our experiments, the proposed codec achieved an average reduction of 13.35% in BD‐rate relative to H.264/AVC for 720p sequences.     

Intratumoral Thermal Reading During Photo‐Thermal Therapy by Multifunctional Fluorescent Nanoparticles

The tremendous development of nanotechnology is bringing us closer to the dream of clinical application of nanoparticles in photothermal therapies of tumors. This requires the use of specific nanoparticles that must be highly biocompatible, efficient light‐to‐heat converters and fluorescent markers. Temperature reading by the heating nanoparticles during therapy appears of paramount importance to keep at a minimum the collateral damage that could arise from undesirable excessive heating. In this work, this thermally controlled therapy is possible by using Nd³⁺ ion‐doped LaF₃ nanocrystals. Because of the particular optical features of Nd³⁺ ions at high doping concentrations, these nanoparticles are capable of in vivo photothermal heating, fluorescent tumor localization and intratumoral thermal sensing. The successful photothermal therapy experiments here presented highlight the importance of controlling therapy parameters based on intratumoral temperature measurements instead of on the traditionally used skin temperature measurements. In fact, significant differences between intratumoral and skin temperatures do exist and could lead to the appearance of excessive collateral damage. These results open a new avenue for the real application of nano­particle‐based photothermal therapy at clinical level.     

Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, solvent vapor annealing in supported thin films of poly(2‐hydroxyethyl methacrylate)‐block‐poly(methyl methacrylate) [PHEMA‐b‐PMMA] by means of grazing incidence small angle X‐ray scattering (GISAXS) is investigated. A spin‐coated thin film of a lamellar block copolymer is solvent vapor annealed to induce microphase separation and improve the long‐range order of the self‐assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents, which are chosen to be preferential for each block, enables selective formation of ordered lamellae, gyroid, hexagonal, or spherical morphologies from a single‐block copolymer with a fixed volume fraction. The selected microstructure is then kinetically trapped in the dry film by rapid drying. This paper describes what is thought to be the first reported case where in situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram.     

Metallic Glass as a Mechanical Material for Microscanners

Microelectromechanical system (MEMS) actuators essentially have movable silicon structures where the mechanical motion can be activated electronically. The microscanner is one of the most successfully commercialized MEMS devices which are widely used for collecting optical information, manipulating light, and displaying images. While silicon is abundant, it is also brittle and stiff and when microprocessed, defects are not uncommon. These defects result in weakness under torsional stress and this has been the key factor limiting the scanning performance of the microscanner. Here a metallic glass (MG)‐based microscanner is reported with MG as the material for the moving torsion bars. The low elastic modulus, high fracture toughness, and high strength of MG offers, for the first time, an ultralarge rotating angle of 146° with power consumption lowered to the microwatt range, and a smaller driving force and better actuation performance, than conventional single crystal silicon and polycrystalline silicon. The high spatial resolution and large scanning field of the MG‐based microscanner are demonstrated in the tomographic imaging of a human finger. This development of an MG‐based MEMS possibly opens a new field of low‐powered MEMS devices with extreme actuation and enhanced sensing.