A Thermoplastic Gel Electrolyte for Stable Quasi‐Solid‐State Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) are receiving considerable attention as low‐cost alternatives to conventional solar cells. In DSSCs based on liquid electrolytes, a photoelectric efficiency of 11 % has been achieved, but potential problems in sealing the cells and the low long‐term stability of these systems have impeded their practical use. Here, we present a thermoplastic gel electrolyte (TPGE) as an alternative to the liquid electrolytes used in DSSCs. The TPGE exhibits a thermoplastic character, high conductivity, long‐term stability, and can be prepared by a simple and convenient protocol. The viscosity, conductivity, and phase state of the TPGE can be controlled by tuning the composition. Using 40 wt % poly(ethylene glycol) (PEG) as the polymeric host, 60 wt % propylene carbonate (PC) as the solvent, and 0.65 M KI and 0.065 M I₂ as the ionic conductors, a TPGE with a conductivity of 2.61 mS cm^–2 is prepared. Based on this TPGE, a DSSC is fabricated with an overall light‐to‐electrical‐energy conversion efficiency of 7.22 % under 100 mW cm^–2 irradiation. The present findings should accelerate the widespread use of DSSCs.     

Influences of Connecting Unit Architecture on the Performance of Tandem Organic Light‐Emitting Devices

The present work investigates the influence of the n‐type layer in the connecting unit on the performance of tandem organic light‐emitting devices (OLEDs). The n‐type layer is typically an organic electron‐transporting layer doped with reactive metals. By systematically varying the metal dopants and the electron‐transporting hosts, we have identified the important factors affecting the performance of the tandem OLEDs. Contrary to common belief, device characteristics were found to be insensitive to metal work functions, as supported by the ultraviolet photoemission spectroscopy results that the lowest unoccupied molecular orbitals of all metal‐doped n‐type layers studied here have similar energy levels. It suggests that the electron injection barriers from the connecting units are not sensitive to the metal dopant used. On the other hand, it was found that performance of the n‐type layers depends on their electrical conductivities which can be improved by using an electron‐transporting host with higher electron mobility. This effect is further modulated by the optical transparency of constituent organic layers. The efficiency of tandem OLEDs would decrease as the optical transmittance decreases.     

Large‐Scale Synthesis,Annealing, Purification,and Magnetic Properties of Crystalline Helical Carbon Nanotubes with Symmetrical Structures

Crystalline helical carbon nanotubes (HCNTs) are synthesized as the main products in the pyrolysis of acetylene at 450 °C over Fe nanoparticles generated by means of a combined sol–gel/reduction method. Transmission electron microscopy (TEM) images reveal that there are two HCNTs attached to each Fe₃C nanoparticle, and that the two HCNTs are mirror images of each other. Annealing in Ar at 750 °C and purification by immersion in hot (90 °C) HCl solution do not significantly change the structure of the HCNTs, despite the partial removal of Fe nanoparticles by the latter treatment. The magnetic properties of the as‐prepared, annealed, and purified HCNTs have been systematically examined. The annealed sample shows relatively high magnetization due to the ferromagnetic α‐Fe nanoparticles encapsulated in the HCNT nodes. In the case of HCl treatment, relatively pure HCNTs are obtained by the removal of ferromagnetic nanoparticles from the double‐HCNT nodes. The effects of the amount of catalyst used in the synthesis process on the morphology and yield of the carbon products have also been investigated.     

Solvent‐Mediated Plasmon Tuning in a Gold‐Nanoparticle–Poly(Ionic Liquid) Composite

The design, synthesis, and characterization of a hierarchically ordered composite whose structure and optical properties can be reversibly switched by adjustment of solvent conditions are described. Solvent‐induced swelling and de‐swelling is shown to provide control over the internal packing arrangement and hence, optical properties of in situ synthesized metal nanoparticles. Specifically, a gold‐nanoparticle‐containing ionic‐liquid‐derived polymer is synthesized in a single step by UV irradiation of a metal‐ion‐precursor‐doped, self‐assembled ionic liquid gel, 1‐decyl‐3‐vinylimidazolium chloride. Small‐angle X‐ray scattering (SAXS) studies indicate that in the de‐swollen state, the freestanding polymer adopts a perforated lamellar structure. Optical spectroscopy of the dried composite reveals plasmon resonances positioned in the near‐IR. Strong particle–particle interactions arise from matrix‐promoted formation of aggregated 1D clusters or chains of gold nanoparticles. Upon swelling in alcohol, the composite undergoes a structural conversion to a disordered structure, which is accompanied by a color change from purple to pale pink and a shift in the surface plasmon resonance to 527 nm, consistent with isolated, non‐interacting particles. These results demonstrate the far‐field tuning of the plasmonic spectrum of gold nanoparticles by solvent‐mediated changes in its encapsulating matrix, offering a straightforward, low‐cost strategy for the fabrication of nanophotonic materials.     

Novel Heteroleptic CuI Complexes with Tunable Emission Color for Efficient Phosphorescent Light‐Emitting Diodes

A series of orange‐red to red phosphorescent heteroleptic Cu^I complexes (the first ligand: 2,2′‐biquinoline (bq), 4,4′‐diphenyl‐2,2′‐biquinoline (dpbq) or 3,3′‐methylen‐4,4′‐diphenyl‐2,2′‐biquinoline (mdpbq); the second ligand: triphenylphosphine or bis[2‐(diphenylphosphino)phenyl]ether (DPEphos)) have been synthesized and fully characterized. With highly rigid bulky biquinoline‐type ligands, complexes [Cu(mdpbq)(PPh₃)₂](BF₄) and [Cu(mdpbq)(DPEphos)](BF₄) emit efficiently in 20 wt % PMMA films with photoluminescence quantum yield of 0.56 and 0.43 and emission maximum of 606 nm and 617 nm, respectively. By doping these complexes in poly(vinyl carbazole) (PVK) or N‐(4‐(carbazol‐9‐yl)phenyl)‐3,6‐bis(carbazol‐9‐yl) carbazole (TCCz), phosphorescent organic light‐emitting diodes (OLEDs) were fabricated with various device structures. The complex [Cu(mdpbq)(DPEphos)](BF₄) exhibits the best device performance. With the device structure of ITO/PEDOT/TCCz:[Cu(mdpbq)(DPEphos)](BF₄) (15 wt %)/TPBI/LiF/Al (III), a current efficiency up to 6.4 cd A^–1 with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.61, 0.39) has been realized. To our best knowledge, this is the first report of efficient mononuclear Cu^I complexes with red emission.     

Solution‐Processible Multi‐component Cyclometalated Iridium Phosphors for High‐Efficiency Orange‐Emitting OLEDs and Their Potential Use as White Light Sources

The synthesis and photophysical studies of several multifunctional phosphorescent iridium(III) cyclometalated complexes consisting of the hole‐transporting carbazole and fluorene‐based 2‐phenylpyridine moieties are reported. All of them are isolated as thermally and morphological stable amorphous solids. Extension of the π‐conjugation through incorporation of electron‐pushing carbazole units to the fluorene fragment leads to bathochromic shifts in the emission profile, increases the highest occupied molecular orbital levels and improves the charge balance in the resulting complexes because of the propensity of the carbazole unit to facilitate hole transport. These iridium‐based triplet emitters give a strong orange phosphorescence light at room temperature with relatively short lifetimes in the solution phase. The photo‐ and electroluminescence properties of these phosphorescent carbazolylfluorene‐functionalized metalated complexes have been studied in terms of the coordinating position of carbazole to the fluorene unit. Organic light‐emitting diodes (OLEDs) using these complexes as the solution‐processed emissive layers have been fabricated which show very high efficiencies even without the need for the typical hole‐transporting layer. These orange‐emitting devices can produce a maximum current efficiency of ～ 30 cd A^–1 corresponding to an external quantum efficiency of ～ 10 % ph/el (photons per electron) and a power efficiency of ～ 14 lm W^–1. The homoleptic iridium phosphors generally outperform the heteroleptic counterparts in device performance. The potential of exploiting these orange phosphor dyes in the realization of white OLEDs is also discussed.     

A Substitution‐Dependent Light‐Up Fluorescence Probe for Selectively Detecting Fe3+ Ions and Its Cell Imaging Application

Deliberate design of specific and sensitive molecular probes with distinctive physical/chemical properties for analyte sensing is of great significance. Herein, by taking advantage of the position‐dependent substituent effects, an aggregation‐induced emission featured iron (III) probe from ortho‐substituted pyridinyl‐functionalized tetraphenylethylene (TPE‐o‐Py) is synthesized. It displays high sensitivity and selectivity toward iron (III) detection. The recognition arises from the position isomer of ortho‐substitution, and the fact that TPE‐o‐Py has a low acid dissociation constant (pK _a) that is close to that of hydrolyzed Fe³⁺. Importantly, TPE‐o‐Py as a light‐up fluorescence probe could be employed for Fe³⁺ sensing in living cells with a pronounced red‐shift in fluorescence emission.     

CdS Quantum Dots Encapsulated in Chiral Nematic Mesoporous Silica: New Iridescent and Luminescent Materials

Simultaneous integration of light emission and iridescence into a semiconducting photonic material is attractive for the design of new optical devices. Here, a straightforward, one‐pot approach for liquid crystal self‐assembly of semiconductor quantum dots into cellulose nanocrystal‐templated silica is developed. Through a careful balance of the intermolecular interactions between a lyotropic tetraalkoxysilane/cellulose nanocrystal dispersion and water‐soluble polyacrylic acid/mercaptopropionic acid‐stabilized CdS quantum dots, CdS/silica/nanocellulose composites that retain both chiral nematic order of the cellulose nanocrystals and emission of the quantum dots are successfully co‐assembled. Subsequent removal of the cellulose template and organic stabilizers in the composites by controlled calcination generates new freestanding iridescent, luminescent chiral nematic mesoporous silica‐encapsulated CdS films. The pores of these materials are accessible to analytes and, consequently, the CdS quantum dots undergo strong luminescence quenching when exposed to TNT solutions or vapor.     

Biocompatible Electromechanical Actuators Composed of Silk‐Conducting Polymer Composites

Single‐component, metal‐free, biocompatible, electromechanical actuator devices are fabricated using a composite material composed of silk fibroin and poly(pyrrole) (PPy). Chemical modification techniques are developed to produce free‐standing films with a bilayer‐type structure, with unmodified silk on one side and an interpenetrating network (IPN) of silk and PPy on the other. The IPN formed between the silk and PPy prohibits delamination, resulting in a durable and fully biocompatible device. The electrochemical stability of these materials is investigated through cyclic voltammetry, and redox sensitivity to the presence of different anions is noted. Free‐end bending actuation performance and force generation within silk‐PPy composite films during oxidation and reduction in a biologically relevant environment are investigated in detail. These silk–PPy composites are stable to repeated actuation, and are able to generate forces comparable with natural muscle (>0.1 MPa), making them ideal candidates for interfacing with biological tissues.     

An adaptive power pricing scheme for improved fairness in energy‐constrained cooperative networks

This paper presents an adaptive power pricing scheme to address the fairness issue with relay selection and power allocation in decode‐and‐forward‐based opportunistic relaying networks, which is focused on the scenario where a distributed energy‐constrained cooperative communication system is employed over Rayleigh fading channels. Specifically, the proposed scheme is conducted analytically by obtaining the mathematical expression for the symbol error probability using the statistical characteristic of the signal‐to‐noise ratio, and it also takes the residual energy of nodes into consideration. Numerical results show that the proposed scheme has the advantage of better system reliability and further improves the throughput of the whole network compared with previous algorithms without considering fairness. Copyright © 2013 John Wiley & Sons, Ltd.