Open‐Shell Donor–Acceptor Conjugated Polymers with High Electrical Conductivity

Conductive polymers largely derive their electronic functionality from chemical doping, processes by which redox and charge‐transfer reactions form mobile carriers. While decades of research have demonstrated fundamentally new technologies that merge the unique functionality of these materials with the chemical versatility of macromolecules, doping and the resultant material properties are not ideal for many applications. Here, it is demonstrated that open‐shell conjugated polymers comprised of alternating cyclopentadithiophene and thiadiazoloquinoxaline units can achieve high electrical conductivities in their native “undoped” form. Spectroscopic, electrochemical, electron paramagnetic resonance, and magnetic susceptibility measurements demonstrate that this donor–acceptor architecture promotes very narrow bandgaps, strong electronic correlations, high‐spin ground states, and long‐range π‐delocalization. A comparative study of structural variants and processing methodologies demonstrates that the conductivity can be tuned up to 8.18 S cm^?1. This exceeds other neutral narrow bandgap conjugated polymers, many doped polymers, radical conductors, and is comparable to commercial grades of poly(styrene‐sulfonate)‐doped poly(3,4‐ethylenedioxythiophene). X‐ray and morphological studies trace the high conductivity to rigid backbone conformations emanating from strong π‐interactions and long‐range ordered structures formed through self‐organization that lead to a network of delocalized open‐shell sites in electronic communication. The results offer a new platform for the transport of charge in molecular systems.     

On-Chip Tightly Confined Guiding and Splitting of Surface Acoustic Waves Using Line Defects in Phononic Crystals

Phononic crystals (PnCs) exhibit acoustic properties that are not usually found in natural materials, which leads to the possibility of new devices for the complex manipulation of acoustic waves. In this article, a micron-scale phononic waveguide constructed by line defects in PnCs to achieve on-chip, tightly confined guiding, bending, and splitting of surface acoustic waves (SAWs) is reported. The PnC is made of a square lattice of periodic nickel pillars on a piezoelectric substrate. The PnC lattice constant, pillar diameter, and pillar height are set to 10, 7.5, and 3.2 µm, respectively, leading to a complete bandgap centered at 195 MHz. Interdigitated transducers are monolithically integrated on the same substrate for SAW excitation. The guiding, bending, and splitting of SAWs in the phononic waveguide are experimentally observed through measurement of the out-of-plane displacement fields using a scanning optical interferometer. The combination of destructive interference due to the Bragg bandgap and the interaction of the propagating wave with the pillars around the channel results in a tight confinement of the displacement field. The proposed phononic waveguides demonstrate the feasibility of precise local manipulation of SAW that is essential for emerging frontier applications, notably for phonon-based classical and quantum information processing.     

Light Amplification and Efficient Electroluminescence from a Solution-Processable Diketopyrrolopyrrole Derivative via Triplet-to-Singlet Upconversion

Over the years, achieving efficient electroluminescence (EL) while simultaneously having low light amplification thresholds under optical excitation has been the key to progression toward the long-thought objective of electrically pumped organic lasers. While significant progress in this regard has been made for organic semiconductors emitting in the blue–green region of the visible spectrum, organic laser dyes with low-energy emission (>600 nm) still suffer from high amplified spontaneous emission (ASE) thresholds and low external quantum efficiencies (EQEs) in devices. Herein, low ASE thresholds and efficient EL are reported from a solution-processable organic laser dye dithiophenyl diketopyrrolopyrrole (DT-DPP). The ASE threshold of 4 µJ cm⁻² at the wavelength of 620 nm is obtained while making constructive use of triplet excitons by doping DT-DPP in a green-emitting host matrix, which exhibits thermally activated delayed fluorescence (TADF). The organic light-emitting diode fabricated from this system gives a high EQE of 7.9% due to the efficient utilization of triplet excitons. Transient EL studies further show that a high reverse intersystem crossing rate is crucial in achieving lasing under electrical pumping from such TADF-assisted fluorescent systems.     

Interpolation techniques for building a continuous map from discrete wireless sensor network data

Wireless sensor networks (WSNs) typically gather data at a discrete number of locations. However, it is desirable to be able to design applications and reason about the data in more abstract forms than in points of data. By bestowing the ability to predict inter‐node values upon the network, it is proposed that it will become possible to build applications that are unaware of the concrete reality of sparse data. This interpolation capability is realised as a service of the network. In this paper, the ‘map’ style of presentation has been identified as a suitable sense data visualisation format. Although map generation is essentially a problem of interpolation between points, a new WSN service, called the map generation service, which is based on a Shepard interpolation method, is presented. A modified Shepard method that aims to deal with the special characteristics of WSNs is proposed. It requires small storage, can be localised and integrates the information about the application domain to further reduce the map generation cost and improve the mapping accuracy. Empirical analysis has shown that the map generation service is an accurate, a flexible and an efficient method. Copyright © 2011 John Wiley & Sons, Ltd.     

Electronic Structure and Optoelectronic Properties of Bismuth Oxyiodide Robust against Percent‐Level Iodine‐, Oxygen‐, and Bismuth‐Related Surface Defects

In the search for nontoxic alternatives to lead‐halide perovskites, bismuth oxyiodide (BiOI) has emerged as a promising contender. BiOI is air‐stable for over three months, demonstrates promising early‐stage photovoltaic performance and, importantly, is predicted from calculations to tolerate vacancy and antisite defects. Here, whether BiOI tolerates point defects is experimentally investigated. BiOI thin films are annealed at a low temperature of 100 °C under vacuum (25 Pa absolute pressure). There is a relative reduction in the surface atomic fraction of iodine by over 40%, reduction in the surface bismuth fraction by over 5%, and an increase in the surface oxygen fraction by over 45%. Unexpectedly, the Bi 4f_7/2 core level position, Fermi level position, and valence band density of states of BiOI are not significantly changed. Further, the charge‐carrier lifetime, photoluminescence intensity, and the performance of the vacuum‐annealed BiOI films in solar cells remain unchanged. The results show BiOI to be electronically and optoelectronically robust to percent‐level changes in surface composition. However, from photoinduced current transient spectroscopy measurements, it is found that the as‐grown BiOI films have deep traps located ≈0.3 and 0.6 eV from the band edge. These traps limit the charge‐carrier lifetimes of BiOI, and future improvements in the performance of BiOI photovoltaics will need to focus on identifying their origin. Nevertheless, these deep traps are three to four orders of magnitude less concentrated than the surface point defects induced through vacuum annealing. The charge‐carrier lifetimes of the BiOI films are also orders of magnitude longer than if these surface defects were recombination active. This work therefore shows BiOI to be robust against processing conditions that lead to percent‐level iodine‐, bismuth‐, and oxygen‐related surface defects. This will simplify and reduce the cost of fabricating BiOI‐based electronic devices, and stands in contrast to the defect‐sensitivity of traditional covalent semiconductors.     

Understanding Local and Macroscopic Electron Mobilities in the Fullerene Network of Conjugated Polymer‐based Solar Cells: Time‐Resolved Microwave Conductivity and Theory

The efficiency of bulk heterojunction (BHJ) organic photovoltaics is sensitive to the morphology of the fullerene network that transports electrons through the device. This sensitivity makes it difficult to distinguish the contrasting roles of local electron mobility (how easily electrons can transfer between neighboring fullerene molecules) and macroscopic electron mobility (how well‐connected is the fullerene network on device length scales) in solar cell performance. In this work, a combination of density functional theory (DFT) calculations, flash‐photolysis time‐resolved microwave conductivity (TRMC) experiments, and space‐charge‐limit current (SCLC) mobility estimates are used to examine the roles of local and macroscopic electron mobility in conjugated polymer/fullerene BHJ photovoltaics. The local mobility of different pentaaryl fullerene derivatives (so‐called ‘shuttlecock’ molecules) is similar, so that differences in solar cell efficiency and SCLC mobilities result directly from the different propensities of these molecules to self‐assemble on macroscopic length scales. These experiments and calculations also demonstrate that the local mobility of phenyl‐C₆₀ butyl methyl ester (PCBM) is an order of magnitude higher than that of other fullerene derivatives, explaining why PCBM has been the acceptor of choice for conjugated polymer BHJ devices even though it does not form an optimal macroscopic network. The DFT calculations indicate that PCBM's superior local mobility comes from the near‐spherical nature of its molecular orbitals, which allow strong electronic coupling between adjacent molecules. In combination, DFT and TRMC techniques provide a tool for screening new fullerene derivatives for good local mobility when designing new molecules that can improve on the macroscopic electron mobility offered by PCBM.     

Multi‐Site Functionalization of Protein Scaffolds for Bimetallic Nanoparticle Templating

The use of biological scaffolds to template inorganic material offers a strategy to synthesize precise composite nanostructures of different sizes and shapes. Proteins are unique biological scaffolds that consist of multiple binding regions or epitope sites that site‐specifically associate with conserved amino acid sequences within protein‐binding partners. These binding regions can be exploited as synthesis sites for multiple inorganic species within the same protein scaffold, resulting in bimetallic inorganic nanostructures. This strategy is demonstrated with the scaffold protein clathrin, which self‐assembles into spherical cages. Specifically, tether peptides that noncovalently associate with distinct clathrin epitope sites, while initiating simultaneous synthesis of two inorganic species within the assembled clathrin protein cage, are designed. The flexibility and diversity of this unique biotemplating strategy is demonstrated by synthesizing two types of composite structures (silver–gold mixed bimetallic and silver–gold core–shell nanostructures) from a single clathrin template. This noncovalent, Template Engineering Through Epitope Recognition, or TEThER, strategy can be readily applied to any protein system with known epitope sites to template a variety of bimetallic structures without the need for chemical or genetic mutations.     

Copper Sulfide (CuxS) Nanowire‐in‐Carbon Composites Formed from Direct Sulfurization of the Metal‐Organic Framework HKUST‐1 and Their Use as Li‐Ion Battery Cathodes

Li‐ion batteries containing cost‐effective, environmentally benign cathode materials with high specific capacities are in critical demand to deliver the energy density requirements of electric vehicles and next‐generation electronic devices. Here, the phase‐controlled synthesis of copper sulfide (Cu_xS) composites by the temperature‐controlled sulfurization of a prototypal Cu metal‐organic framework (MOF), HKUST‐1 is reported. The tunable formation of different Cu_xS phases within a carbon network represents a simple method for the production of effective composite cathode materials for Li‐ion batteries. A direct link between the sulfurization temperature of the MOF and the resultant Cu_xS phase formed with more Cu‐rich phases favored at higher temperatures is further shown. The Cu_xS/C samples are characterized through X‐ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy, and energy dispersive X‐ray spectroscopy (EDX) in addition to testing as Li‐ion cathodes. It is shown that the performance is dependent on both the Cu_xS phase and the crystal morphology with the Cu_1.8S/C‐500 material as a nanowire composite exhibiting the best performance, showing a specific capacity of 220 mAh g^?1 after 200 charge/discharge cycles.     

Identifying a Threshold Impurity Level for Organic Solar Cells: Enhanced First‐Order Recombination Via Well‐Defined PC84BM Traps in Organic Bulk Heterojunction Solar Cells

Small amounts of impurity, even one part in one thousand, in polymer bulk heterojunction solar cells can alter the electronic properties of the device, including reducing the open circuit voltage, the short circuit current and the fill factor. Steady state studies show a dramatic increase in the trap‐assisted recombination rate when [6,6]‐phenyl C₈₄ butyric acid methyl ester (PC₈₄BM) is introduced as a trap site in polymer bulk heterojunction solar cells made of a blend of the copolymer poly[N‐9″‐hepta‐decanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PCDTBT) and the fullerene derivative [6,6]‐phenyl C₆₁ butyric acid methyl ester (PC₆₀BM). The trap density dependent recombination studied here can be described as a combination of bimolecular and Shockley–Read–Hall recombination; the latter is dramatically enhanced by the addition of the PC₈₄BM traps. This study reveals the importance of impurities in limiting the efficiency of organic solar cell devices and gives insight into the mechanism of the trap‐induced recombination loss.     

Broadband,High‐Speed,and Large‐Amplitude Dynamic Optical Switching with Yttrium‐Doped Cadmium Oxide

Transparent conducting oxides, such as doped indium oxide, zinc oxide, and cadmium oxide (CdO), have recently attracted attention as tailorable materials for applications in nanophotonic and plasmonic devices such as low‐loss modulators and all‐optical switches due to their tunable optical properties, fast optical response, and low losses. In this work, optically induced extraordinarily large reflection changes (up to 135%) are demonstrated in bulk CdO films in the mid‐infrared wavelength range close to the epsilon near zero (ENZ) point. To develop a better understanding of how doping level affects the static and dynamic optical properties of CdO, the evolution of the optical properties with yttrium (Y) doping is investigated. An increase in the metallicity and a blueshift of the ENZ point with increasing Y‐concentrations is observed. Broadband all‐optical switching from near‐infrared to mid‐infrared wavelengths is demonstrated. The major photoexcited carrier relaxation mechanisms in CdO are identified and it is shown that the relaxation times can be significantly reduced by increasing the dopant concentration in the film. This work could pave the way to practical dynamic and passive optical and plasmonic devices with doped CdO spanning wavelengths from the ultraviolet to the mid‐infrared region.