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In this article, a natural biological porous material, from living diatoms, is used to prepare new UV-protection hybrid materials with an Eu3+-complex. By removing the organic protoplasm of living diatoms, the exoskeleton with a regular pore structure arrangement was obtained. The Eu3+-complex was chemically bonded to the exoskeleton modified by the silane coupling agent (3-aminopropyl)trimethoxy silane (APTMS). Compared with pure Eu3+-complexes, the fluorescence intensity of this hybrid material was increased by approximately 10 times. For illustrating its applications in the field of UV-protection, we mixed the USDU with polyacrylonitrile to produce flexible and transparent polymer films. The hybrid composite film (USDU@PAN) achieved partial absorption of ultraviolet light between 200 and 400 nm. At the same time, it also emits visible fluorescence and the intensity of the fluorescence is greatly increased. Therefore, the USDU@PAN film has wide application prospects in areas such as photoelectric sensors and UV-protection devices. More importantly, we transform natural organisms into materials with excellent optical properties. Therefore, it can be used in the field of UV-protection.

Deoxyribonucleic acid (DNA) and a self-doped conjugated polyelectrolyte, poly(4-(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl-methoxy)-1-butanesulfonic acid (PEDOT-S), are assembled for organic optoelectronics and bioelectronics. The DNA’s helix–coil phase transition in water is studied as a function of composition by thermo-optical analysis. DNA and PEDOT-S are functionalized by using a surfactant, cetyltrimethylammonium chloride (CTMA), and DNA:CTMA, PEDOT-S:CTMA, and DNA:CTMA:PEDOT-S:CTMA complexes were characterized regarding thermal, optical, morphological, and structural properties. Finally, DNA and DNA:PEDOT-S mixtures are processed in water for fabricating organized films through brushing. The electrical properties of these films are characterized using an interdigitated electrode. The films show an electronic conductivity of ∼10–6–10–5 S/cm in a range of semiconductors.

Transparent organic electrodes printed from high-conductivity PEDOT:PSS have become essential for upscaling all-carbon based, low-cost optoelectronic devices. In the printing process, low-work-function PEDOT:PSS electrodes (cathode) are achieved by coating an ultra-thin, non-conjugated polyelectrolyte that is rich in amine groups, such as poly(ethylene imine) (PEI) or its ethoxylated derivative (PEIE), onto PEDOT:PSS surfaces. Here, we mapped the physical and chemical processes that occur at the interface between thin PEIx (indicating either PEI or PEIE) and PEDOT:PSS during printing. We identify that there is a dedoping effect of PEDOT induced by the PEIx. Using infrared spectroscopy, we found that the amine-rich PEIx can form chemical bonds with the dopant, PSS. At lower PSS concentration, PEIx also shows an electron-transfer effect to the charged PEDOT chain. These interface reactions lock the surface morphology of PEDOT:PSS, preventing the redistribution of PSS, and reduce the work function. Subsequent exposure to oxygen during the device fabrication process, on the other hand, can result in redoping of the low-work-function PEDOT:PSS interface, causing problems for printing reproducible devices under ambient conditions. Funding Agencies|Swedish Energy AgencySwedish Energy Agency; Swedish Science Council; Swedish Strategic Research Foundation through the project SiOs; Knut and Alice Wallenberg foundation (KAW) through Wallenberg Scholar grant; Knut and Alice Wallenberg foundation (KAW) through Proof of Concept project for upscaling organic solar cells

The desired attributes of organic photovoltaics (OPV) as a low cost and sustainable energy harvesting technology demand the use of non-halogenated solvent processing for the photoactive layer (PAL) materials, preferably of low synthetic complexity (SC) and without compromising the power conversion efficiency (PCE). Despite their record PCEs, most donor–acceptor conjugated copolymers in combination with non-fullerene acceptors are still far from upscaling due to their high cost and SC. Here we present a non-halogenated and low SC ink formulation for the PAL of organic solar cells, comprising PTQ10 and PC61BM as donor and acceptor materials, respectively, showing a record PCE of 7.5% in blade coated devices under 1 sun, and 19.9% under indoor LED conditions. We further study the compatibility of the PAL with 5 different electron transport layers (ETLs) in inverted architecture. We identify that commercial ZnO-based formulations together with a methanol-based polyethyleneimine-Zn (PEI-Zn) chelated ETL ink are the most suitable interlayers for outdoor conditions, providing fill factors as high as 74% and excellent thickness tolerance (up to 150 nm for the ETL, and >200 nm for the PAL). In indoor environments, SnO2 shows superior performance as it does not require UV photoactivation. Semi-transparent devices manufactured entirely in air via lamination show indoor PCEs exceeding 10% while retaining more than 80% of the initial performance after 400 and 350 hours of thermal and light stress, respectively. As a result, PTQ10:PC61BM combined with either PEI-Zn or SnO2 is currently positioned as a promising system for industrialisation of low cost, multipurpose OPV modules., The authors are thankful to Prof. Hans Arwin (Linköping University) for his valuable help in ellipsometry measurements and their corresponding optical modelling. The authors acknowledge Dr Luis Ever Aguirre (Epishine AB) for the acquisition of the indoor LED spectrum employed with laminated devices and Prof. Fengling Zhang (Linköping University) for lending the QE-Pro spectrometer. X. R.-M., S. R.-G., J. C. and O. I. acknowledge the Knut and Alice Wallenberg foundation for funding. The authors thank Dr Bernhard Dörling for building the electronic controller to make the speed profiles with the blade coater, and M. Gibert-Roca for designing and building the multiplexor for the sequential and rapid measurement of the 24 pixels in each sample. M. C. Q. greatly acknowledges funding by the Ministry of Science and Innovation through grants (CEX2019-000917-S) and PGC2018-095411-B-I00, and by the European Research Council through grant agreement no. 648901., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Spin-cast intermolecular interactions in conjugated polymer films lead to the formation of excited states delocalized over a few oriented and tightly packed conjugated segments. The optoelectronic ...

The contributions of Jean-Luc Bredas to the science of organic optoelectronics are immense, and so are the skills of communication in his talks and papers. They have been very influential and shaped the development of organic optoelectronics over a long period of time. This Festschrift contribution is a narrative of the impact of his work on my own scientific and technological studies and a way of acknowledging his great influence. Thanks!

Lignin has been proposed as electricity storage materials due to the redox activity of quinone (Q) and hydroquinone (QH(2)) groups, which can be formed in lignin. Scalable and low-cost lignosulfonate (LS)/graphite hybrid material electrodes have been developed. It is important to investigate the self discharge mechanism for these electrodes since a high self-discharge rate was observed, which results in loss of energy density and power density. In this work, self-discharge measurements and models are applied to clarify the self-discharge mechanism of the LS/graphite electrodes. A combination of diffusion controlled, activation controlled and charge equilibration mechanisms are indicated during the self discharge process at different charging voltages, due to the faradaic reactions of the Q/QH(2) confined in the electrodes. Our work contributes deeper understanding of the structure and the self-discharge mechanisms of the biopolymer/graphite hybrid electrodes. (C) 2021 The Author(s). Published by Elsevier Ltd.

The organic Eu3+-complex [Eu(TTA)3Phen] has been incorporated into the channels of surface-modified frustules from diatoms as a key material to absorb and convert UV-photons to visible luminescence. Systematic investigation results indicate that the organic Eu3+-complex encapsulated in the functionalized diatomite channels exhibits enhanced luminescence and longer lifetime, owning to the Eu(TTA)3Phen complex interacting with its surrounding silylating agents. The organic Eu3+-complex-anchored porous diatomite hybrid luminescent material was compounded with polyethylene terephthalate (PET) by using a mini-twin screw extruder to prepare a self-supporting film of the hybrid material. Besides, the UV absorption properties of the composite films were investigated. These films will potentially be related to the UV protection of photovoltaic devices., Graphical abstract

The mass implementation of renewable energies is limited by the absence of efficient and affordable technology to store electrical energy. Thus, the development of new materials is needed to improve the performance of actual devices such as batteries or supercapacitors. Herein, the facile consecutive chemically oxidative polymerization of poly(1-amino-5-chloroanthraquinone) (PACA) and poly(3,4-ethylenedioxythiophene (PEDOT) resulting in a water dispersible material PACA-PEDOT is shown. The water-based slurry made of PACA-PEDOT nanoparticles can be processed as film coated in ambient atmosphere, a critical feature for scaling up the electrode manufacturing. The novel redox polymer electrode is a nanocomposite that withstands rapid charging (16 A g−1) and delivers high power (5000 W kg−1). At lower current density its storage capacity is high (198 mAh g−1) and displays improved cycling stability (60% after 5000 cycles). Its great electrochemical performance results from the combination of the redox reversibility of the quinone groups in PACA that allows a high amount of charge storage via Faradaic reactions and the high electronic conductivity of PEDOT to access to the redox-active sites. These promising results demonstrate the potential of PACA-PEDOT to make easily organic electrodes from a water-coating process, without toxic metals, and operating in non-flammable aqueous electrolyte for large scale pseudocapacitors.

In recent years, all-polymer solar cells (all-PSCs), incorporating active layers based on blends of electron-donor (D) and acceptor (A) polymers, have drawn attention because of the advantages they hold in the flexibility of choosing the D:A combinations to modulate their energy levels and to improve their overall open-circuit voltages (V oc ) and power conversion efficiencies (PCE)s. V oc is one of the key parameters for the determination of the PCEs of PSCs. In this work, we synthesized six donor polymers with three different side chains appended to the 4,8-di(thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene (BDT) units. By substituting carbon with sulfur and silicon atoms at the 5-position of the thiophenes attached to the BDT units, the highest occupied molecular orbital (HOMO) levels of the donor polymers could be successfully lowered. As anticipated, the V oc values of the resulting all-PSCs increased along with the lowering of the HOMO levels of the donor polymers. Among the six all-PSCs, the PBDT-BDD:PNDI-T10 all-PSC realized a balance between the photovoltage and photocurrent, where a decent PCE of 5.6% was obtained with a V oc of 0.9 V and a photocurrent of 10.5 mA/cm 2 .

Vapour phase polymerized (VPP) PEDOT obtained using triblock copolymer PEG–PPG–PEG:Fe(III) tosylate polymeric oxidative layers has shown record-high conductivity and unique thermoelectric properties. These properties are related to the molecular weight, morphology and doping of PEDOT. Here we show that in its unwashed condition, the PEDOT chain adopts a neutral benzenoid conformation. The polymer chain converts into the charged quinoid structure after the removal of oxidizers with solvent washing. X-ray diffraction results suggest that the dopant is also incorporated into the packed polymer after the washing process. The changes in the chain structure and doping lead to the characteristic polaron and bipolaron absorption in the 800 and 1200 nm range. We observed a large contraction of the film after washing that is likely due to these changes, along with the removal of excessive polymer:oxidizer trapped in the PEDOT matrix. The contraction of films can be completely suppressed by mechanical clamping. PEDOT films without contraction show both a higher conductivity and higher optical transparency.

Counterion exchange has been introduced as a method to modify properties of anionic conjugated polyelectrolyte (CPE) blends. Blending of two self-doped CPEs having metallic and semiconducting behavior has been achieved from two different solvents, by exchanging the counterion of the metallic component. Different blending conditions lead to films exhibiting different optical properties, depending on the aggregation states of the CPEs. Conductance responses for the blends showed the opportunity to tune threshold voltage of the films both by blending and counterion exchange. Therefore, the blends have been exploited for the fabrication of accumulation mode organic electrochemical transistors. These devices exhibit short switching times and high transconductance, up to 15.3 mS, as well as high stability upon fast pulsed cycles, retaining 88% of the drain currents after 2 × 103 cycles.

This paper presents the work carried out within the European project RENAISSANCE-ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications. Within the project different types of innovative polyelectrolytes were synthesized such as poly(ionic liquid)s coming from renewable or natural ions, thiazolium cations, catechol functionalities or from a new generation of cheap deep eutectic monomers. Further, macromolecular architectures such as new poly(ionic liquid) block copolymers and new (semi)conducting polymer/polyelectrolyte complexes were also developed. As the final goal, the application of these innovative polymers in energy and the environment was investigated. Important advances in energy storage technologies included the development of new carbonaceous materials, new lignin/conducting polymer biopolymer electrodes, new iongels and single-ion conducting polymer electrolytes for supercapacitors and batteries and new poly(ionic liquid) binders for batteries. On the other hand, the use of innovative polyelectrolytes in sustainable environmental technologies led to the development of new liquid and dry water, new materials for water cleaning technologies such as flocculants, oil absorbers, new recyclable organocatalyst platforms and new multifunctional polymer coatings with antifouling and antimicrobial properties. All in all this paper demonstrates the potential of poly(ionic liquid)s for high-value applications in energy and enviromental areas. © 2017 Society of Chemical Industry

The use of semi-transparent photovoltaic devices causes an inevitable loss of photocurrent, as light transmitted has not been absorbed. This trivial effect also leads to a loss of photovoltage, an effect partially due to the lower photocurrent but also due to the geometry of the semi-transparent photovoltaic device. We here demonstrate and evaluate this photovoltage loss in semi-transparent organic photovoltaic devices, compared with non-transparent solar cells of the same material. Semi-transparent solar cells in addition introduce photovoltage loss when formed by lamination. We document and analyze these effects for a number of polymer blends in the form of bulk heterojunctions. Funding Agencies|Knut and Alice Wallenberg foundation (KAW), through a Wallenberg Scholar grant; China Scholarship CouncilChina Scholarship Council

Humic acid (HA) is a biopolymer formed from degraded plants, making it a ubiquitous, renewable, sustainable, and low cost source of biocarbon materials. HA contains abundant functional groups, such as carboxyl-, phenolic/alcoholic hydroxyl-, ketone-, and quinone/hydroquinone (Q/QH2)-groups. The presence of Q/QH2 groups makes HA redox active and, accordingly, HA is a candidate material for energy storage. However, as HA is an electronic insulator, it is essential to combine it with conductive materials in order to enable fabrication of HA electrodes. One of the lowest cost types of conductive materials that can be considered is carbon-based conductors such as graphite. Herein, we develop a facile method allowing the biocarbon to meet carbon, HA (in the form of a sodium salt) is mixed with graphite by a solvent-free mechanochemical method involving ball milling. Few-layer graphene sheets are formed and the HA/graphite mixtures can be used to fabricate HA/graphite hybrid material electrodes. These electrodes exhibit a conductivity of up to 160 S&middot, m&minus, 1 and a discharge capacity as large as 20 mAhg&minus, 1. Our study demonstrates a novel methodology enabling scalable fabrication of low cost and sustainable organic electrodes for application as supercapacitors.

Counterion exchange strategies are used to modify the hydrophilic character of the self-doped conjugated polyelectrolyte PEDOTS. The supramolecular complexes, soluble in organic solvents, are suitable to fabricate finely performing thin active layers in organic electrochemical transistors (OECTs). We demonstrate that ionic transport in these PEDOTS based complexes, thus their performance in OECT devices, is governed by a delicate balance among degree of doping, wettability and porosity, which can be controlled by a precise tuning of the polyelectrolyte/hydrophobic counterion ratio. We also show that the device operation can be modulated by varying the composition of the aqueous electrolyte in a range compatible with biological processes, making these materials suitable candidates to be interfaced with living cells. Funding Agencies|Knut and Alice Wallenberg foundation, through a Wallenberg Scholar grant; Advanced Functional Materials (AFM) at Linkoping University a Swedish Government Strategic Research Area

Printed and flexible organic electronics is a steadily expanding field of research and applications. One of the most attractive features of this technology is the possibility of large area and high throughput production to form low-cost electronics on different flexible substrates. With an increasing demand for sustainable energy production, low-cost and large volume technologies to store high-quality energy become equally important. These devices should be environmentally friendly with respect to their entire life cycle. Supercapacitors and batteries based on paper hold great promise for such applications due to the low cost and abundance of cellulose and other forest-derived components. We report a thick-film paper-supercapacitor system based on cellulose nanofibrils, the mixed ion-electron conducting polymer PEDOT: PSS and sulfonated lignin. We demonstrate that the introduction of sulfonated lignin into the cellulose-conducting polymer system increases the specific capacitance from 110 to 230 F g(-1) and the areal capacitance from 160 mF cm(-2) to 1 F cm(-2). By introducing lignosulfonate also into the electrolyte solution, equilibrium, with respect to the concentration of the redox molecule, was established between the electrode and the electrolyte, thus allowing us to perform beyond 700 charge/discharge cycles with no observed decrease in performance. Funding Agencies|Knut and Alice Wallenberg foundation [KAW 2011.0050]; Swedish Foundation for Strategic Research [GMT14-0058]; Onnesjo Foundation; Swedish Energy Agency; Advanced Functional Materials Center at Linkoping University

Two self-doped conjugated polyelectrolytes, having semiconducting and metallic behaviors, respectively, have been blended from aqueous solutions in order to produce materials with enhanced optical and electrical properties. The intimate blend of two anionic conjugated polyelectrolytes combine the electrical and optical properties of these, and can be tuned by blend stoichiometry. In situ conductance measurements have been done during doping of the blends, while UV–vis and EPR spectroelectrochemistry allowed the study of the nature of the involved redox species. We have constructed an accumulation/depletion mode organic electrochemical transistor whose characteristics can be tuned by balancing the stoichiometry of the active material.

Typically a donor-acceptor (D-A) design strategy is used for engineering the bandgap of polymers for solar cells. However, in this work, a series of alternating D-A(1-)D-A(2) copolymers PnTQTI(F) were synthesized and characterized with oligothiophenes (nT, n = 1, 2, 3) as the donor and two electron-deficient moieties, quinoxaline and isoindigo, as the acceptors in the repeating unit. We have studied the influence of the donor segments with different numbers of thiophene units and the effect of the addition of fluorine to the quinoxaline unit of the D-A(1)-D-A(2) polymers. The photophysical, electrochemical, and photovoltaic properties of the polymers were examined via a range of techniques and related to theoretical simulations. On increasing the length of the donor thiophene units, broader absorption spectra were observed in addition to a sequential increase in HOMO levels, while the LUMO levels displayed very small variations. The addition of fluorine to the quinoxaline unit not only decreased the HOMO levels of the resulting polymers but also enhanced the absorption coefficients. A superior photovoltaic performance was observed for the P3TQTI-F-based device with a power conversion efficiency (PCE) of 7.0%, which is the highest efficiency for alternating D-A(1)-D-A(2) polymers reported to date. The structureproperty correlations of the PnTQTI(F) polymers demonstrate that varying of the length of the donor segments is a valuable method for designing high-performance D-A(1)-D-A(2) copolymers and highlight the promising nature of D-A(1)-D-A(2) copolymers for efficient bulk-heterojunction solar cells.

Herein we report on the investigation of self-assembled protein nanofibrils functionalized with metallic organic compounds. We have characterized the electronic behaviour of individual nanowires using conductive atomic force microscopy. In order to follow the self assembly process we have incorporated fluorescent molecules into the protein and used the energy transfer between the internalized dye and the metallic coating to probe the binding of the polyelectrolyte to the fibril.

Photoexcitation of conjugated polymer–fullerene blends results in population of a local charge transfer (CT) state at the interface between the two materials. The competition between recombination and dissociation of this interfacial state limits the generation of fully separated free charges. Therefore, a detailed understanding of the CT states is critical for building a comprehensive picture of the organic solar cells operation. We applied a new fluorescence microscopy method called two-dimensional polarization imaging to gain insight into the orientation of the transition dipole moments of the CT states, and the associated excitation energy transfer processes in TQ1:PCBM blend films. The polymer phase was oriented mechanically to relate the polymer dipole moment orientation to that of the CT states. CT state formation was observed to be much faster than energy transfer in the polymer phase. However, after being formed an emissive CT state does not exchange excitation energy with other CT states, sugges...

We present a detailed investigation of the refractive index of polymer:fullerene blends for photovoltaic applications. The donor polymers poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(4,7-di-2-thienyl-2,1,3-benzothiadiazole)] (APFO3), poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1), and poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(5,10-di-2-thienyl-2,3,7,8-tetraphenyl-pyrazino[2,3-g]quinoxaline)] (APFO-Green9) were blended with either [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) or [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). We measured variable angle spectroscopic ellipsometry for three systems, namely APFO3:PCBM, TQ1:PC71BM and APFO-Green9:PC71BM, as a function of composition and analyze the data employing a number of models. We found that Bruggeman effective medium approximations (EMA) are not precise for the description of the optical properties of these blends. This is due to a number of reasons. First, we find that there are energy shifts associated to changes in conjugation length that cannot be accounted for using EMA. Second, blending results in a strong reduction of anisotropy. Finally, our data suggest that there is some degree of vertical segregation between components. Therefore, our results support the idea that the optical properties of polymer:fullerene mixtures should be treated as alloys rather than non-interacting blends.

Organic solar cells with a high degree of thermal stability require bulk-heterojunction blends that feature a high glass transition, which must occur considerably above the temperatures encountered during device fabrication and operation. Here, we demonstrate for the first time a polymer : fullerene blend with a glass transition temperature above 200 degrees C, which we determine by plasmonic nanospectroscopy. We achieve this strong tendency for glass formation through the use of an alloy of neat, unsubstituted C-60 and C-70, which we combine with the fluorothieno-benzodithiophene copolymer PTB7. A stable photovoltaic performance of PTB7 : C60 : C70 ternary blends is preserved despite annealing the active layer at up to 180 degrees C, which coincides with the onset of the glass transition. Rapid deterioration of the power conversion efficiency from initially above 5% only occurs upon exceeding the glass transition temperature of 224 degrees C of the ternary blend. Funding Agencies|Swedish Research Council; Swedish Foundation for Strategic Research [RMA11-0037, RMA15-0052]; Swedish Energy Agency

A polymeric conducting hydrogel of autopolymerized polypyrrole (PPY) and poly(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl-methoxy)-1-butanesulfonic acid (PEDOT-S) cast-deposited on a glassy carbon ...

A pronounced enhancement of the power conversion efficiency (PCE) by 38% is achieved in one-step doctor-blade printing organic solar cells (OSCs) via a simple solvent vapor annealing (SVA) step. The organic blend composed of a donor polymer, a nonfullerene acceptor, and an interfacial layer (IL) molecular component is found to phase-separate vertically when exposed to a solvent vapor-saturated atmosphere. Remarkably, the spontaneous formation of a fine, self-organized IL between the bulk heterojunction (BHJ) layer and the indium tin oxide (ITO) electrode facilitated by SVA yields solar cells with a significantly higher PCE (11.14%) than in control devices (8.05%) without SVA and in devices (10.06%) made with the more complex two-step doctor-blade printing method. The stratified nature of the ITO/IL/BHJ/cathode is corroborated by a range of complementary characterization techniques including surface energy, cross-sectional scanning electron microscopy, grazing incidence wide angle X-ray scattering, and X-ray photoelectron spectroscopy. This study demonstrates that a spontaneously formed IL with SVA treatment combines simplicity and precision with high device performance, thus making it attractive for large-area manufacturing of next-generation OSCs. Funding Agencies|NSFCNational Natural Science Foundation of China (NSFC) [61774077, 61274062, 11204106]; Guangzhou Science and Technology Plan Project [201804010295]; Research and Development Program in Key Areas of Guangdong Province [2019B090921002]; Fundamental Research Funds for the Central UniversitiesFundamental Research Funds for the Central Universities; Sunflare Institute of Solar Energy, Jinan University; Swedish Government Research Area in Materials Science on Functional Materials at Linkoping University [200900971]; Jinan UniversityJinan University; King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) [OSR-2018-CARF/CCF-3079]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; National Science FoundationNational Science Foundation (NSF) [DMR-1332208]

Two polymers with polar side chains, namely poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(5',8'-di-2-thienyl-(2',3'-bis(3''-(2-(2-methoxyethoxy)ethoxy)phenyl)quinoxaline))] (P1) and poly[2,7-(9,9-bis(2-(2-methoxyethoxy)ethyl)fluorene)-alt-5,5-(5',8'-di-2-thienyl-(2',3'-bis(3''-(2-(2-methoxyethoxy)-ethoxy)phenyl)quinoxaline))] (P2), were synthesized for solar cell application. A series of bulk heterojunction solar cells were systematically fabricated and characterized by varying the electron-acceptor materials, processing solvents and thickness of the active layer. The results show that P1, with a higher molecular weight and good film-forming properties, performed better. The best device showed an open circuit voltage of 0.87 V, a short circuit current of 6.81 mA cm(-2) and a power conversion efficiency of 2.74% with 1:4 polymer:[6,6]-phenyl-C71-butyric acid methyl ester (PCBM[70]) mixture using o-dichlorobenzene (o-DCB) as processing solvent. P2 on the other hand showed a poorer performance with chlorobenzene as processing solvent, but a much improved performance was obtained using o-DCB instead. Thus, an open circuit voltage of 0.80 V, short circuit current of 6.21 mA cm(-2) and an overall power conversion efficiency of 2.22% were recorded for a polymer:PCBM[70] mixing ratio of 1:4. This is presumably due to the improvement of the morphology of the active layer using o-DCB as processing solvent. (c) 2013 Society of Chemical Industry

Geometric confinement and interface effects can significantly alter the thermodynamic properties of thin polymer films. Phase transition temperatures have been shown to strongly depend on film thickness below a critical thickness threshold. It has been suggested that this behavior is due to an interface-induced continuous variation in phase transition temperatures throughout the depth of the films. Here we employ variable-temperature spectroscopic ellipsometry to demonstrate the existence of these depth profiles. We examine four different polymer semiconductors that are of interest for organic light-emitting diodes, solar cells, and field-effect transistors. In contrast to insulating polymers, these light-absorbing materials provide detailed information about structural changes as a function of depth due to wavelength-dependent attenuation. This concept enables us to investigate a broad range of thermodynamic processes including the glass transition, crystallization as well as crystalline and liquid-cryst...

Using raster-scanning wide-angle X-ray scattering, we investigate oriented fibres of the low bandgap conjugated polymer, poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (F8TBT), that was developed in particular for polymer solar cells. For the first time, structural data are provided for F8TBT. Our results demonstrate that the nano-scale structure of this polymer is closely related to the externally observable features of the fibre, and thus emphasise the importance of having full control over the local molecular conformation. Liquid-crystalline phases are observed at elevated temperatures, and the molecular alignment in the drawn fibres yields scattering patterns that are dominated by broad peaks of equatorial diffuse scattering. The significant degree of preferred orientation facilitates the analysis, leading to estimates of (average) nearest-neighbour packing distances and coherence length of this macromolecule. In particular, we observe a pronounced broad signal assigned to packing of the conjugated backbone with an approximate spacing of 4.00–4.39 A that is coherent over 5-6 polymer segments.

Optical and structural properties of a hybrid metallic chevron sculptured thin film from titanium coated with the semiconducting polymer poly(3-dodecylthiophene) (P3DDT) are reported. The nanostructured thin film with two subsequent layers of oppositely slanted nanocolumns was fabricated by glancing angle deposition and coated with P3DDT by a spin-cast process. Spectroscopic generalized ellipsometry is employed to determine geometrical structure properties and the anisotropic optical constants of the coated and uncoated film in the spectral range from 400 to 1700 nm. The nanostructured thin films before and after hybridization show highly anisotropic optical properties. The complex refractive indices along major polarizability directions of the hybridized chevrons are increased in the entire investigated spectral range with respect to the as-deposited chevrons. Changes in birefringence and dichroism upon polymer infiltration are observed.

A new benzodithiophene (BDT)-based polymer, poly(4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b]dithiophene vinylene) (PBDTV), was synthesized by Pd-catalyzed Stille-coupling method. The polymer is soluble in common organic solvents and possesses high thermal stability. PBDTV film shows a broad absorption band covering from 350 nm to 618 nm, strong photoluminescence peaked at 545 nm and high hole mobility of 4.84 x 10(-3) cm(2)/Vs. Photovoltaic properties of PBDTV were studied by fabricating the polymer solar cells based on PBDTV as donor and PC70BM as acceptor. With the weight ratio of PBDTV: PC70BM of 1:4 and the active layer thickness of 65 nm, the power conversion efficiency of the device reached 2.63% with V-oc = 0.71 V, I-sc = 6.46 mA/cm(2), and FF = 0.57 under the illumination of AM1.5, 100 mW/cm(2).

We demonstrate the shaping and forming of organic electronic polymers into designer nanostructures using biomacromolecules. In order to create nanowires, nanohelixes and assemblies of these, we coordinate semiconducting or metallic polymers to biomolecular polymers in the form of DNA and misfolded proteins. Optoelectronic and electrochemical devices utilizing these shaped materials are discussed.

Using extraction of photogenerated charge carriers by linearly increasing voltage (photo-CELIV), we investigated two key transport parameters in photovoltaic materials based on the donor APFO-3 and acceptor PCBM: the mobility and lifetime of photogenerated charge carriers, in bilayers of varying geometry and in blends with various acceptors loading. We find that mobility depends strongly on delay time for shorter delay time in all devices. The observed recombination kinetics is found to be monomolecular. The mean lifetime of charge carriers is 2-3 mu s in blends and is slightly greater than 4 mu s in bilayer devices. In addition, the implications of mobility and lifetime values on the collection efficiency of the devices are presented.

Chemical polymerization of a 3,4-ethylenedioxythiophene derivative bearing a sulfonate group (EDOT-S) is reported. The polymer, PEDOT-S, is fully water-soluble and has been produced by polymerizing EDOT-S in water, using Na2S2O8 and a catalytic amount of FeCl3. Elemental analysis and XPS measurements indicate that PEDOT-S is a material with a substantial degree of self-doping, but also contains free sulfate ions as charge-balancing counterions of the oxidized polymer. Apart from self-doping PEDOT-S, the side chains enable full water solubility of the material; DLS studies show an average cluster size of only 2 nm. Importantly, the solvation properties of the PEDOT-S are reflected in spin-coated films, which show a surface roughness of 1.2 nm and good conductivity (12 S/cm) in ambient conditions. The electro-optical properties of this material are shown with cyclic voltammetry and spectroelectrochemical experiment reveals an electrochromic contrast (∼48% at λmax = 606 nm).

In this work we report the coating of a biological template with a polar, but uncharged, luminescent conjugated polymer, soluble in organic solvents but not in water, to produce a nanowire. Amyloid fibrils from bovine insulin were decorated with an alternating polyfluorene derivative. Decorated fibrils were partially aligned on hydrophobic surfaces as separate and bundled fibrils, by means of molecular combing. The single molecule spectroscopy technique utilizing excitation by rotating linearly polarized light and fluorescence detection through a rotating polarizer showed a high degree of anisotropy of the polymer chains on the individual fibrils. The high degree of polarization indicated highly oriented polymer chains with the preferential orientation of the polymer backbone along the fibrils. The anisotropy ratios are comparable with those of well-oriented polymer chains in films.

There is a need for highly sensitive, multi-parallel protein sensors within diagnostics and proteomic research. Conjugated polymers (CPs) have been demonstrated as highly sensitive optical probes for protein biosensing. Compared to small molecules, the polymeric probe has the possibility of multiple interactions and a collective response, which enhances the sensor signal. The optical output is colorimetric or, more sensitive, fluorescence based, including Forster energy transfer and changes in the emission wavelengths and/or intensity. Using CPs, many interesting protein detection events have been demonstrated, e.g., protein interactions, enzymatic activity, amyloid fibril formation, and detection by aptamers. CPs have also been successfully used to stain bacterial, cellular, and tissue samples. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

Non-ideal behavior in organic field effect transistors, in particular threshold voltage drift and light sensitivity, is argued to be due to intrinsic carrier dynamics. The discussion is based on the theory for hopping transport within a Gaussian density of states. Carrier concentration is shown to be of fundamental importance, and the time required to reach equilibrium at different bias is responsible for device behavior, with implications for mobility evaluation. Experimental results from various conjugated polymers in a field effect transistor illustrate the theory.

A prototype solar cell with a transparent polymer cathode and an ITO/poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) anode was fabricated. As an active layer, a thin film of a bulk heterojunction of polyfluorene copolymer, poly[2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (APFO-3) and an electron acceptor mol. [6,6]-phenyl-C61-butyric acid Me ester (PCBM) (1:4 by wt.) was sandwiched between the 2 transparent polymer electrodes. The cathode is another form of PEDOT formed by vapor phase polymd. PEDOT (VPP PEDOT) with a cond. 102-103 S/cm. The cathode is supported on an elastomeric substrate and forms a conformal contact to the APFO-3/PCBM blend. Transparent solar cells are useful for building multilayer and tandem solar cells. [on SciFinder (R)]

We investigate charge formation in bulk-heterojunction solar cells based on conjugated polymers in the form of alternating polyfluorene copolymers and the methanofullerene PCBM. Using transient absorption spectroscopy we show that optimal charge formation is obtained with 20-50 wt% PCBM. This is in contrast to the maximum short circuit current density obtained at similar to 80 wt% PCBM as determined by steady state current density-voltage characterization. Hence, we show explicitly that the solar cell performance of these interpenetrating polymer networks containing PCBM is limited by charge transport rather than by formation of charges. (c) 2006 Elsevier B.V. All rights reserved.

Charge transport in a near infrared absorbing polyfluorene copolymer (APFO-Green1) and its blends with methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM), and 3′-(3,5-bis-trifluorom ...

Low-bandgap alternating polyfluorenes with different donor-acceptor-donor moieties were synthesized. Electrochem. and optical absorption measurement show that onset bandgaps of these polymers range from 1.2 to 1.5 eV. These polymers, blended with a C70-deriv. as acceptor, are used for solar cell fabrication. Devices show promising photovoltaic properties, and the spectral response of photocurrent covers all visible and near-IR wavelength regions with its onset extended to 1 mm. The best data gives a photocurrent d. of 3.4 mA/cm2, open circuit voltage of 0.58 V and power conversion efficiency of 0.7% under illumination of AM1.5 (1000 W/m2) from a solar simulator. [on SciFinder (R)]

An alternating polyfluorene (APFO) with low band-gap segments. APFO-Green1, was synthesized for use in optoelectronic devices. The low band-gap segment consists of an electron acceptor (A), fenced by electron donors (D). This D-A-D configuration leads to partial charge transfer in the polymer backbone and a low band-gap of 1.3 eV. Characterization of APFO-Green1 include measurement of light absorption and emission at extended wavelengths and high hole mobility was found. Blends of the polymer with different fullerene derivs. exhibit unusually high photovoltaic performance at long wavelengths, making this type of conjugated polymers promising for application in plastic solar cells. [on SciFinder (R)]

Computer screen photo-asssited detection of complementary DNA strands using a luminescent zwitterionic polythiophene derivative

Two new alternating polyfluorene copolymers containing different low band gap segments have been designed and synthesized for use in optoelectronic devices. The low band gap segments consist of electron donating and accepting moieties which induce a partial charge transfer in the polymer backbone and thereby, a lower band gap. Results obtained from characterization of the new materials, called APFO-Green1 and APFO-Green2, include absorption and emission at extended wavelengths as well as high stability. Furthermore, blends of the new copolymers with different fullerene derivatives exhibit unprecedented photovoltaic behavior at long wavelengths.

Two new, alkoxyphenyl-substituted polyfluorenes, poly(9,9-bis(4'-hexyloxyphenyl)fluorene) and poly(9,9-bis(4'-hexyloxyphenyl)fluorene-alt-9,9-bis(4'-(2''-(2'''-methoxyethoxy)ethoxy)phenyl)fluorene), were synthesized using the Suzuki coupling reaction. The polymers were designed to obtain stable and efficient materials for light-emitting applications. Both polymers exhibit high PL-efficiencies and show PL- and EL-emission in the blue spectral region, with emission maxima in a narrow range around 427 nm. Annealing (200 DegC, 2 h) of polymer films exposed to normal indoor light in ambient atm., results in an addnl. emission band at higher wavelengths, indicating degrdn. by photo oxidn. [on SciFinder (R)]

The interactions between a zwitterionic polythiophene derivative, POWT, and DNA oligonucleotides in solution have been studied by FRET (fluorescence resonance energy transfer). When POWT and ssDNA ...

The synthesis of two chiral isomers of 3-substituted polythiophenes, with cationic side-chain functionalities, and their use as conformational sensitive optical probes for the recording of pH-induced conformational changes in a synthetic peptide are reported. The conformational changes of the synthetic peptide gives rise to geometrical changes of the conjugated polyelectrolytes, and these changes are shown as alterations of the absorption-, emission-, two-photon excitation emission and circular dichroism spectra of the conjugated polyelectrolytes. Interaction between a four-helix bundle conformation of the peptide and the conjugated polyelectrolytes will lead to a more planar conformation of the polyelectrolyte backbone and separation of polyelectrolyte chains, observed as a red shift and an increase of the emitted light from conjugated polyelectrolyte. As the peptide adopts a random-coil conformation, the intensity of the emitted light is further red shifted and the intensity is decreasing, associated with aggregation of the polyelectrolyte chains. Moreover, it is demonstrated how the specific chiral recognition can be quantified as differences in fluorescence emission based on both single- and two-photon excitation from the two enantiomeric isomers which interact differently with the peptide.

Electrophosphorescence has been observed in doped polythiophene light-emitting diodes (LEDs) with poly(3-methyl-4-octylthiophene) [PMOT] as host and the phosphorescent compounds bis(2-phenylbenzothiazole) iridium acetylacetonate (BTIr) or platinum(II) 2,8,12,17-tetraethyl-3,7,13,18-tramethyl porphyrin (PtOX) as guest. The photoluminescence (PL) and electroluminescence (EL) of host–phosphorescent guest blends PMOT:BTIr (or PMOT:PtOX) showed the existence of energy transfer from host to guest, which were guest concentration-dependent. At a certain guest concentration, emission from host PMOT was completely quenched in both blends based LEDs, and this gave rise to electrophosphorescence. The PL from host PMOT in the PMOT:BTIr blend film could not be quenched completely but was totally quenched in PMOT:PtOX. This implies a more efficient energy transfer from PMOT to PtOX than that from PMOT to BTIr under optical excitation. Comparison of PL and EL showed that the mechanism of exciton formation at the guest site under electrical excitation was not identical for these two systems. Energy transfer was a dominating route for exciton formation in PMOT:PtOX-based LEDs; charge trapping effect additionally contributed to the formation of exciton at BTIr in PMOT:BTIr-based LEDs. This study demonstrates a new direction in which polythiophene can be a candidate as a host to realize electrophosphorescence in polymer light-emitting diodes (PLEDs). Authors further indicate that to optimize the performance of the polythiophe/phosphorescent complexes, LEDs proper polythiophenes with large bang gap are needed.

Electronic polymers in aqueous media offer bioelectronic detection of biomolecular processes. Here we report fluorometric detection of calcium-induced conformational changes in calmodulin based on noncovalent assembly of calmodulin to a water-soluble zwitterionic polythiophene derivative. Assembly with calmodulin will induce a planar geometry and aggregation of the polymer chains, detected as a decrease of the intensity and a red shift of the fluorescence. Upon addition of Ca2+ the intensity of the emitted light is increased and blue-shifted. The geometrical alteration of the polymer chains can further be utilized for recording of the binding of calcineurin to the calcium-activated POWT−calmodulin complex. This novel methodology, using a conformation-sensitive probe, allows fluorometric detection of conformational changes in biomolecules and protein−protein interactions without any covalent modifications of the biomolecules. The rapid and selective method is based on noncovalent interactions between a zwi...