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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]

Molecular hybrid materials based on widely available polymers crosslinked with an inorganic species have received increasing interest for their unique property sets outside of the usual range of commodity plastics and/or nanocomposites. Here, we provide a mini‐review on molecular hybrids based on metal oxide hydrates—compounds that readily react with, for example, hydroxylated polymers to form inorganic:organic materials systems with many desirable features and properties. Focusing on titanium oxide hydrates, we discuss here that such molecular hybrids can exhibit a broad refractive index range in addition to an increased glass transition temperature, mechanical stiffness and swelling resistance in comparison to the neat polymer, which illustrates that such hybrid systems offer a new, low‐cost, robust and versatile functional materials platform with great promise for, for example, solution‐processed photonics, catalysts and antimicrobial coatings. Generally, our mini‐review seeks to provide a concise and accessible overview of titanium oxide hydrate:polymer hybrid systems, focusing on their unique properties and processability as well as their broad and largely untapped potential as functional materials. © 2024 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

In the broader polymer field, the term 'crystallinity' is often used rather loosely. However, increasingly, it becomes critical to clearly distinguish between degree of crystallinity, which provides the fractional amount of crystalline phase in a polymer, and the crystalline quality, which describes the perfection of the crystalline moieties that may form in a polymer. The reason is that these different structural features dictate important properties of plastic materials, including the mechanical properties of commodity polymers and the behavior of macromolecular ferroelectrics; they also determine which photophysical processes occur in semiconducting polymers. Hence, rigor needs to be applied when establishing structure/processing/property interrelations; and it should become a general practice that specific functions are clearly attributed to the degree of crystallinity, the crystalline quality or a combination of the two. In this perspective, in memoriam of Professor Dick Jones, a long‐time member of IUPAC's Polymer Division, we discuss the challenges of identifying—and distinguishing between—these important structural characteristics when using commonly applied measuring techniques and/or theoretical approaches. This task is often elaborate, as small changes in the chemical nature of the polymer and/or processing conditions selected can have drastic effects on both the crystalline quality and the degree of crystallinity, an issue that combined with the general ambiguity of data obtained with methodologies used to characterize polymer structures, theoretically or experimentally based. © 2023 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry. [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]

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]

Since doped polymers require a charge‐neutralizing counter‐ion to maintain charge neutrality, tailored and high degrees of doping in organic semiconductors requires an understanding of the coupling between ionic and electronic carrier motion. A method of counter‐ion exchange is utilized using the polymeric semiconductor poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] ‐C14 to deconvolute the effects of ionic/polaronic interactions with the electrical properties of doped semiconducting polymers. In particular, exchanging the counter‐ions of the dopant nitrosonium hexafluorophosphate enables investigation into the role of counter‐ion size from 5.2 to 8.2 Å in diameter. The orientational order of the polymeric crystallites is not affected with this exchange process while effectively modifying the counter‐ion distance to the charge carrier. Doped films have electrical conductivities of 320 S cm−1 and are not sensitive to an increased ion‐polaron distance. It is posited that other factors dominate the electrical properties at a device scale, such as the morphology and presence of domain boundaries. Interestingly, the temperature stability of the doped film can be drastically improved with the use of counter‐ions containing less labile bonds. This platform serves as a unique way to retain the morphology of polymeric thin films while studying charge interactions at the local scale. [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]

This special issue includes 16 contributions and broadly covers the articles within the domain of synthesis of novel organic semiconductors, understanding of charge transport in devices, exciton dynamics in organic solar cells, doping of organic semiconductors, novel characterization of such materials by energy resolved electrochemical impedance spectroscopy or charge modulation microscopy. Organic semiconductors continue to draw increasing attention from different disciplines because of the plethora of unique and attractive properties. These articles will be beneficial for researchers working within the domain of the theme of the special issue i.e. materials science, chemistry, engineering, and physics. [Extracted from the article]

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]

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]

Abstract: Many typical organic optoelectronic devices, such as light‐emitting diodes, field‐effect transistors, and photovoltaic cells, use an ultrathin active layer where the organic semiconductor is confined within nanoscale dimensions. However, the question of how this spatial constraint impacts the active material is rarely addressed, although it may have a drastic influence on the phase behavior and microstructure of the active layer and hence the final performance. Here, the small‐molecule semiconductor p‐DTS(FBTTh2)2 is used as a model system to illustrate how sensitive this class of material can be to spatial confinement on device‐relevant length scales. It is also shown that this effect can be exploited; it is demonstrated, for instance, that spatial confinement is an efficient tool to direct the crystal orientation and overall texture of p‐DTS(FBTTh2)2 structures in a controlled manner, allowing for the manipulation of properties including photoluminescence and charge transport characteristics. This insight should be widely applicable as the temperature/confinement phase diagrams established via differential scanning calorimetry and grazing‐incidence X‐ray diffraction are used to identify specific processing routes that can be directly extrapolated to other functional organic materials, such as polymeric semiconductors, ferroelectrics or high‐refractive‐index polymers, to induce desired crystal textures or specific (potentially new) polymorphs. [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]

Many technological applications that have had tremendous impact on our society and lifestyle are exploiting the emission properties of organic species such as conjugated polymers and organic small-molecule semiconductors. The most prominent case-in-point here are possibly organic light-emitting diodes, which have found use in information displays, touch screens and beyond. To further advance the rapid development of these powerful and versatile technologies, it will be of paramount importance to gain fundamental insights about which strategies and processes we can employ to alter, control and eventually enhance the emission properties of this interesting class of material. In this work, we focus on macromolecular systems and review the most important categories of tools that can be employed to efficiently alter their emission properties by manipulating their molecular architecture and electronic structure; by influencing their molecular ordering, packing motifs and overall microstructure; as well as by utilizing the ability of some of these materials to respond to external stimuli and other physical parameters (pressure, light exposure etc.) and/or to interact with other compounds, including systems of different functionalities. © 2015 Society of Chemical Industry [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]

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]

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]

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]

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]

The bulk-heterojunction nanostructure of non-crystalline polymer:fullerene blends has the tendency to rapidly coarsen when heated above its glass transition temperature, which represents an important degradation mechanism. We demonstrate that fullerene nucleating agents can be used to thermally arrest the nanostructure of photovoltaic blends that comprise a non-crystalline thiophene-quinoxaline copolymer and the widely used fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). To this end, C60 fullerene is employed to efficiently nucleate PCBM crystallization. Sub-micrometer-sized fullerene crystals are formed when as little as 2 wt% C60 with respect to PCBM is added to the blend. These reach an average size of only 200 nanometers upon introduction of more than 8 wt% C60. Solar cells based on C60-nucleated blends indicate significantly improved thermal stability of the bulk-heterojunction nanostructure even after annealing at an elevated temperature of 130 °C, which lies above the glass transition temperature of the blend. Moreover, we find that various other compounds, including C70 fullerene, single-walled carbon nanotubes, and sodium benzoate, as well as a number of commercial nucleating agents-commonly used to clarify isotactic polypropylene-permit to control crystallization of the fullerene phase. [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 The microstructure of neat conjugated polymers is crucial in determining the ultimate morphology and photovoltaic performance of polymer/fullerene blends, yet until recently, little work has focused on controlling the former. Here, we demonstrate that both the long-range order along the (100)-direction and the lamellar crystal thickness along the (001)-direction in neat poly(3-hexylthiophene) (P3HT) and poly[(3,3″-didecyl[2,2′:5′,2″-terthiophene]-5,5″-diyl)] (PTTT-10) thin films can be manipulated by varying crystallization temperature. Changes in crystalline domain size impact the yield and dynamics of photogenerated charge carriers. Time-resolved microwave conductivity measurements show that neat polymer films composed of larger crystalline domains have longer photoconductance lifetimes and charge carrier yield decreases with increasing crystallite size for P3HT. Our results suggest that the classical polymer science description of temperature-dependent crystallization of polymers from solution can be used to understand thin-film formation in neat conjugated polymers, and hence, should be considered when discussing the structural evolution of organic bulk heterojunctions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 700-707 [ABSTRACT FROM AUTHOR]

The physical organisation, from the molecular to the macroscale, of functional organic matter such as polymer semiconductors can profoundly affect the properties and features of the resulting architectures and their consequent performance when used as active layers in organic optoelectronic devices, including organic thin-film field-effect transistors, organic light-emitting diodes or organic photovoltaic cells. Here, we present a survey on the principles of structure development from the liquid phase of this interesting and broad class of materials with focus on how to manipulate their phase transformations and solid-state order to tailor and manipulate the final 'morphology' towards technological and practical applications. Copyright © 2012 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

The effect of the addition of 1,8-octanedithiol (ODT) during processing on the microstructure of blend films of poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)- alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) and [6,6]-phenyl-C71 butyric acid methyl ester ([70]PCBM) is studied. Grazing incidence X-ray diffraction and absorption spectroscopy show that the crystalline order of PCPDTBT increases when ODT is introduced in the solution phase either to neat polymer systems or to blends with [70]PCBM. The increased crystalline order is accompanied by less dispersive hole transport in the polymer, and leads to a more efficient formation of a percolating fullerene network within the blend. This contributes to an increase in photocurrent generation. However, the bimolecular recombination rate as determined from photovoltage transients increases upon addition of ODT, limiting the power conversion efficiency to values well below those expected from the energy levels of PCPDTBT. We propose some explanations for this increase in bimolecular recombination, based also on variable angle spectroscopic ellipsometry measurements. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 [ABSTRACT FROM AUTHOR]