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.     

A Direct Approach to Organic/Inorganic Semiconductor Hybrid Particles via Functionalized Polyfluorene Ligands

Controlled Suzuki–Miyaura coupling polymerization of 7′‐bromo‐9′,9′‐dioctyl‐fluoren‐2′‐yl‐4,4,5,5‐tetramethyl‐[1,3,2]dioxaborolane initiated by bromo(4‐tert‐butoxycarbonylamino‐phenyl)(tri‐tert‐butylphosphine)palladium ( 1 ) or bromo(4‐diethoxyphosphoryl‐phenyl)(tri‐tert‐butylphosphine)palladium ( 2 ) yields functionalized polyfluorenes (M_n = 4 × 10³ g mol^?1, M_w/M_n < 1.2) with a single amine or phosphonic acid, respectively, end‐group. High temperature synthesis of cadmium selenide quantum dots with these functionalized polyfluorenes as stabilizing ligands yields hybrid particles consisting of good quality (e.g. emission full width at half maximum of 30 nm; size distribution σ < 10%) inorganic nanocrystals with polyfluorene attached to the surface, as corroborated by transmission electron microscopy analysis and analytical ultracentrifugation. Sedimentation studies on particle dispersions show that a substantial portion (ca. half) of the phosphonic acid terminated polyfluorene ligands is bound to the inorganic nanocrystals, versus ca. 5% for the amino‐functionalized polyfluorene ligands. Single particle micro‐photoluminescence spectroscopy shows an efficient and complete energy transfer from the polyfluorene layer to the inorganic quantum dot.     

Streaming analysis in wireless sensor networks

Two new incremental models for online anomaly detection in data streams at nodes in wireless sensor networks are discussed. These models are incremental versions of a model that uses ellipsoids to detect first, second, and higher‐ordered anomalies in arrears. The incremental versions can also be used this way but have additional capabilities offered by processing data incrementally as they arrive in time. Specifically, they can detect anomalies ‘on‐the‐fly’ in near real time. They can also be used to track temporal changes in near real‐time because of sensor drift, cyclic variation, or seasonal changes. One of the new models has a mechanism that enables graceful degradation of inputs in the distant past (fading memory). Three real datasets from single sensors in deployed environmental monitoring networks are used to illustrate various facets of the new models. Examples compare the incremental version with the previous batch and dynamic models and show that the incremental versions can detect various types of dynamic anomalies in near real time. Copyright © 2012 John Wiley & Sons, Ltd.     

Multisensor Data Product Fusion for Aerosol Research

Combining data sets from multiple satellite sensors is a powerful method for studying Earth-atmosphere problems. By fusing data, we can utilize the strengths of the individual sensors that may not be otherwise possible. In this paper, we provide the framework for combining level 2 data products, using data from three sensors aboard the National Aeronautics and Space Administration (NASA)'s Terra satellite. These data include top-of-the-atmosphere (TOA) radiative energy fluxes obtained from the Clouds and the Earth's Radiant Energy System (CERES), aerosol optical thickness from the multispectral Moderate Resolution Imaging Spectroradiometer (MODIS), and aerosol properties from the Multi-angle Imaging SpectroRadiometer (MISR). The CERES Single Scanner Footprint (SSF) contains the pixel level CERES TOA fluxes and the level 2 MODIS aerosol data. We specifically focus upon fusing the CERES SSF with the MISR aerosol products. Although this project was undertaken specifically to address aerosol research, the methods employed for fusing data products can be used for other problems requiring synergistic data sets. We present selected case studies over different aerosol regimes and indicate that multisensor information provides value-added information for aerosol research that is not available from a single sensor.     

Matrix Metalloproteinase Responsive,Proximity‐Activated Polymeric Nanoparticles for siRNA Delivery

Small interfering RNA (siRNA) has significant potential to evolve into a new class of pharmaceutical inhibitors, but technologies that enable robust, tissue‐specific intracellular delivery must be developed before effective clinical translation can be achieved. A pH‐responsive, smart polymeric nanoparticle (SPN) with matrix metalloproteinase (MMP)‐7‐dependent proximity‐activated targeting (PAT) is described here. The PAT‐SPN is designed to trigger cellular uptake and cytosolic delivery of siRNA once activated by MMP‐7, an enzyme whose overexpression is a hallmark of cancer initiation and progression. The PAT‐SPN is composed of a corona‐forming polyethylene glycol (PEG) block, an MMP‐7‐cleavable peptide, a cationic siRNA‐condensing block, and a pH‐responsive, endosomolytic terpolymer block that drives self‐assembly and forms the PAT‐SPN core. With this novel design, the PEG corona shields cellular interactions until it is cleaved in MMP‐7‐rich environments, shifting the SPN ζ‐potential from +5.8 to +14.4 mV and triggering a 2.5 fold increase in carrier internalization. The PAT‐SPN exhibits pH‐dependent membrane disruptive behavior that enables siRNA escape from endo‐lysosomal pathways. Intracellular siRNA delivery and knockdown of the model enzyme luciferase in R221A‐Luc mammary tumor cells is significantly increased by MMP‐7 pre‐activation (p < 0.05). These combined data indicate that the PAT‐SPN provides a promising new platform for tissue‐specific, proximity‐activated siRNA delivery to MMP‐rich pathological environments.     

Long‐Term Electrical and Mechanical Function Monitoring of a Human‐on‐a‐Chip System

The goal of human‐on‐a‐chip systems is to capture multiorgan complexity and predict the human response to compounds within physiologically relevant platforms. The generation and characterization of such systems is currently a focal point of research given the long‐standing inadequacies of conventional techniques for predicting human outcome. Functional systems can measure and quantify key cellular mechanisms that correlate with the physiological status of a tissue, and can be used to evaluate therapeutic challenges utilizing many of the same endpoints used in animal experiments or clinical trials. Culturing multiple organ compartments in a platform creates a more physiologic environment (organ–organ communication). Here is reported a human 4‐organ system composed of heart, liver, skeletal muscle, and nervous system modules that maintains cellular viability and function over 28 days in serum‐free conditions using a pumpless system. The integration of noninvasive electrical evaluation of neurons and cardiac cells and mechanical determination of cardiac and skeletal muscle contraction allows the monitoring of cellular function, especially for chronic toxicity studies in vitro. The 28‐day period is the minimum timeframe for animal studies to evaluate repeat dose toxicity. This technology can be a relevant alternative to animal testing by monitoring multiorgan function upon long‐term chemical exposure.     

Study of metal barrier deposition-induced damage to porous low-k materials

A unique test structure based on a metal-insulator-semiconductor planar capacitor (Pcap) design was used to investigate several aspects of metal barrier-induced low-k damage. A special term called Effective Damage Thickness was introduced to describe the degree of damage. Ta(N) barrier was deposited on various dielectric films with porosity up to 32%. It has been found that the Effective Damage Thickness increases as the porosity increases. The damage is influenced more by the porosity of low-k films than the film density. Furthermore, the damage was modulated by Ta(N) deposition conditions. More damage was observed when higher target and/or substrate bias power was used, suggesting that the ion energy of the barrier material plays an important role in the low-k damage mechanism. A same degree of damage was observed for Ta barrier as for Ta(N), suggesting that Ta(N) deposition-induced low-k damage was primarily caused by Ta ions not nitrogen. Impact of Ru(Ta) and Cu(Mn) self forming barrier on low-k damage was also investigated. Among all the barriers studied in this work, the Ta-based barriers caused the most damage while the Cu(Mn) self forming barrier had the least damage to the low-k. The atomic masses for Ta, Ru, and Cu are 181, 101, and 64, respectively, corresponding with the observed degree of damage in the low-k material.     

Electrophysiological imaging of brain activity and connectivity-challenges and opportunities

Unlocking the dynamic inner workings of the brain continues to remain a grand challenge of the 21st century. To this end, functional neuroimaging modalities represent an outstanding approach to better understand the mechanisms of both normal and abnormal brain functions. The ability to image brain function with ever increasing spatial and temporal resolution has made a significant leap over the past several decades. Further delineation of functional networks could lead to improved understanding of brain function in both normal and diseased states. This paper reviews recent advancements and current challenges in dynamic functional neuroimaging techniques, including electrophysiological source imaging, multimodal neuroimaging integrating fMRI with EEG/MEG, and functional connectivity imaging.     

Quantification of Temperature-Dependent Charge Separation and Recombination Dynamics in Non-Fullerene Organic Photovoltaics

Transient optical spectroscopy is used to quantify the temperature-dependence of charge separation and recombination dynamics in P3TEA:SF-PDI₂ and PM6:Y6, two non-fullerene organic photovoltaic (OPV) systems with a negligible driving force and high photocurrent quantum yields. By tracking the intensity of the transient electroabsorption response that arises upon interfacial charge separation in P3TEA:SF-PDI₂, a free charge generation rate constant of ≈2.4 × 10¹⁰ s⁻¹ is observed at room temperature, with an average energy of ≈230 meV stored between the interfacial charge pairs. Thermally activated charge separation is also observed in PM6:Y6, and a faster charge separation rate of ≈5.5 × 10¹⁰ s⁻¹ is estimated at room temperature, which is consistent with the higher device efficiency. When both blends are cooled down to cryogenic temperature, the reduced charge separation rate leads to increasing charge recombination either directly at the donor-acceptor interface or via the emissive singlet exciton state. A kinetic model is used to rationalize the results, showing that although photogenerated charges have to overcome a significant Coulomb potential to generate free carriers, OPV blends can achieve high photocurrent generation yields given that the thermal dissociation rate of charges outcompetes the recombination rate.     

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.