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It is increasingly obvious that the molecular conformations and the long-range arrangement that conjugated polymers can adopt under various experimental conditions in bulk, solutions or thin films, significantly impact their resulting optoelectronic properties. As a consequence, the functionalities and efficiencies of resulting organic devices, such as field-effect transistors, light-emitting diodes, or photovoltaic cells, also dramatically change due to the close structure/property relationship. A range of structure/optoelectronic properties relationships have been investigated over the last few years using various experimental and theoretical methods, and, further, interesting correlations are continuously revealed by the scientific community. In this review, we discuss the latest findings related to the structure/optoelectronic properties interrelationships that exist in organic devices fabricated with conjugated polymers in terms of charge mobility, absorption, photoluminescence, as well as photovoltaic properties. [ABSTRACT FROM AUTHOR]

We have investigated the ferroelectric phase diagramof poly(vinylidenefluoride) (PVDF) and poly(methyl methacrylate) (PMMA). The binarynonequilibrium temperature composition diagram was determined andmelting of α- and β-phase PVDF was identified. Ferroelectricβ-PVDF:PMMA blend films were made by melting, ice quenching,and subsequent annealing above the glass transition temperature ofPMMA, close to the melting temperature of PVDF. Addition of PMMA suppressesthe crystallization of PVDF and, as a consequence, the roughness ofblend films was found to decrease with increasing PMMA content. Usingtime-dependent 2D numerical simulations based on a phase–fieldmodel, we qualitatively reproduced the effect of PMMA on the crystallizationrate and the spherulite shape of PVDF. The remnant polarization scaledwith the degree of crystallinity of PVDF. The thermal stability ofthe polarization is directly related to the Curie temperature. Weshow that, at high temperature, the commodity ferroelectric PVDF:PMMAblends outperform the commonly employed specialty copolymer poly(vinylidenefluoride–trifluoroethylene) (P(VDF–TrFE)). [ABSTRACT FROM AUTHOR]

One grand challenge for printed organic electronics is the development of a knowledge platform that describes how polymer semiconductors assemble from solution, which requires a unified picture of the complex interplay of polymer solubility, mass transport, nucleation and, e.g., vitrification. One crucial aspect, thereby, is aggregate formation, i.e., the development of electronic coupling between adjacent chain segments. Here, it is shown that the critical aggregation temperatures in solution (no solvent evaporation allowed) and during film formation (solvent evaporation occurring) are excellent pointers to i) establish reliable criteria for polymer assembly into desired aggregates, and ii) advance mechanistic understanding of the overall polymer assembly. Indeed, important insights are provided on why aggregation occurs via a 1‐ or 2‐step process depending on polymer solubility, deposition temperature and solvent evaporation rate; and the selection of deposition temperatures for specific scenarios (e.g., good vs bad solvent) is demystified. Collectively, it is demonstrated that relatively straightforward, concurrent in situ time‐resolved absorbance and photoluminescence spectroscopies to monitor aggregate formation lead to highly useful and broadly applicable criteria for processing functional plastics. In turn, improved control over their properties and device performance can be obtained toward manufacturing sensors, energy‐harvesting devices and, e.g., bioelectronics systems at high yield. [ABSTRACT FROM AUTHOR]

The article offers information on the 10th European Conference on Molecular Electronics (ECME) 2009 held in Copenhagen, Denmark. The topics covered at the conference included all areas related to organic and plastic ellectronics including chemistry, physics, and nanoscience. Jens Wenzel Andreasen from the Technical University of Denmark in Copenhagen Denmark discussed the need for more direct control of the nanostructure of polymer solar cells.

Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets (S(λ1,T2,λ3)) along the population time (T2) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps (S(λ1,ν̃2,λ3)). We found that the vibrational coherence from pure excited electronic states appears at positive frequency (+ν̃2) in the rephasing beating map and at negative frequency (-ν̃2) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems. [ABSTRACT FROM AUTHOR]

Large strides have been made in designing an ever-increasing set of modern organic materials of high functionality and thus, often, of high complexity, including semiconducting polymers, organic ferroelectrics, light-emitting small molecules, and beyond. Here, we review how broadly applied thermal analysis methodologies, especially differential scanning calorimetry, can be utilized to provide unique information on the assembly and solid-state structure of this extensive class of materials, as well as the phase behavior of intrinsically intricate multicomponent systems. Indeed, highly relevant insights can be gained that are useful, e.g., for further materials-discovery activities and the establishment of reliable processing protocols, in particular if combined with X-ray diffraction techniques, spectroscopic tools, and scanning electron microscopy enabled by vapor-phase infiltration staining. We, hence, illustrate that insights far richer than simple melting point– and glass-transition identification can be obtained with differential scanning calorimetry, rendering it a critical methodology to understand complex matter, including functional macromolecules and blends. [ABSTRACT FROM AUTHOR]

To bolster the series of Brief Guides released by International Union of Pure and Applied Chemistry (IUPAC), here we introduce the first Brief Guide to Polymer Characterization. This article provides a concise overview of characterization methods for teachers, students, non-specialists, and newcomers to polymer science as well as being a useful manual for researchers and technicians. Unlike pure low molar mass chemical substances, polymers are not composed of identical molecules. The macromolecules which comprise a single polymer sample vary from one another, primarily in terms of size and shape, but often also in the arrangement or positioning of atoms within macromolecules (e.g., chain branching, isomerism, etc.). Polymer properties are often drastically different from those of other substances and their characterization relies on specialist equipment and/or common equipment used in a specialized way (e.g., particular sample preparation or data analysis). This Brief Guide focuses uniquely on the structural characterization (i.e., analyzing the molecular and multi-molecular aspects) of polymers. The complex nature of the structural variables possible in macromolecular materials often presents a challenge with regard to the detailed structural characterization of polymers. This Brief Guide provides a useful starting point to direct the reader to the most commonly used and useful techniques to characterize these structural variables. [ABSTRACT FROM AUTHOR]

The use of thermoelectric technology is attractive in many potential applications, such as energy scavenging from waste heat. The basic principles for harvesting electricity from a temperature gradient were first discovered around 180 years ago, but the contemporary technology utilising inorganic semiconductors was only developed since the early 1950s. The widespread use of this platform has so far been limited by a combination of relatively low efficiency in energy conversion or by issues related to the utilisation of rare, expensive and/or toxic elements that can be difficult to process. Recently much interest has been focused on the use of organic materials in thermoelectric devices, prompted by the possibility of developing large-area, low-cost devices. Considerable research in the last 20 years has been focused on understanding and improving organic thermoelectric properties, with remarkable progress recently published for compounds such as PEDOTand others. Here we provide an overview into thermoelectricity, from the initial discoveries made by Johann Seebeck to modern practical applications including the current trends in organic thermoelectric research. [ABSTRACT FROM AUTHOR]

The use of thermoelectric technology is attractive in many potential applications, such as energy scavenging from waste heat. The basic principles for harvesting electricity from a temperature gradient were first discovered around 180 years ago, but the contemporary technology utilising inorganic semiconductors was only developed since the early 1950s. The widespread use of this platform has so far been limited by a combination of relatively low efficiency in energy conversion or by issues related to the utilisation of rare, expensive and/or toxic elements that can be difficult to process. Recently much interest has been focused on the use of organic materials in thermoelectric devices, prompted by the possibility of developing large-area, low-cost devices. Considerable research in the last 20 years has been focused on understanding and improving organic thermoelectric properties, with remarkable progress recently published for compounds such as PEDOT and others. Here we provide an overview into thermoelectricity, from the initial discoveries made by Johann Seebeck to modern practical applications including the current trends in organic thermoelectric research. [ABSTRACT FROM AUTHOR]

Abstract: By blending poly(3-hexylthiophene) with poly(vinylidene fluoride) and with careful solvent selection, field-effect transistors are fabricated from solution with deposition temperatures suitable for use in low-cost roll-to-roll manufacturing techniques. A percolation threshold of only ∼3wt.% P3HT is demonstrated, with field-effect mobilities of 0.04cm2/Vs obtained in such PVDF-rich blend devices being equal to neat P3HT field-effect transistors. We illustrate the potential of this material system by the fabrication of working field-effect transistor devices, wherein the semiconductor blend is deposited via flexo-printing. Flexible polyethylene naphthalate substrates and an organic gate dielectric were utilized for this purpose. [Copyright &y& Elsevier]

These recommendations are specifically for polymers and polymer systems showing a significant response to an electromagnetic field or one of its components (electric field or magnetic field), i.e., for electromagnetic-field-responsive polymer materials. The structures, processes, phenomena and quantities relating to this interdisciplinary field of materials science and technology are herein defined. Definitions are unambiguously explained and harmonized for wide acceptance by the chemistry, physics, polymer and materials science communities. A survey of typical electromagnetic-field-responsive polymers is included. [ABSTRACT FROM AUTHOR]

Organic solar cells incorporating non‐fullerene acceptors (NFAs) have reached remarkable power conversion efficiencies of over 18%. Unlike fullerene derivatives, NFAs tend to crystallize from solutions, resulting in bulk heterojunctions that include a crystalline acceptor phase. This must be considered in any morphology‐function models. Here, it is confirmed that high‐performing solution‐processed indacenodithienothiophene‐based NFAs, i.e., ITIC and its derivatives ITIC‐M, ITIC‐2F, and ITIC‐Th, exhibit at least two crystalline forms. In addition to highly ordered polymorphs that form at high temperatures, NFAs arrange into a low‐temperature metastable phase that is readily promoted via solution processing and leads to the highest device efficiencies. Intriguingly, the low‐temperature forms seem to feature a continuous network that favors charge transport despite of a poorly order along the π–π stacking direction. As the optical absorption of the structurally more disordered low‐temperature phase can surpass that of the more ordered polymorphs while displaying comparable—or even higher—charge transport properties, it is argued that such a packing structure is an important feature for reaching highest device efficiencies, thus, providing guidelines for future materials design and crystal engineering activities. [ABSTRACT FROM AUTHOR]

Cross-talk in memories using resistive switches in a cross-bar geometry can be prevented by integration of a rectifying diode. We present a functional cross bar memory array using a phase separated blend of a ferroelectric and a semiconducting polymer as storage medium. Each intersection acts simultaneously as a bistable rectifying diode. A logic table of a 4-bit memory and integration into a 3×3 cross bar array are demonstrated. The most difficult state, a high resistance bit completely surrounded by low resistance bits could be unambiguously identified. [ABSTRACT FROM AUTHOR]

Electrocaloric refrigeration is one of the most promising environmentally‐friendly technologies to replace current cooling platforms—if a notable electrocaloric effect (ECE) is realized around room temperature where the highest need is. Here, a straight‐forward, one‐pot chemical modification of P(VDF‐ter‐TrFE‐ter‐CTFE) is reported through the controlled introduction of small fractions of double bonds within the backbone that, very uniquely, decreases the lamellar crystalline thickness while, simultaneously, enlarging the crystalline coherence along the a‐b plane. This increases the polarizability and polarization without affecting the degree of crystallinity or amending the crystal unit cell—undesirable effects observed with other approaches. Specifically, the permittivity increases by >35%, from 52 to 71 at 1 kHz, and ECE improves by >60% at moderate electric fields. At 40 °C, an adiabatic temperature change >2 K is realized at 60 MV m−1 (>5.5 K at 192 MV m−1), compared to ≈1.3 K for pristine P(VDF‐ter‐TrFE‐ter‐CTFE), highlighting the promise of a simple, versatile approach that allows direct film deposition without requiring any post‐treatment such as mechanical stretching or high‐temperature annealing for achieving the desired performance. [ABSTRACT FROM AUTHOR]

As increasingly smaller molecular materials and material structures are devised or developed for technological applications, the demands on the processes of lithography now routinely include feature sizes that are of the order of 10 nm. In reaching such a fine level of resolution, the methods of lithography have increased markedly in sophistication and brought into play 2terminology that is unfamiliar, on the one hand, to scientists tasked with the development of new lithographic materials or, on the other, to the engineers who design and operate the complex equipment that is required in modern-day processing. Publications produced by scientists need to be understood by engineers and vice versa, and these commonly arise from collaborative research that draws heavily on the terminology of two or more of the traditional disciplines. It is developments in polymer science and material science that lead progress in areas that cross traditional boundaries, such as microlithography. This document provides the exact definitions of a selection of unfamiliar terms that researchers and practitioners from different disciplines might encounter. [ABSTRACT FROM AUTHOR]

The ever increasing library of materials systems developed for organic solar‐cells, including highly promising non‐fullerene acceptors and new, high‐efficiency donor polymers, demands the development of methodologies that i) allow fast screening of a large number of donor:acceptor combinations prior to device fabrication and ii) permit rapid elucidation of how processing affects the final morphology/microstructure of the device active layers. Efficient, fast screening will ensure that important materials combinations are not missed; it will accelerate the technological development of this alternative solar‐cell platform toward larger‐area production; and it will permit understanding of the structural changes that may occur in the active layer over time. Using the relatively high‐efficiency poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′′′‐di(2‐octyldodecyl)‐2,2′;5′,2′′;5′′,2′′′‐quaterthiophen‐5,5′′′‐diyl)] (PCE11):phenyl‐C61‐butyric acid‐methyl‐ester acceptor (PCBM) blend systems, it is demonstrated that by means of straight‐forward thermal analysis, vapor‐phase‐infiltration imaging, and transient‐absorption spectroscopy, various blend compositions and processing methodologies can be rapidly screened, information on promising combinations can be obtained, reliability issues with respect to reproducibility of thin‐film formation can be identified, and insights into how processing aids, such as nucleating agents, affect structure formation, can be gained. [ABSTRACT FROM AUTHOR]

The correlation between morphology and optoelectronic performance in organic thin‐film transistors based on blends of photochromic diarylethenes (DAE) and poly(3‐hexylthiophene) (P3HT) is investigated by varying molecular weight (Mw = 20–100 kDa) and regioregularity of the conjugated polymer as well as the temperature of thermal annealing (rt‐160 °C) in thin films. Semicrystalline architectures of P3HT/DAE blends comprise crystalline domains, ensuring efficient charge transport, and less aggregated regions, where DAEs are located as a result of their spontaneous expulsion from the crystalline domains during the self‐assembly. The best compromise between field‐effect mobility (μ) and switching capabilities is observed in blends containing P3HT with Mw = 50 kDa, exhibiting μ as high as 1 × 10−3 cm2 V−1 s−1 combined with a >50% photoswitching ratio. Higher or lower Mw than 50 kDa are found to be detrimental for field‐effect mobility and to lead to reduced device current switchability. The microstructure of the regioregular P3HT blend is found to be sensitive to the thermal annealing temperature, with an increase in μ and a decrease in current modulation being observed as a response to the light‐stimulus likely due to an increased P3HT‐DAE segregation, partially hindering DAE photoisomerization. The findings demonstrate the paramount importance of fine tuning the structure and morphology of bicomponent films for leveraging the multifunctional nature of optoelectronic devices. [ABSTRACT FROM AUTHOR]

In view of a rapid development and increase in efficiency of organic solar cells, reaching their long‐term operational stability represents now one of the main challenges to be addressed on the way toward commercialization of this photovoltaic technology. However, intrinsic degradation pathways occurring in organic solar cells under realistic operational conditions remain poorly understood. The light‐induced dimerization of the fullerene‐based acceptor materials discovered recently is considered to be one of the main causes for burn‐in degradation of organic solar cells. In this work, it is shown that not only the fullerene derivatives but also different types of conjugated polymers and small molecules undergo similar light‐induced crosslinking regardless of their chemical composition and structure. In the case of conjugated polymers, crosslinking of macromolecules leads to a rapid increase in their molecular weight and consequent loss of solubility, which can be revealed in a straightforward way by gel permeation chromatography analysis via a reduction/loss of signal and/or smaller retention times. Results of this work, thus, shift the paradigm of research in the field toward designing a new generation of organic absorbers with enhanced intrinsic photochemical stability in order to reach practically useful operation lifetimes required for successful commercialization of organic photovoltaics. [ABSTRACT FROM AUTHOR]

Organic blend thin films consisting of semiconducting poly(3-hexylthiophene) (P3HT) and insulating high-density polyethylene (HDPE) have been fabricated by novel application of a large area wire-bar coating technique in air. The microstructure of P3HT:HDPE blend films reveals a strong structural dependence on initial composition. Preferential segregation of P3HT toward the film surface is observed for all blend compositions, while P3HT (or P3HT-rich) columnar structures enclosed by HDPE (or HDPE-rich) lamellar matrix is distinctive for 50:50 (by weight) blends. The transistors fabricated with P3HT:HDPE blend films show a clear field effect behavior, exhibiting charge carrier mobilities up to 5 × 10-2 cm2/Vs, comparable to the values reported in spin-coated similar blends and of neat P3HT devices. The wire-bar coated blend films and devices are highly repeatable and spatially uniform over large areas (few cm by few cm), demonstrating the suitability of this technique for manufacturing of large area organic electronic devices. [ABSTRACT FROM AUTHOR]

The family of soluble fullerene derivatives comprises a widely studied group of electron transporting molecules for use in organic electronic and optoelectronic devices. For electronic applications, electron transporting (n-channel) materials are required for implementation into organic complementary logic circuit architectures. To date, few soluble candidate materials have been studied that fulfill the stringent requirements of high carrier mobility and air stability. Here we present a study of three soluble fullerenes with varying electron affinity to assess the impact of electronic structure on device performance and air stability. Through theoretical and experimental analysis of the electronic structure, characterization of thin-film structure, and characterization of transistor device properties we find that the air stability of the present series of fullerenes not only depends on the absolute electron affinity of the semiconductor but also on the disorder within the thin-film. [ABSTRACT FROM AUTHOR]

This paper provides a list of the most important terms from all areas of polymer science including polymer chemistry, polymer physics, polymer technology and polymer properties. These have been assembled into a representative list of terms that serves as an IUPAC recommended list of keywords for polymer science. [ABSTRACT FROM AUTHOR]

ABSTRACT: Aggregates – that is short‐ranged ordered moieties in the solid‐state of π‐conjugated polymers – play an important role in the photophysics and performance of various optoelectronic devices. We have previously shown that many polymers change from a disordered to a more ordered conformation when cooling a solution below a characteristic critical temperature T c. Using in situ time‐resolved absorption spectroscopy on the prototypical semiconducting polymers P3HT, PFO, PCPDTBT, and PCE11 (PffBT4T‐2OD), we show that spin‐coating at a temperature below T c can enhance the formation of aggregates with strong intra‐chain coupling. An analysis of their time‐resolved spectra indicates that the formation of nuclei in the initial stages of film formation for substrates held below T c seems responsible for this. We observe that the growth rate of the aggregates is thermally activated with an energy of 310 meV, which is much more than that of the solvent viscosity (100 meV). From this we conclude that the rate controlling step is the planarization of a chain that is associated with its attachment to a nucleation center. The success of our approach for the rather dynamic deposition method of spin‐coating holds promise for other solution‐based deposition methods. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 532–542 [ABSTRACT FROM AUTHOR]

Electronic and optical properties of conjugated polymers are strongly affected by their solid-state microstructure. In nematic polymers, mesoscopic order and structure can be theoretically understood using Maier-Saupe (MS) models, motivating us to apply them to conjugated macromolecular systems and consider the problem of their material-specific parametrization. MS models represent polymers by worm-like chains (WLC) and can describe collective polymer alignment through anisotropic MS interactions. Their strength is controlled by a phenomenological temperature-dependent parameter, ν(T). We undertake the challenging task of estimating material-specific ν(T), combining experiments and Self-Consistent Field theory (SCFT). Considering three different materials and a spectrum of molecular weights, we cover the cases of rod-like, semiflexible, and flexible conjugated polymers. The temperature of the isotropic-nematic transition, TIN, is identified via polarized optical microscopy and spectroscopy. The polymers are mapped on WLC with temperature-dependent persistence length. Fixed persistence lengths are also considered, reproducing situations addressed in earlier studies. We estimate ν(T) by matching TIN in experiments and SCFT treatment of the MS model. An important conclusion is that accounting explicitly for changes of persistence length with temperature has significant qualitative effects on ν(T). We moreover correlate our findings with earlier discussions on the thermodynamic nature of phenomenological MS interactions. [ABSTRACT FROM AUTHOR]

ABSTRACT The microstructure dependence of carrier mobility and recombination rates of neat films of poly 3-hexylthyophene (P3HT) were determined for a range of materials of weight-average molecular weights, Mw, ranging from 14 to 331 kDa. This variation has previously been shown to modify the polymer microstructure, with low molecular weights forming a one-phase, paraffinic-like structure comprised of chain-extended crystallites, and higher molecular weights forming a semicrystalline structure with crystalline domains being embedded in an amorphous matrix. Using Charge Extraction by Linearly Increasing Voltage (CELIV), we show here that the carrier mobility in P3HT devices peaks for materials of Mw = 48 kDa, and that the recombination rate decreases monotonically with increasing molecular weight. This trend is likely due to the development of a semicrystalline, two-phase structure with increasing Mw, which allows for the spatial separation of holes and electrons into the amorphous and crystalline regions, respectively. This separation leads to decreased recombination. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 31-35 [ABSTRACT FROM AUTHOR]

Low-molecular-weight organic gelators are widely used to influence the solidification of polymers, with applications ranging from packaging items, food containers to organic electronic devices, including organic photovoltaics. Here, this concept is extended to hybrid halide perovskite-based materials. In situ time-resolved grazing incidence wide-angle X-ray scattering measurements performed during spin coating reveal that organic gelators beneficially influence the nucleation and growth of the perovskite precursor phase. This can be exploited for the fabrication of planar n-i-p heterojunction devices with MAPbI3 (MA = CH3NH3+) that display a performance that not only is enhanced by ≈25% compared to solar cells where the active layer is produced without the use of a gelator but that also features a higher stability to moisture and a reduced hysteresis. Most importantly, the presented approach is straightforward and simple, and it provides a general method to render the film formation of hybrid perovskites more reliable and robust, analogous to the control that is afforded by these additives in the processing of commodity 'plastics.' [ABSTRACT FROM AUTHOR]

Electrocaloric device structures have been developed as multilayer ceramics ( MLCs) based on fundamental research carried out on PMN-8 PT bulk ceramics. Two different MLC structures were prepared with nine layers each and layer thicknesses of 86 μm and 39 μm. The influence of the device design on its properties has been characterized by microstructural, dielectric, ferroelectric, and direct electrocaloric measurement. For direct characterization two different methods, ie temperature reading (thermistor and thermocouple) and heat flow measurement (differential scanning calorimetry), were used. A comparison of results revealed a highly satisfactory agreement between the different methods. This study confirms that MLCs are promising candidates for implementation into energy-efficient electrocaloric cooling systems providing large refrigerant volume and high electrocaloric effect. Due to their micron-sized active layers, they allow for the application of high electric fields under low operation voltages. We measured a maximum electrocaloric temperature change of Δ T=2.67 K under application/withdrawal of an electric field of Δ E=16 kV mm−1, which corresponds to operation voltages below 1.5 kV. [ABSTRACT FROM AUTHOR]

Herein, we elucidate the impact of tubular confinement on the structure and relaxation behavior of poly(vinylidene difluoride) (PVDF) and how these affect the para-/ferroelectric behavior of this polymer. We use PVDF nanotubes that were solidified in anodic aluminum oxide (AAO) templates. Dielectric spectroscopy measurements evidence a bimodal relaxation process for PVDF nanotubes: besides the bulk-like α-relaxation, we detect a notably slower relaxation that is associated with the PVDF regions of restricted dynamics at the interface with the AAO pore. Strikingly, both the bulk-like and the interfacial relaxation tend to become temperature independent as the temperature increases, a behavior that has been observed before in inorganic relaxor ferroelectrics. In line with this, we observe that the real part of the dielectric permittivity of the PVDF nanotubes exhibits a broad maximum when plotted against the temperature, which is, again, a typical feature of relaxor ferroelectrics. As such, we propose that, in nanotubular PVDF, ferroelectric-like nanodomains are formed in the amorphous phase regions adjacent to the AAO interface. These ferroelectric nanodomains may result from an anisotropic chain conformation and a preferred orientation of local dipoles due to selective H-bond formation between the PVDF macromolecues and the AAO walls. Such relaxor-ferroelectric-like behavior has not been observed for nonirradiated PVDF homopolymer; our findings thus may enable in the future alternative applications for this bulk commodity plastic, e.g., for the production of electrocaloric devices for solid-state refrigeration which benefit from a relaxor-ferroelectric-like response. [ABSTRACT FROM AUTHOR]

We report the synthesis of a novel naphthalene diimide (NDI) monomer containing two (tributylstannyl)vinyl groups. The utility of this building block is demonstrated by its copolymerization with five different electron-rich comonomers under Stille conditions. The resulting high molecular weight polymers show red-shifted optical absorptions in comparison to the analogous polymers without the vinylene spacer and a significant increase in the intensity of the low-energy intramolecular charge transfer band. The polymers all exhibit ambipolar behavior in bottom-gate, top-contact organic thin-film transistors. The insertion of a solution-processed barium hydroxide layer between the polymer and the gold electrode led to unipolar behavior with improved electron mobilities. [ABSTRACT FROM AUTHOR]

A trimer of diketopyrrolopyrole (DPP), Tri-BTDPP, was synthesized and characterized. Tri-BTDPP has a HOMO level of −5.34 eV, a low band gap of 1.33 eV, and a hole mobility of ∼10 −3 cm 2 V −1 s −1 in organic field effect transistors (OFETs). Organic photovoltaic (OPV) devices using the donor/acceptor blends of Tri-BTDPP and PC 71 BM exhibited low power conversion efficiencies (PCE) of up to 0.72%, even though the desirable optical and electronic characteristics of this compound as a donor semiconductor for achieving high performance for OPV. Through an intensive study of the active layer using AFM, XRD, and DSC, it was found that Tri-BTDPP and PC 71 BM were unable to intermix and formed oversized Tri-BTDPP phases, resulting in poor charge separation. Some guidance on how to improve the OPV performance of Tri-DPP compounds is provided. [ABSTRACT FROM AUTHOR]

Typical device architectures in polymer-based optoelectronic devices, such as field effect transistors organic light emitting diodes and photovoltaic cells include sub-100 nm semiconducting polymer thin-film active layers, whose microstructure is likely to be subject to finite-size effects. The aim of this study was to investigate effect of the two-dimensional spatial confinement on the internal structure of the semiconducting polymer poly(9,9-dioctylfluorene) (PFO). PFO melts were confined inside the cylindrical nanopores of anodic aluminium oxide (AAO) templates and crystallized via two crystallization strategies, namely, in the presence or in the absence of a surface bulk reservoir located at the template surface. We show that highly textured semiconducting nanowires with tuneable crystal orientation can be thus produced. The results presented here demonstrate the simple fabrication and crystal engineering of ordered arrays of PFO nanowires; a system with potential applications in devices where anisotropic optical properties are required, such as polarized electroluminescence, waveguiding, optical switching and lasing. [ABSTRACT FROM AUTHOR]

We report high-resolution, traceable atomic force microscopy measurements of high-quality, solvent-free single crystals of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). These were grown by drop-casting PCBM solutions onto the spectrosil substrates and by removing the residual solvent in a vacuum. A home-built atomic force microscope featuring a plane mirror differential optical interferometer, fiber-fed from a frequency-stabilized laser (emitting at 632.8 nm), was used to measure the crystals' height. The optical interferometer together with the stabilized laser provides traceability (via the laser wavelength) of the vertical measurements made with the atomic force microscope. We find that the crystals can conform to the surface topography, thanks to their height being significantly smaller compared to their lateral dimensions (namely, heights between about 50nm and 140 nm, for the crystals analysed, vs. several tens of microns lateral dimensions). The vast majority of the crystals are flat, but an isolated, non-flat crystal provides insights into the growth mechanism and allows identification of "molecular terraces" whose height corresponds to one of the lattice constants of the single PCBM crystal (1.4 nm) as measured with X-ray diffraction. [ABSTRACT FROM AUTHOR]

The synthesis of a novel 3,3'-difluoro-4,4'-dihexadecyl-2,2'-bithiophene monomer and its copolymerization with thieno[3,2-b]thiophene to afford the fluorinated analogue of the well-known poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]-thiophene) (PBTTT) polymer is reported. Fluorination is found to have a significant influence on the physical properties of the polymer, enhancing aggregation in solution and increasing melting point by over 100 °C compared to nonfluorinated polymer. On the basis of DFT calculations these observations are attributed to inter and intramolecular S...F interactions. As a consequence, the fluorinated polymer PFBTTT exhibits a fourfold increase in charge carrier mobility compared to the nonfluorinated polymer and excellent ambient stability for a nonencapsulated transistor device. [ABSTRACT FROM AUTHOR]

Ferroelectric nanostructures offer a promising route for novel integrated electronic devices such as non-volatile memories. Here we present a facile fabrication route for ferroelectric capacitors comprising a linear array of the ferroelectric random copolymer of vinylidenefluoride and trifluoroethylene (P(VDF-TrFE)) interdigitated with the electrically insulating polymer polyvinyl alcohol (PVA). Micrometer size line gratings of both polymers were fabricated over large area by solution micromolding, a soft lithography method. The binary linear arrays were realized by backfilling with the second polymer. We investigated in detail the device physics of the patterned capacitors. The electrical equivalent circuit is a linear capacitor of PVA in parallel with a ferroelectric capacitor of P(VDF-TrFE). The binary arrays are electrically characterized by both conventional Sawyer-Tower and shunt measurements. The dependence of the remanent polarization on the array topography is explained by numerical simulation of the electric field distribution. [ABSTRACT FROM AUTHOR]

We report the advantageous properties of the inorganic molecular semiconductor copper(I) thiocyanate (CuSCN) for use as a hole collection/transport layer (HTL) in organic photovoltaic (OPV) cells. CuSCN possesses desirable HTL energy levels [i.e., valence band at -5.35 eV, 0.35 eV deeper than poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS)], which produces a 17% increase in power conversion efficiency (PCE) relative to PEDOT:PSS-based devices. In addition, a two-fold increase in shunt resistance for the solar cells measured in dark conditions is achieved. Ultimately, CuSCN enables polymer:fullerene based OPV cells to achieve PCE>8%. CuSCN continues to offer promise as a chemically stable and straightforward replacement for the commonly used PEDOT:PSS. [ABSTRACT FROM AUTHOR]

A series of new, easily synthesized C60–fullerene derivatives is introduced that allow for optimization of the interactions between rr-P3HT and the fullerene by systematic variation of the size of the ester group. Two compounds gave overall cell efficiencies of 4.8%, clearly outperforming [60]PCBM which gives 4.3% under identical conditions. [ABSTRACT FROM AUTHOR]

Side-chain engineering is increasingly being utilized as a technique to impact the structural order and enhance the electronic properties of semiconducting polymers. However, the correlations drawn between structural changes and the resulting charge transport properties are typically indirect and qualitative in nature. In the present work, a combination of grazing incidence X-ray diffraction and crystallographic refinement calculations is used to determine the precise molecular packing structure of two thiophene-based semiconducting polymers to study the impact of side-chain modifications. The optimized structures provide high-quality fits to the experimental data and demonstrate that in addition to a large difference in interchain spacing between the two materials, there exists a significant disparity in backbone orientation as well. The calculated structures are utilized in density functional theory calculations to determine the band structure of the two materials and are shown to exhibit a dramatic disparity in interchain dispersion which accounts for the large observed difference in charge carrier mobility. The techniques presented here are meant to be general and are therefore applicable to many other highly diffracting semicrystalline polymers. [ABSTRACT FROM AUTHOR]

Here we show that the charge transfer (CT) absorption signal in bulk-heterojunction solar cell blends, measured by photothermal deflection spectroscopy, is directly proportional to the density of molecular donor:acceptor interfaces. Since the optical transitions from the ground state to the interfacial CT state are weakly allowed at photon energies below the optical gap of both the donor and acceptor, we can exploit the use of this sensitive linear absorption spectroscopy for such quantification. Moreover, we determine the absolute molar extinction coefficient of the CT transition for an archetypical polymer:fullerene interface. The latter is ~100 times lower than the extinction coefficient of the donor chromophore involved, allowing us to experimentally estimate the transition dipole moment as 0.3 D and the electronic coupling between the ground and CT states to be on the order of 30 meV. [ABSTRACT FROM AUTHOR]

We reveal some of the key mechanisms during charge generation in polymenfullerene blends exploiting our well-defined understanding of the microstructures obtained in pBTTT:PCBM systems via processing with fatty acid methyl ester additives. Based on ultrafast transient absorption, electro-absorption, and fluorescence up-conversion spectroscopy, we find that exciton diffusion through relatively phase-pure polymer or fullerene domains limits the rate of electron and hole transfer, while prompt charge separation occurs in regions where the polymer and fullerene are molecularly intermixed (such as the co-crystal phase where fullerenes intercalate between polymer chains in pBTTT:PCBM). We moreover confirm the importance of neat domains, which are essential to prevent geminate recombination of bound electron-hole pairs. Most interestingly, using an electro-absorption (Stark effect) signature, we directly visualize the migration of holes from intermixed to neat regions, which occurs on the subpicosecond time scale. This ultrafast transport is likely sustained by high local mobility (possibly along chains extending from the co-crystal phase to neat regions) and by an energy cascade driving the holes toward the neat domains. [ABSTRACT FROM AUTHOR]

ABSTRACT It has been demonstrated that the 0-0 absorption transition of poly(3-hexylthiophene) (P3HT) in blends with poly(ethylene oxide) (PEO) could be rationally tuned through the control of the liquid-liquid phase separation process during solution deposition. Pronounced J-like aggregation behavior, characteristic for systems of a low exciton band width, was found for blends where the most pronounced liquid-liquid phase separation occurred in solution, leading to domains of P3HT and PEO of high phase purity. Since liquid-liquid phase separation could be readily manipulated either by the solution temperature, solute concentration, or deposition temperature, to name a few parameters, our findings promise the design from the out-set of semiconductor:insulator architectures of pre-defined properties by manipulation of the interaction parameter between the solutes as well as the respective solute:solvent system using classical polymer science principles. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 304-310 [ABSTRACT FROM AUTHOR]

The use of copper thiocyanate (CuSCN) as a universal solution‐processable and highly transparent hole‐transporting layer in organic bulk‐heterojunction photo­voltaic cells is demonstrated. When CuSCN is employed as a replacement for the commonly used poly(3,4‐ethyl­­enedioxythiophene):polystyrenesulfonate (PEDOT:PSS), organic solar cells with maximum power conversion efficiency of 8%, are realized; this value is 1.27 times higher than that for optimized control cells based on PEDOT:PSS. [ABSTRACT FROM AUTHOR]

Review: 130 refs. [ABSTRACT FROM AUTHOR]

We report on the enhancement of photoluminescence in thin films of poly[2-methoxy-5-((2′-ethylhexyl)oxy)-1,4-phenylenvinylene], neat or embedded in polystyrene, upon illumination with light as a function of annealing temperature, with our data emphasizing the picture of a light-induced conformation change that leads to the altered photophysical response of this polymer. [ABSTRACT FROM AUTHOR]

We report the synthesis of an electron-richfused dithienogemolodithiophenemonomer containing straight chain tetradecyl solubilizing groups.Copolymers were prepared with four different electron accepting monomersof varying reduction potential. We report how the choice of acceptorinfluences the optical properties and molecular energy levels as wellas the solid state packing. Field effect transistor devices were fabricatedusing silver source-drain electrodes, with a promising charge carriermobility up to 0.26 cm2V−1s−1for films depositedfrom non-chlorinated solvents. These results suggest dithienogemolodithiopheneis a useful building block for the development of high performancesemiconducting polymers. [ABSTRACT FROM AUTHOR]

The microstructure of blend films of conjugated polymer and fullerene, especially the degree of mixing and crystallization, impacts the performance of organic photovoltaic devices considerably. Mixing and crystallization affect device performance in different ways. These phenomena are not easy to screen using traditional methods such as imaging. In this paper, the amorphous regiorandom poly(3-hexylthiophene) is blended with the potentially crystalline fullerene [6,6]-phenyl-C61-butyric acid methyl ester PCBM and the amorphous bis-adduct. First, the degree of mixing of polymer: fullerene blends is evaluated using UV-Vis absorption, steady-state and ultra-fast photoluminescence spectroscopy. The blue-shift of the polymer emission and absorption onset are used in combination with the saturation of the polymer emission decay time upon fullerene addition in order to infer the onset of aggregation of the blends. Second, the crystallinity of the fullerene is probed using variable angle spectroscopic ellipsometry (VASE), electroluminescence and photoluminescence spectroscopy. It is shown that the red-shift of charge transfer emission in the case of PCBM based blends cannot be explained solely by a variation of optical dielectric constant as probed by VASE. A combination of optical spectroscopy techniques, therefore, allows to probe the degree of mixing and can also distinguish between aggregation and crystallization of fullerenes. [ABSTRACT FROM AUTHOR]