Influence of blend microstructure on bulk heterojunction organic photovoltaic performance

The performance of organic photovoltaic devices based upon bulk heterojunction blends of donor and acceptor materials has been shown to be highly dependent on the thin film microstructure. In this tutorial review, we discuss the factors responsible for influencing blend microstructure and how these affect device performance. In particular we discuss how various molecular design approaches can affect the thin film morphology of both the donor and acceptor components, as well as their blend microstructure. We further examine the influence of polymer molecular weight and blend composition upon device performance, and discuss how a variety of processing techniques can be used to control the blend microstructure, leading to improvements in solar cell efficiencies.     

Poly(3-alkylthiophene) diblock copolymers with ordered microstructures and continuous semiconducting pathways

Conjugated rod-coil diblock copolymers self-assemble due to a balance of liquid crystalline (rod-rod) and enthalpic (rod-coil) interactions. Previous work has shown that while classical block copolymers self-assemble into a wide variety of nanostructures, when rod-rod interactions dominate self-assembly in rod-coil block copolymers, lamellar structures are preferred. Here, it is demonstrated that other, potentially more useful, nanostructures can be formed when these two interactions are more closely balanced. In particular, hexagonally packed polylactide (PLA) cylinders embedded in a semiconducting poly(3-alkylthiophene) (P3AT) matrix can be formed. This microstructure has been long-sought as it provides an opportunity to incorporate additional functionalities into a majority phase nanostructured conjugated polymer, for example in organic photovoltaic applications. Previous efforts to generate this phase in polythiophene-based block copolymers have failed due to the high driving force for P3AT crystallization. Here, we demonstrate that careful design of the P3AT moiety allows for a balance between crystallization and microphase separation due to chemical dissimilarity between copolymer blocks. In addition to hexagonally packed cylinders, P3AT-PLA block copolymers form nanostructures with long-range order at all block copolymer compositions. Importantly, the conjugated moiety of the P3AT-PLA block copolymers retains the crystalline packing structure and characteristic high time-of-flight charge transport of the homopolymer polythiophene (μ(h) ~10(-4) cm(2) V(-1) s(-1)) in the confined geometry of the block copolymer domains.     

Einstein's Equations and Associated Linear Systems

The relationship between Einstein's field equations and classical higher spin field equations is investigated using two-component spinor valued differential forms. Linear systems of equations associated to both the vacuum and coupled gravitational matter field equations are constructed. The latter equations are shown to be the integrability conditions of the linear systems.     

Dark field microscopy for diffraction analysis of amorphous carbon solids

Diffraction methods for determining structure in non-crystalline materials often rely solely on the determination of pair correlation functions, extracted from measurements of the diffracted intensity. A dark field image of a non-crystalline solid taken with a conventional transmission electron microscope contains phase information lost in the measurement of the diffracted intensity which can be accessed by evaluating a variance function. This variance function is defined in terms of spherical averages of the diffracted intensity and the mean square of the diffracted intensity. The latter contains higher order correlation information derived from correlations between two pairs of atoms. We examine the sensitivity of the variance function, to subtle atomic structural differences between carbon network structures. The structures have similar pair correlations, but different levels of diamond like bonding. The variance function is shown to give improved discrimination between the networks.     

Fluorinated NLO polymers with improved optical transparency in the near infrared

The absorption from vibrational overtones in the near infrared and specifically at 1.55 μm, is a major contribution to the optical loss of NLO polymer waveguides. In an effort to reduce this value, the specific molecular vibrations responsible, which had previously been predicted by theoretical means, were identified by solvent spectra analysis. A scheme was proposed to reduce the intrinsic absorption through synthetic modification of the polymer by replacement of appropriate aliphatic C? H bonds with C? F bonds. Specific bonds were chosen for replacement based on a consideration of both contribution to intrinsic absorption as well as ease of synthetic modification. The target polymer was synthesized and its absorption measured by a solution technique. A reduction in optical loss at 1.55 µ from 0.75 to 0.35 dB cm^?1 was achieved. © 1995 John Wiley & Sons, Inc.     

Analytical electron microscopy of a reaction-bonded Si3N4-based ceramic containing oxide additions

The microstructure of a silicon nitride (Si₃N₄)-based ceramic, prepared by a process combining direct nitridation and reactive liquid phase sintering of silicon/ceramic oxide powder compacts, has been characterised using analytical transmission electron microscopy. The presence of the reactive liquid phase, promoted by the addition of oxides from the CaO-Al₂O₃-SiO₂ ternary system, resulted in an as-fired microstructure containing a mixture of crystalline phases based on -Si₃N₄, β-Si₃N₄ and Si₂ N₂O, and distinct amorphous regions rich in Si, Al and Ca. X-ray microanalysis revealed the calcium to be wholly partitioned to the glassy phase, while significant concentrations of aluminium were detected in both β-Si₃N₄ and Si₂N₂O. The observed compositions of these phases, together with measured lattice parameters systematically in excess of those of the pure compounds, imply that they are in fact β- and O-sialons respectively. Semi-quantitative energy dispersive X-ray spectroscopy, using an ultra-thin window detector, is demonstrated to be capable of distinguishing clearly between these phases according to their oxygen content and of determining the aluminium content of both phases to within ± 1 equ.%, even at concentration levels of <5 equ.%.     

Molecular packing of high-mobility diketo pyrrolo-pyrrole polymer semiconductors with branched alkyl side chains

We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm(2) V(-1) s(-1), with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packing and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.     

Quantum: Einstein,Bohr and the Great Debate About the Nature of Reality,by Manjit Kumar

The history of absolute measurements of gravity is mentioned and the reasons for making absolute measurements are indicated. The principles and main advantages and difficulties of the main method—reversible pendulum, free fall, symmetrical free motion—are discussed and examples of each method are described. Problems of comparison of different determinations and of estimating systematic errors are considered.     

Chermak–Delgado simple groups

This paper provides the first steps in classifying the finite solvable groups having Property A, which is a property involving abelian normal subgroups. We see that this classification is reduced to classifying the solvableChermak–Delgado simple groups, which the author defines. The notion of “Chermak–Delgado simple,” or “CD-simple” for short, is a generalization of simple groups through the Chermak–Delgado lattice. The author completes a classification of Chermak–Delgado simple groups under certain restrictions on the primes involved in the group order.     

A new synthesis of substituted α-methylene-γ-lactones

Ene reactions of suitably substituted olefins with dimethyl acetylenedicarboxylate give substituted 1,4-pentadiene-1,2-dicarboxylates, which undergo acid-catalyzed cyclization to α-carbomethoxymethylene γ-lactones.