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Push-pull-type conjugated polymers applied in organic electronics do not always contain a perfect alternation of donor and acceptor building blocks. Misscouplings can occur, which have a noticeable effect on the device performance. In this work, the influence of homocoupling on the optoelectronic properties and photovoltaic performance of PDTSQx ff polymers is investigated, with a specific focus on the quinoxaline acceptor moieties. A homocoupled biquinoxaline segment is intentionally inserted in specific ratios during the polymerization. These homocoupled units cause a gradually blue-shifted absorption, while the highest occupied molecular orbital energy levels decrease only significantly upon the presence of 75-100% of homocouplings. Density functional theory calculations show that the homocoupled acceptor unit generates a twist in the polymer backbone, which leads to a decreased conjugation length and a reduced aggregation tendency. The virtually defect-free PDTSQx ff affords a solar cell efficiency of 5.4%, which only decreases substantially upon incorporating a homocoupling degree over 50%., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Although micelles are commonly used for drug delivery purposes, their long-term fate is often unknown due to photobleaching of the fluorescent labels or the use of toxic materials. Here, we present a metal-free, nontoxic, nonbleaching, fluorescent micelle that can address these shortcomings. A simple, yet versatile, profluorescent micellar system, built from amphiphilic poly(p-phenylenevinylene) (PPV) block copolymers, for use in drug delivery applications is introduced. Polymer micelles made from PPV show excellent stability for up to 1 year and are successfully loaded with anticancer drugs (curcumin or doxorubicin) without requiring introduction of physical or chemical cross-links. The micelles are taken up efficiently by the cells, which triggers disassembly, releasing the encapsulated material. Disassembly of the micelles and drug release is conveniently monitored as fluorescence of the single polymer chains appear, which enables not only to monitor the release of the payload, but in principle also the fate of the polymer over longer periods of time.

Organic photovoltaics (OPV) have attracted great interest as a solar cell technology with appealing mechanical, aesthetical, and economies-of-scale features. To drive OPV toward economic viability, low-cost, large-scale module production has to be realized in combination with increased top-quality material availability and minimal batch-to-batch variation. To this extent, continuous flow chemistry can serve as a powerful tool. In this contribution, a flow protocol is optimized for the high performance benzodithiophene-thienopyrroledione copolymer PBDTTPD and the material quality is probed through systematic solar-cell evaluation. A stepwise approach is adopted to turn the batch process into a reproducible and scalable continuous flow procedure. Solar cell devices fabricated using the obtained polymer batches deliver an average power conversion efficiency of 7.2 %. Upon incorporation of an ionic polythiophene-based cathodic interlayer, the photovoltaic performance could be enhanced to a maximum efficiency of 9.1 %., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The true structure of alternating conjugated polymers—the state‐of‐the‐art materials for many organic electronics—often deviates from the idealized picture. Homocoupling defects are in fact inherent to the widely used cross‐coupling polymerization methods. Nevertheless, many polymers still perform excellently in the envisaged applications, which raises the question if one should really care about these imperfections. This article looks at the relevance of chemical precision (and lack thereof) in conjugated polymers covering the entire spectrum from the molecular scale, to the micro and mesostructure, up to the device level. The different types of polymerization errors for the alkoxylated variant of the benchmark (semi)crystalline polymer poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (PBTTT) are identified, visualized, and quantified and a general strategy to avoid homocoupling is introduced. Through a combination of experiments and supported by simulations, it is shown that these coupling defects hinder fullerene intercalation and limit device performance as compared to the homocoupling‐free analog. This clearly demonstrates that structural defects do matter and should be generally avoided, in particular when the geometrical regularity of the polymer is essential. These insights likely go beyond the specific PBTTT derivatives studied here and are of general relevance for the wider organic electronics field. [ABSTRACT FROM AUTHOR]

The influence of the interface of the dielectric SiO2 on the performance of bottom-contact, bottom-gate poly(3-alkylthiophene) (P3 AT) field-effect transistors (FETs) is investigated. In particular, the operation of transistors where the active polythiophene layer is directly spin-coated from chlorobenzene (CB) onto the bare SiO2 dielectric is compared to those where the active layer is first spin-coated then laminated via a wet transfer process such that the film/air interface of this film contacts the SiO2 surface. While an apparent alkyl side-chain length dependent mobility is observed for films directly spin-coated onto the SiO2 dielectric (with mobilities of ≈10−3 cm2 V−1 s−1 or less) for laminated films mobilities of 0.14 ± 0.03 cm2 V−1 s−1 independent of alkyl chain length are recorded. Surface-sensitive near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements indicate a strong out-of-plane orientation of the polymer backbone at the original air/film interface while much lower average tilt angles of the polymer backbone are observed at the SiO2/film interface. A comparison with NEXAFS on crystalline P3 AT nanofibers, as well as molecular mechanics and electronic structure calculations on ideal P3 AT crystals suggest a close to crystalline polymer organization at the P3 AT/air interface of films from CB. These results emphasize the negative influence of wrongly oriented polymer on charge carrier mobility and highlight the potential of the polymer/air interface in achieving excellent 'out-of-plane' orientation and high FET mobilities. [ABSTRACT FROM AUTHOR]

C14‐alkoxy/alkyl PBTTT‐OR‐R, a derivative of the prototype PBTTT polymer, is relevant for optoelectronic applications because it combines PBTTT‐like intercalation behavior with enhanced charge‐transfer absorption at longer wavelengths. Additionally, fundamental insights are achieved by comparing this alternating conjugated polymer in the presence and absence of homocoupling defects. While the homocoupling‐free oxidative variant, PBTTT‐OR‐R(O), as well as the Stille polymer with 19% homocoupling defects, PBTTT‐OR‐R(S), can both form co‐crystals when stoichiometrically mixed with PC61BM, the co‐crystal of the latter shows properties which are highly dependent on the thermal processing conditions because of the presence of these defects. The PBTTT‐OR‐R(S):PC61BM co‐crystal shows a low thermal stability and PC61BM can progressively be expelled upon heating. In cooling from the melt and depending on the cooling rate, mixtures of PBTTT‐OR‐R(S) and PC61BM show a competition between co‐crystallization (fast cooling) and separate crystallization (slow cooling). The PBTTT‐OR‐R(O):PC61BM co‐crystal is much more stable up to at least 260 °C and is not influenced by the applied cooling rate. These findings also translate to the device level. The performance of PBTTT‐OR‐R:PC61BM photodiodes is severely deteriorated after isothermal annealing in case of PBTTT‐OR‐R(S), whereas the thermally robust co‐crystals of PBTTT‐OR‐R(O) allow a more flexible design of optimized devices. [ABSTRACT FROM AUTHOR]

The effect of poly(3-alkylthiophene) (P3AT) crystallinity in (nanofiber P3AT):PCBM photovoltaic devices on the energy of the charge-transfer state (ECT) and on the open-circuit voltage (Voc) is investigated for poly(3-butythiophene), poly(3-pentylthiophene) and poly(3-hexylhiophene). P3AT crystallinity, expressed as the crystalline nanofiber mass fraction f to the total P3AT mass in the spin-coating dispersion, is varied between ∼0.1 and ∼0.9 by temperature control. ECT, as obtained by Fourier-transform photocurrent spectroscopy decreased with f as ECT=ECT0-0.2f eV. Alkyl side-chain length only influences ECT0. Voc relates to ECT as Voc=ECT/q-0.6 V. [ABSTRACT FROM AUTHOR]

Two π-conjugated monomers based on bis-(1-cyano-2-thienyl-vinylene)phenylene derivatives were synthesized by Knoevenagel condensation. Both monomers are found to form electroactive polymers upon electrochemical oxidation. The withdrawing effect due to the cyano-substituent allows for the reversible n-doping of the polymer. Thus, the band gap Eg was measured using electrochemical techniques and compared with that obtained by UV–VIS–NIR spectroscopy. Based on the measured band gap of 1.87 and 1.58 eV, these polymers appear to be interesting candidates for solar-cell applications. [Copyright &y& Elsevier]

A significant number of organic electronic devices rely on blends of electron-donating and electron-accepting molecules. In bulk heterojunction organic photovoltaics, the nanoscopic phase behavior of the two individual components within the photoactive layer has a major impact on the charge separation and charge transport properties. For polymer:fullerene solar cells, it has been hypothesized that an increased accessibility of the electron-deficient monomer unit in push-pull type low bandgap polymers allows for fullerene 'docking'. The close proximity of electron donor and acceptor molecules enables more efficient charge transfer, which is beneficial for the device efficiency. With this in mind, we synthesized a series of PBDTTPD [poly(benzodithiophene-thienopyrroledione)] low bandgap copolymers with varying side chains. Solar cells were fabricated for all polymers and the device characteristics were compared. The combination of proton wideline solid-state NMR (ssNMR) relaxometry and sensitive external quantum efficiency (sEQE) measurements was shown to provide essential information on donor-acceptor interactions and phase separation in bulk heterojunction organic photovoltaics. The reduced charge transfer state absorption and the observed phase separation of crystalline PC 71 BM domains for the polymers containing the most accessible methyl-TPD unit indicate a diminished contact between donor and acceptor, leading to a loss in performance. Image 1 • PBDTTPD low bandgap copolymers are synthesized. • The polymers are applied in bulk heterojunction organic solar cells. • Steric control of the fullerene approach is realized through side chain variation. • Efficiencies go down when introducing short methyl (TPD) side chains. • ssNMR relaxometry and sEQE give detailed insights on the nanoscale organization. [ABSTRACT FROM AUTHOR]

Abstract Fullerene-free organic photovoltaics have recently reached impressive power conversion efficiencies above 14% for single junctions, increasing their competitiveness with respect to alternative thin-film technologies. In most record devices, electron-donating conjugated polymers are combined with novel generation small molecule acceptors. All-polymer organic solar cells, on the other hand, still lag behind in efficiency, although they have specific advantages in terms of ink formulation and long-term operational stability. Another point of attention is the synthetic complexity of the active layer materials, notably on the side of the new acceptor molecules. Therefore, the present study focuses on the implementation of the stable and cost-effective perylene diimide structure as the key component of high-performance electron-accepting polymers. The synthesis, structural and optoelectronic characterization of four push-pull type copolymers containing the electron-deficient bis(perylene diimide) (bis-PDI) unit is reported, as well as the photovoltaic analysis of these acceptor materials in combination with a well-known donor polymer (PTB7-Th). The acceptor polymers differ in the electron-rich part of the alternating push-pull structure and their solar cell power conversion efficiencies range from 3.2 to 4.7%. The maximum efficiency - the best performance achieved with a bis-PDI polymer so far - is obtained for the structurally most simple polymer, containing merely thiophene as the electron-rich building block. Controlled degradation under blue light in air is monitored by the bleaching of the relevant UV–Vis absorption bands, demonstrating high stability for the bis-PDI-thiophene containing polymers as compared to some prototype small molecule acceptors (FBR and ITIC). Graphical abstract Image 1 Highlights • A series of electron acceptor polymers based on bis(perylene diimide) is prepared. • All-polymer solar cells are fabricated in combination with PTB7-Th. • The best efficiency (4.7%) is obtained for the structurally most simple polymer. • The acceptor polymers have a low synthetic complexity and high photostability. [ABSTRACT FROM AUTHOR]

Although research in the field of organic photovoltaics (OPV) still merely focuses on efficiency, efforts to increase the sustainability of the production process and the materials encompassing the device stack are of equally crucial importance to fulfil the promises of a truly renewable source of energy. In this study, a number of steps in this direction are taken. The photoactive polymers all contain an electron-deficient building block inspired on the natural indigo dye, bay-annulated indigo, combined with electron-rich thiophene and 4 H -dithieno[3,2- b :2′,3′- d ]pyrrole units. The synthetic protocol (starting from indigo) is optimized and the final materials are thoroughly analyzed. MALDI-TOF mass spectrometry provides detailed information on the structural composition of the polymers. Best solar cell efficiencies are obtained for polymer:fullerene blends spin-coated from a pristine non-halogenated solvent ( o -xylene), which is highly recommended to reduce the ecological footprint of OPV and is imperative for large scale production and commercialization. [ABSTRACT FROM AUTHOR]

Abstract: Poly(p-fluoranthenevinylenes) and their dithiocarbamate precursors have been deposited on indium–tin oxide electrodes and electrochemical properties of the obtained films have been investigated by means of cyclic voltammetry studies in acetonitrile solutions containing 0.1M (n-C4H9)4NBF4 as supporting electrolyte. It has been found that all investigated polymers display well pronounced n-doping processes. Electrochemical reduction of the dithiocarbamate precursors seems to be associated with C–S bond cleavage with elimination of –SC(S)N(C2H5)2 group. In view of UV–vis spectroscopic data the obtained products, tentatively identified as polymers containing fluoranthene units connected by –CH2–CH2– bridges, are somewhat less conjugated than the corresponding poly(p-fluoranthenevinylenes). Reversible electrochemical reduction of poly(p-fluoranthenethanes) occurs at potentials only somewhat (ca. 0.1V) more negative as found for their poly(p-fluoranthenevinylenes) analogues suggesting relatively weak coupling between fluoranthene kernels in both kinds of investigated polymers. [Copyright &y& Elsevier]

Abstract: We report on the comparison of photophysical and photovoltaic properties of three different soluble alkyl derivatives of the low bandgap poly(2,5-thienylene vinylene) (PTV), synthesized using the dithiocarbamate precursor route. The solubility of the precursor material in dichlorobenzene is enhanced by the addition of hexyl, dihexyl and dodecyl sidegroups to the polymer chain. The materials were characterized in solid state by means of absorption, ellipsometry and atomic force microscopy of films made from both the pristine alkyl-PTVs and alkyl-PTVs:([6,6]-phenyl C61-butyric acid methyl ester) (PCBM) mixtures in a 1:1 ratio. The materials showed an optical bandgap below 1.7eV, derived from the absorption spectrum of the polymers. Field-effect transistors made of these materials showed hole mobilities in the range of 10−7 to 10−6 cm2/Vs. Bulk heterojunction solar cells made with the polymer:PCBM blend reached efficiencies above 0.6%. [Copyright &y& Elsevier]

Abstract: A new approach is presented in order to improve the thermal stability of polymer: [6-6]-phenyl C61 butyric acid methyl ester (PCBM) bulk heterojunction solar cells. The central idea in this approach is the use of a polymer with high glass transition temperature (T g), well above the normal operating temperatures of the devices. In this paper, a PPV-derivative with a T g of 150°C was used as an electron donor and the thermal stability of the obtained solar cells was compared with solar cells based on the reference material poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) with a T g of 45°C. The use of the material with higher glass transition temperature resulted in a significant improvement of the thermal stability of the photovoltaic parameters. Furthermore, a systematic transmission electron microscope (TEM) study demonstrates that the better thermal stability of performance coincides with a more stable active layer morphology. Both improvements are attributed to the reduced free movement of the electron donor material (PCBM) within the active layer of the solar cell. [Copyright &y& Elsevier]

An analytical model has been developed to estimate the short-circuit current density of conjugated polymer/fullerene bulk heterojunction solar cells. The model takes into account the solvent-dependent molecular morphology of the donor/acceptor blend, which was revealed by transmission electron microscopy. Field-effect transistors based on single and composite organic layers were fabricated to determine values for the charge carrier mobilities of such films. These values served as input parameters of the model. It is shown that the difference in short-circuit current density that was measured between toluene-cast and chlorobenzene-cast conjugated polymer/fullerene photovoltaic cells (Appl. Phys. Lett. 78 (2001) 841) could be very well simulated with the model. Moreover, the calculations illustrate how increasing the hole and electron mobilities in the photoactive blend can improve the overall short-circuit current density of the solar cell. [Copyright &y& Elsevier]