Durable Ultraflexible Organic Photovoltaics with Novel Metal‐Oxide‐Free Cathode

Flexible and stretchable organic photovoltaics (OPVs) are promising as a power source for wearable devices with multifunctions ranging from sensing to locomotion. Achieving mechanical robustness and high power conversion efficiency for ultraflexible OPVs is essential for their successful application. However, it is challenging to simultaneously achieve these features by the difficulty to maintain stable performance under a microscale bending radius. Ultraflexible OPVs are proposed by employing a novel metal‐oxide‐free cathode that consists of a printed ultrathin metallic transparent electrode and an organic electron transport layer to achieve high electron‐collecting capabilities and mechanical robustness. In fact, the proposed ultraflexible OPV achieves a power conversion efficiency of 9.7% and durability with 74% efficiency retention after 500 cycles of deformation at 37% compression through buckling. The proposed approach can be applied to active layers with different morphologies, thus suggesting its universality and potential for high‐performance ultraflexible OPV devices.     

Transistor Paint: Environmentally Stable N‐alkyldithienopyrrole and Bithiazole‐Based Copolymer Thin‐Film Transistors Show Reproducible High Mobilities without Annealing

New solution processable 4‐(2‐hexyldecan)‐4H‐bisthieno[2,3‐d:3′,2′‐b]pyrrole and 4,4′‐dialkyl‐2,2′‐bithiazole‐based copolymers (PBTzDTPs) are synthesized with excellent FET performance. These novel copolymers have considerable potential in printable electronics as they have high charge carrier mobilities, excellent air stability, good solution processibility, and no requirement for post‐deposition thermal annealing, all requirements for this field of application. The thin film transistors fabricated from PBTzDTPs achieve field effect mobilities as high as 0.14 cm² V^?1 s^?1 with current on/off ratios up to 10⁶ without thermal annealing. In addition, the devices exhibit stable performance in air, showing no significant degradation over 60 days. Moreover, the polymers described here provide an excellent example of the systems in which higher mobility performance does not require higher crystalline, long‐range ordered structures. Such a system appears to be particularly promising for rapid fabrication techniques, where kinetic conditions usually prevent the development of long‐range order.     

Degradation of the covalent carbon–carbon bond between fullerene‐C60 and poly(1,3‐cyclohexadiene)

The degradation of fullerene‐C₆₀ (C₆₀) end‐capped poly(1,3‐cyclohexadiene) (C₆₀‐PCHD) with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) was examined to reveal the nature of the covalent carbon–carbon bond between C₆₀ and PCHD (C₆₀‐PCHD bond). The number average molecular weight (M_n) of C₆₀‐PCHD decreased with an increase in the degree of dehydrogenation, and the elimination of a PCHD arm from a C₆₀ occurred. The degradation of the C₆₀‐PCHD bond via a 1,4‐CHD unit was faster than that via a 1,2‐CHD unit, whereas the C₆₀‐poly(cyclohexane) bond was stable. The degradation of the C₆₀‐PCHD bond with DDQ was caused by the dehydrogenation of a CHD unit adjoining a C₆₀ core. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(4-diphenylaminostyrene) with a well-defined polymer chain structure: Controllable optical and electrical properties

The effect of polymer chain structure on the optical and electrical properties are reported for poly(4-diphenylaminostyrene) (PDAS), which was prepared by the living anionic polymerization of 4-diphenylaminostyrene (DAS) with the benzyllithium (BzLi)/N,N,N′,N′-tetramethylethylenediamine (TMEDA) system. The optical properties of PDAS are strongly affected by the stereoregularity of the PDAS polymer chain; intramolecular excimer-forming fluorescence was observed from PDAS with a syndiotactic-rich configuration. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PDAS were approximately −5.4 and −2.0 eV, respectively, regardless of the polymer chain structure. The hole and electron drift mobilities for PDAS were in the order of 10⁻⁴ to 10⁻⁵ (cm²/V s) and 10⁻⁵ (cm²/V s), respectively, with negative slopes. The distance of each triphenylamino (TPA) group in the polymer chain was a major factor influencing the drift mobility of PDAS. The current-voltage (I-V) characteristics of PDAS were controllable according to the polymer chain structure of PDAS.     

Thermal and electrical conduction properties of vertically aligned carbon nanotubes produced by water-assisted chemical vapor deposition

We present both thermal and electrical conduction properties of vertically aligned carbon nanotubes (VACNTs), synthesized by the water-assisted chemical vapor deposition method using Fe–Ti–O nanoparticles as catalyst. Thermal diffusivity and electrical resistance of VACNTs have been measured by the laser flash method and direct-current four-terminal method, respectively. The VACNTs are found to have thermal diffusivities of the same order as isotropic graphite and the electrical characteristics of semiconductors. The electrical resistance shows a T^−1/4 temperature dependence, which implies that the conduction of electrons is dominated by 3D Mott variable range hopping.     

Organic–silicate hybrid catalysts based on various defined structures for Knoevenagel condensation

Two types of organic–inorganic hybrid base catalysts are prepared. Organic-functionalized molecular sieves (OFMSs), particularly “amine-immobilized porous silicates”, are designed based on common idea to immobilize catalytic active sites on silicate surface. Silicate–organic composite materials (SOCMs), such as “ordered porous silicate–quaternary ammonium composite materials”, are the precursors of ordered porous silicates obtained during the synthesis. Both the OFMS and the SOCM are used as the catalysts for Knoevenagel condensation. Among the OFMSs, there is clear tendency that the use of molecular sieve with larger pore volume and/or surface area gives the product in higher yield. Aminopropylsilyl (AP)-functionalized mesoporous silicates such as AP-MCM-41 gives the product in high yield under mild conditions. No loss of activity is observed after repeated use for three times. The SOCMs are also active for the same reaction. The precursors of the mesoporous silicates are more active than those of microporous silicates. This material can be repeatedly used without significant loss of activity. High activity is not due to the leached species. The active sites of the SOCM catalysts are considered to be SiO⁻ moieties located on the pore-mouth. Activity of the SOCM increases when the reaction is carried out without solvent, whereas decrease in activity of the OFMS is observed in the solvent-free system.     

Synthesis of porphyrin-end-functionalized poly(p-phenylene) as a leaf-green-colored soluble semiconducting polymer: Control of π–π interactions for visible-light absorption

The synthesis of tetraphenylporphyrin (H₂TPP)-end-functionalized poly(p-phenylene) (H₂TPP-PPP) as a leaf-green-colored soluble semiconducting polymer with a well-controlled and defined polymer chain structure was achieved for the first time. Chloromethyl-end-functionalized poly(1,3-cyclohexadiene) (CM-PCHD) was prepared by the living anionic polymerization of 1,3-cyclohexadiene and the post-polymerization reaction of poly(1,3-cyclohexadienyl)lithium and chloro(chloromethyl)dimethylsilane. H₂TPP-end-functionalized PCHD (H₂TPP-PCHD) was then prepared by the addition of 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin to CM-PCHD. The dehydrogenation of H₂TPP-PCHD with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was performed under ultrasonic irradiation, and H₂TPP-PPP was obtained as a target polymer in almost quantitative yield. The –Si(CH₃)₂–CH₂–O– bond in H₂TPP-PPP effectively inhibited the coordination of the H₂TPP end-group onto the PPP moiety, and the aggregation of H₂TPP-PPP with the accumulation of the H₂TPP end-group was formed. H₂TPP-PPP exhibited a leaf-green color and had a very broad absorption band overlapping the visible-light region, similar to chlorophyll a.     

Evaluation of environmentally friendly lubricants for cold forging

The authors proposed double-layer-type environmentally friendly lubricants, which were composed of an undercoat, superior in adhering to a material, and an overcoat, superior in reducing the friction between the material and the die. The performance of these lubricants for cold forging was evaluated by the ring compression test, the combined forward rod-backward can extrusion-type friction test and the combined forward conical can-backward straight can extrusion-type friction test. The double-layer-type lubricants showed comparable friction characteristics and anti-pick-up properties to a conversion coating lubricant, when the film thickness and surface treatment before coating were improved. In a practical application by cold multistage forging, the double-layer-type lubricants showed a similar performance to a conversion coating lubricant.     

Experimental study on method of estimating strength of weld metal in steel structure

We conducted the welding experiment using three kinds of test piece, actual size, diaphragm and butt joint. Then, we examined the influence on strength, cooling time and carbon equivalent of weld metal by welding conditions on the different test pieces. We calculated an estimate of cooling time and chemical components. Consequently, we concluded that the strength of weld metal can be estimated by heat input, interpass temperature, carbon equivarent of welding wire and shape of test piece.     

Preparation and rate capability of Li4Ti5O12 hollow-sphere anode material

Spinel lithium titanate, Li₄Ti₅O₁₂, with novel hollow-sphere structure was fabricated by a sol–gel process using carbon sphere as template. The effect of the hollow-sphere structure as well as the wall thickness on the Li storage capability and high rate performance was electrochemically evaluated. High specific capacity, especially better high rate performance was achieved with this Li₄Ti₅O₁₂ hollow-sphere electrode material with thin wall thickness. It is believed that this macroporous hollow-sphere structure has shortened the Li diffusion distance, increased the contact area between Li₄Ti₅O₁₂ and electrolyte, and also led to better mixing of the active material with AB. All these factors have resulted in the good rate capability of the hollow-sphere structured Li₄Ti₅O₁₂ electrode material.