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The directed self-assembly (DSA) of block copolymers (BCP) is an emerging resolution enhancement tool that can multiply or subdivide the pitch of a lithographically defined chemical or topological pattern and is a resolution enhancement candidate to augment conventional lithography for patterning sub-20 nm features. Continuing the development of this technology will require an improved understanding of the polymer physics involved as well as experimental confirmation of the simulations used to guide the design process. Both of these endeavors would be greatly facilitated by a metrology, which is capable of probing the internal morphology of a DSA film. We have developed a new measurement technique, resonant critical-dimension small-angle X-ray scattering (res-CDSAXS), to evaluate the 3D buried features inside the film. This is an X-ray scattering measurement where the sample angle is varied to probe the 3D structure of the film, while resonant soft X-rays are used to enhance the scattering contrast. By measuring the same sample with both res-CDSAXS and traditional CDSAXS (with hard X-rays), we are able to demonstrate the dramatic improvement in scattering obtained through the use of resonant soft X-rays. Analysis of the reciprocal space map constructed from the res-CDSAXS measurements allowed us to reconstruct the complex buried features in DSA BCP films. We studied a series of DSA BCP films with varying template widths, and the internal morphologies for these samples were compared to the results of single chain in mean-field simulations. The measurements revealed a range of morphologies that occur with changing template width, including results that suggest the presence of mixed morphologies composed of both whole and necking lamella. The development of res-CDSAXS will enable a better understanding of the fundamental physics behind the formation of buried features in DSA BCP films.

Organic semiconductors hold immense promise for the development of a wide range of innovative devices with their excellent electronic and manufacturing characteristics. Of particular interest are nonmagnetic organic semiconductors that show unusual magnetic field effects (MFEs) at small subtesla field strength that can result in substantial changes in their optoelectronic and electronic properties. These unique phenomena provide a tremendous opportunity to significantly impact the functionality of organic-based devices and may enable disruptive electronic and spintronic technologies. Here, we present an approach to vary the MFEs on the electrical resistance of organic-based systems in a simple yet reliable fashion. We experimentally modify the interfacial characteristics by adding a self-assembled monolayer between the metal electrode and the organic semiconductor, thus enabling the tuning of competing MFE mechanisms coexisting in organic semiconductors. This approach offers a robust method for tuning the magnitude and sign of magnetoresistance in organic semiconductors without compromising the ease of processing.

We employed nanobeam X-ray diffraction using an X-ray spot size of 150 nm to investigate the local structure of P3HT thin films. We derived nanoscale real space maps of the X-ray diffraction properties at the π-π (020) diffraction peak. The X-ray data reveal a complex nanoscale structure of the polymer network with strong local variation where some areas of the film display a rather high degree of angular order. We quantify both the magnitude and direction of the angular order. Our results provide new insights into the local structural properties and connectivity of P3HT films.

Ion-conductive polymers, or ionomers, are critical materials for a wide range of electrochemical technologies. For optimizing the complex heterogeneous structures in which they occur, there is a need to elucidate the governing structure-property relationships, especially at nanoscale dimensions where interfacial interactions dominate the overall materials response due to confinement effects. It is widely acknowledged that polymer physical behavior can be drastically altered from the bulk when under confinement and the literature is replete with examples thereof. However, there is a deficit in the understanding of ionomers when confined to the nanoscale, although it is apparent from literature that confinement can influence ionomer properties. Herein we show that as one particular ionomer, Nafion, is confined to thin films, there is a drastic increase in the modulus over the bulk value, and we demonstrate that this stiffening can explain previously observed deviations in materials properties such as water transport and uptake upon confinement. Moreover, we provide insight into the underlying confinement-induced stiffening through the application of a simple theoretical framework based on self-consistent micromechanics. This framework can be applied to other polymer systems and assumes that as the polymer is confined the mechanical response becomes dominated by the modulus of individual polymer chains.

One of the most inspiring and puzzling developments in the organic electronics community in the last few years has been the emergence of solution-processable semiconducting polymers that lack significant long-range order but outperform the best, high-mobility, ordered semiconducting polymers to date. Here we provide new insights into the charge-transport mechanism in semiconducting polymers and offer new molecular design guidelines by examining a state-of-the-art indacenodithiophene-benzothiadiazole copolymer having field-effect mobility of up to 3.6 cm(2) V(-1) s(-1) with a combination of diffraction and polarizing spectroscopic techniques. Our results reveal that its conjugated planes exhibit a common, comprehensive orientation in both the non-crystalline regions and the ordered crystallites, which is likely to originate from its superior backbone rigidity. We argue that charge transport in high-mobility semiconducting polymers is quasi one-dimensional, that is, predominantly occurring along the backbone, and requires only occasional intermolecular hopping through short π-stacking bridges.

The molecular packing in a polymer: fullerene bimolecular crystal is determined using X-ray diffraction (XRD), molecular mechanics (MM) and molecular dynamics (MD) simulations, 2D solid-state NMR spectroscopy, and IR absorption spectroscopy. The conformation of the electron-donating polymer is significantly disrupted by the incorporation of the electron-accepting fullerene molecules, which introduce twists and bends along the polymer backbone and 1D electron-conducting fullerene channels., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The depth-dependent structure of a poly(styrene- b -methylmethacrylate) (PS-PMMA) line grating (46 nm pitch) was calculated from quantitative analysis of small-angle X-ray scattering profiles. These data demonstrate that domain shapes are significantly deformed near the substrate interface, where the local PS domain shape resembles an hourglass. The bulk equilibrium dimension is recovered near the center of a 64 nm thick film. Simulations based on self-consistent field theory suggest that deformations near the substrate are caused by extensive penetration of the copolymer domains into the underlying substrate coating (a PS-brush). These findings suggest that new coatings for block copolymer directed self-assembly should consider copolymer penetration lengths in addition to tailoring surface energetics. Furthermore, given the resolution and ensemble-averaging features of synchrotron X-ray scattering, we argue that it has the potential to emerge as a "gold-standard" or "benchmark" dimensional metrology and library validation tool for high density, sub-10 nm features.

Nonapeptides and their receptors have important functions in mediating social behavior across vertebrates. Where these nonapeptides are synthesized in the brain has been studied extensively in most vertebrate lineages, yet we know relatively little about the neural distribution of nonapeptide receptors outside of mammals. As nonapeptides play influential roles in behavioral regulation in all vertebrates, including teleost fish, we mapped the distributions of the receptors for arginine vasotocin (AVT; homolog of arginine vasopressin) and isotocin (IST; homolog of oxytocin/mesotocin) throughout the forebrain of Astatotilapia burtoni, an African cichlid fish with behavioral phenotypes that are plastic and reversible based on the immediate social environment. We characterized the distribution of the AVT V1a2 receptor (V1aR) and the IST receptor (ITR) using both immunohistochemistry for protein detection and in situ hybridization for mRNA detection, as well as AVT and IST using immunohistochemistry. Expression of the neuropeptide receptors was widely distributed throughout the fore- and midbrain, including the proposed teleost homologs of the mammalian amygdala complex, striatum, hypothalamus, and ventral tegmental area. We conclude that although the location of nonapeptide synthesis is restricted compared to tetrapod vertebrates, the distribution of nonapeptide receptors is highly conserved across taxa. Our results significantly extend our knowledge of where nonapeptides act in the brains of teleosts to mediate social transitions and behavior., (Copyright © 2012 Elsevier B.V. All rights reserved.)

We use a systematic approach that combines experimental X-ray diffraction (XRD) and computational modeling based on molecular mechanics and two-dimensional XRD simulations to develop a detailed model of the molecular-scale packing structure of poly(2,5-bis (3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT-C(14)) films. Both uniaxially and biaxially aligned films are used in this comparison and lead to an improved understanding of the molecular-scale orientation and crystal structure. We then examine how individual polymer components (i.e., conjugated backbone and alkyl side chains) contribute to the complete diffraction pattern, and how modest changes to a particular component orientation (e.g., backbone or side-chain tilt) influence the diffraction pattern. The effects on the polymer crystal structure of varying the alkyl side-chain length from C(12) to C(14) and C(16) are also studied. The accurate determination of the three-dimensional polymer structure allows us to examine the PBTTT electronic band structure and intermolecular electronic couplings (transfer integrals) as a function of alkyl side-chain length. This combination of theoretical and experimental techniques proves to be an important tool to help establish the relationship between the structural and electronic properties of polymer thin films., (© 2012 American Chemical Society)

We report the first synthesis of a fused germaindacenodithiophene monomer and its polymerisation with 2,1,3-benzothiadiazole by Suzuki polycondensation. The resulting polymer, PGeTPTBT, is semicrystalline, despite the presence of four bulky 2-ethylhexyl groups. Blends with P(70)CBM afford solar cells with efficiencies of 5.02%.

We report quantitative measurements of ordering, molecular orientation, and nanoscale morphology in the active layer of bulk heterojunction (BHJ) organic photovoltaic cells based on a thieno[3,4-b]thiophene-alt-benzodithiophene copolymer (PTB7), which has been shown to yield very high power conversion efficiency when blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC(71)BM). A surprisingly low degree of order was found in the polymer-far lower in the bulk heterojunction than in pure PTB7. X-ray diffraction data yielded a nearly full orientation distribution for the polymer π-stacking direction within well-ordered regions, revealing a moderate preference for π-stacking in the vertical direction ("face-on"). By combining molecular orientation information from polarizing absorption spectroscopies with the orientation distribution of ordered material from diffraction, we propose a model describing the PTB7 molecular orientation distribution (ordered and disordered), with the fraction of ordered polymer as a model parameter. This model shows that only a small fraction (≈20%) of the polymer in the PTB7/PC(71)BM blend is ordered. Energy-filtered transmission electron microscopy shows that the morphology of PTB7/PC(71)BM is composed of nanoscale fullerene-rich aggregates separated by polymer-rich regions. The addition of diiodooctane (DIO) to the casting solvent, as a processing additive, results in smaller domains and a more finely interpenetrating BHJ morphology, relative to blend films cast without DIO.

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.

The present study describes the distribution of an arginine vasotocin (AVT) V1a receptor (AVTr) throughout the brain of a sex-changing grouper, rock hind Epinephelus adscensionis. The objectives of this study were to describe the AVTr distribution in the brain of rock hind for potential linkages of the AVT hormone system with sex-specific behaviors observed in this species and to examine sex-specific differences that might exist. An antibody was designed for rock hind AVTr against the deduced amino acid sequence for the third intracellular loop. Protein expression, identified with immunohistochemistry showed high concordance with mRNA expression, identified with in situ hybridization. AVTr protein and mRNA expression was widely distributed throughout the brain, indicating that AVT may act as a neuromodulator via this V1a receptor subtype. AVTr protein and mRNA were present in regions associated with behavior, reproduction and spatial learning, as well as sensory functions such as vision, olfaction and lateral line sensory processing. We observed high AVTr expression in granular cell formations in the internal cellular layer of olfactory bulbs, torus longitudinalis, granular layer of the corpus cerebellum, valvula of the cerebellum, nuclei of the lateral and posterior recesses, and granular eminence. High protein and mRNA expression was also observed in the preoptic area, anterior hypothalamus, and habenular nucleus. No obvious sex differences were noted in any region of the rock hind brain., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The blend films of small-molecule semiconductors with insulating polymers exhibit not only excellent solution processability but also superior performance characteristics in organic thin-film transistors (OTFTs) over those of neat small-molecule semiconductors. To understand the underlying mechanism, we studied triethylsilylethynyl anthradithiophene (TESADT) with small amounts of impurity formed by weak UV exposure. OTFTs with neat impure TESADT had drastically reduced field-effect mobility (<10(-5) cm(2)/(V s)), and a disappearance of the high-temperature crystal phase was observed for neat impure TESADT. However, the mobility of the blend films of the UV-exposed TESADT with poly(α-methylstyrene) (PαMS) is recovered to that of a fresh TESADT-PαMS blend (0.040 cm(2)/(V s)), and the phase transition characteristics partly return to those of fresh TESADT films. These results are corroborated by OTFT results on "aged" TIPS-pentacene. These observations, coupled with the results of neutron reflectivity study, indicate that the formation of a vertically phase-separated layer of crystalline small-molecule semiconductors allows the impurity species to remain preferentially in the adjacent polymer-rich layer. Such a "zone-refinement effect" in blend semiconductors effectively removes the impurity species that are detrimental to organic electronic devices from the critical charge-transporting interface region.

Organic electronics have emerged as a viable competitor to amorphous silicon for the active layer in low-cost electronics. The critical performance of organic electronic materials is closely related to their morphology and molecular packing. Unlike their inorganic counterparts, polymers combine complex repeat unit structure and crystalline disorder. This combination prevents any single technique from being able to uniquely solve the packing arrangement of the molecules. Here, a general methodology for combining multiple, complementary techniques that provide accurate unit cell dimensions and molecular orientation is described. The combination of measurements results in a nearly complete picture of the organic film morphology., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hermaphroditism, associated with territoriality and dominance behavior, is common in the marine environment. While male sex-specific coloration patterns have been documented in groupers, particularly during the spawning season, few data regarding social structure and the context for these color displays are available. In the present study, we define the social structure and male typical behavior of rock hind (Epinephelus adscensionis) in the wild. In addition, we detail the captive conditions and time period necessary to induce the onset of the sex-specific coloration and sexual change. At six oil production platform locations in the Gulf of Mexico, rock hind social group size and typical male rock hind social behavior were documented. We observed a rapid temporary color display in rock hind that could be turned on and off within three seconds and was used for confronting territory intruders and displays of aggression towards females. The male-specific "tuxedo" pattern consists of a bright yellow tail, a body with alternating dark brown and white patches and a dark bar extending from the upper mandible to the operculum. Identification and size ranges of male, female and intersex fish collected from oil platforms were determined in conjunction with gonadal histology. Rock hind social order is haremic with one dominant male defending a territory and a linear dominance hierarchy among individuals. In five captive experiments, the largest remaining female rock hind displayed the male specific color pattern within 32d after dominant male removal from the social group. To our knowledge, this is the first evidence in a grouper species of color patterning used to display territoriality and dominance outside of spawning aggregations. The behavioral paradigm described here is a key advance that will enable mechanistic studies of this complex sex change process.

The elastic moduli of polythiophenes, regioregular poly(3-hexylthiophene) (P3HT) and poly-(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (pBTTT), are compared to their field effect mobility showing a proportional trend. The elastic moduli of the films are measured using a buckling-based metrology, and the mobility is determined from the electrical characteristics of bottom contact thin film transistors. Moreover, the crack onset strain of pBTTT films is shown to be less than 2.5%, whereas that of P3HT is greater than 150%. These results show that increased long-range order in polythiophene semiconductors, which is generally thought to be essential for improved charge mobility, can also stiffen and enbrittle the film. This work highlights the critical role of quantitative mechanical property measurements in guiding the development of flexible organic semiconductors.

The performance of semiconducting polymers has been steadily increasing in the last 20 years. Improved control over the microstructure of these materials and a deeper understanding of how the microstructure affects charge transport are partially responsible for such trend. The development and widespread use of techniques that allow to characterize the microstructure of semiconducting polymers is therefore instrumental for the advance of these materials. This article is a review of the characterization techniques that provide information used to enhance the understanding of structure/property relationships in semiconducting polymers. In particular, the applications of optical and X-ray spectroscopy, X-ray diffraction, and scanning probe techniques in this context are described.

The large-scale manufacture of organic electronics devices becomes more feasible if the molecular orientation and morphology of the semiconductor can be controlled. Here, we report on a previously unidentified crystal shape of terraced nanoscale "ribbons" in thin films of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT). The ribbons form after a pBTTT film is heated above its highest temperature phase transition. In contrast to the wide terrace crystal shape previously reported, terraced ribbons have lateral widths of approximately 60 nm and lengths greater than 10 microm, with a common orientation between adjacent ribbons. Further, we report a simple and scalable flow coating process that can control the ribbon orientation without requiring special substrates or external fields. The degree of molecular orientation is small after coating but increases dramatically after the terraced ribbons are formed, indicating that an oriented minority templates the whole film structure. The large extent of orientation obtained in these polythiophene crystallites provides potential opportunities to exploit anisotropic electrical properties and to obtain detailed information about the structure of organic semiconductor thin films.

The use of organic materials presents a tremendous opportunity to significantly impact the functionality and pervasiveness of large-area electronics. Commercialization of this technology requires reduction in manufacturing costs by exploiting inexpensive low-temperature deposition and patterning techniques, which typically lead to lower device performance. We report a low-cost approach to control the microstructure of solution-cast acene-based organic thin films through modification of interfacial chemistry. Chemically and selectively tailoring the source/drain contact interface is a novel route to initiating the crystallization of soluble organic semiconductors, leading to the growth on opposing contacts of crystalline films that extend into the transistor channel. This selective crystallization enables us to fabricate high-performance organic thin-film transistors and circuits, and to deterministically study the influence of the microstructure on the device characteristics. By connecting device fabrication to molecular design, we demonstrate that rapid film processing under ambient room conditions and high performance are not mutually exclusive.

Poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene), PBTTT, is a semiconducting polymer that forms thin film transistors (TFTs) with high field effect mobility on silicon dioxide dielectrics that are treated with alkyltrichlorosilanes ( approximately 0.2 to 0.5 cm2/V s) but forms TFTs with poor mobility on bare silicon dioxide (<0.005 cm2/V s). The microstructure of spin-coated thin films of PBTTT on these surfaces was studied using synchrotron X-ray diffraction and atomic force microscopy. PBTTT crystallizes with lamellae of pi-stacked polymer chains on both surfaces. The crystalline domains are well-oriented relative to the substrate in the as-spun state and become highly oriented and more ordered with thermal annealing in the liquid crystalline mesophase. Although the X-ray scattering from PBTTT is nearly identical on both surfaces, atomic force microscopy showed that the domain size of the crystalline regions depends on the substrate surface. These results suggest that electrical transport in PBTTT films is strongly affected by the domain size of the crystalline regions and the disordered regions between them.

Organic semiconductors that can be fabricated by simple processing techniques and possess excellent electrical performance, are key requirements in the progress of organic electronics. Both high semiconductor charge-carrier mobility, optimized through understanding and control of the semiconductor microstructure, and stability of the semiconductor to ambient electrochemical oxidative processes are required. We report on new semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices. Relatively large crystalline domain sizes on the length scale of lithographically accessible channel lengths ( approximately 200 nm) were exhibited in thin films, thus offering the potential for fabrication of single-crystal polymer transistors. Good transistor stability under static storage and operation in a low-humidity air environment was demonstrated, with charge-carrier field-effect mobilities of 0.2-0.6 cm(2) V(-1) s(-1) achieved under nitrogen.