The structural anisotropy of various poly(alkylthiophene) films have been studied by X-ray diffraction, using both conventional methods and synchrotron radiation at grazing incidence. Solution-cast films orient with the side chains preferably normal to the film surface, whereas spin-cast films of nonstereoregular material orient with both the main and the side chains in the film plane. For thick (10-50 µm) solution-cast films, the degree of orientation depends strongly on the solvent used for casting, and on the stereoregularity of the polymer, films of stereoregular materials being more oriented than those of nonregular materials. The most oriented nonregular films are those cast from mixtures of chloroform and tetrahydrofuran. Thin (50-500 nm) solution-cast films are more oriented than the thicker ones, and the effects of different stereoregularity or different casting solvents are small. For spin-cast films, the degree of orientation is independent of substrate and solvent. Spin-cast films of stereoregular material have two different phases: One with the side chains normal to the substrate, and another where they are parallel to the substrate. The diffraction peaks of spin-cast poly(octylthiophene) narrow considerably upon heating.
Electrochemical dedoping and redoping of p-toluene sulfonate doped poly(3,4-ethylenedioxythiophene) (PEDOT) has been studied with in situ grazing incidence diffraction with water used as an electrolyte. The diffraction peak positions and integrated intensities do not change significantly during doping and dedoping, while the peak widths increase upon dedoping and decrease upon doping. This implies that the lattice parameters and the relative positions of the polymer chains and the p-toluene sulfonate ions remain unchanged, the redox processes being carried out by the motion of smaller ions between the polymer and the electrolyte, and that the structural order decreases upon dedoping and increases upon doping in a reversible manner.
Various substituted poly(phenylthiophene)s have been studied by X-ray diffraction. They are semicrystalline, with very different degrees of crystallinity. Those with para-substituted phenyl groups have a low degree of crystallinity, whereas those with ortho-substituted phenyl groups are more crystalline. The most crystalline materials in this study have two equally long substituents on the phenyl ring, one at the ortho position and the other at the ortho or meta position on the opposite side of the phenyl ring. Poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT) was most thoroughly studied, and a structural model is proposed. The structure of PDOPT is quite different from previously studied substituted polythiophenes in that the octyl side chains are directed normal to the thiophene planes. In this way, the conjugated polymer chains are kept separated from each other. Solution-cast and spin-cast PDOPT films are anisotropic, with the octyl side chains oriented normal to the film surface in both cases. This is contrary to the situation for poly(3-alkylthiophene)s, where solution-cast and spin-cast films orient in different ways.
The electrochromic polymer poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) spin-coated on ITO/glass was patterned with a soft lithographic method in order to diffract the incident light and thereby modify absorption of light by the film to improve the electrochromic efficiency of the polymer. The absorbance peak at around 610 nm was found to be much higher in the patterned PEDOT-PSS film than the one observed in the unpatterned film. Values of coloration efficiencies varying from 107 to 174 cm2/C were obtained for three different unpatterned PEDOT-PSS films, whereas for three different patterned PEDOT-PSS films higher values ranging from 211 to 371 cm2/C were found. These increased values of the electrochromic efficiencies are attributed to diffraction. © 2004 The Electrochemical Society. All rights reserved.
Powering the future, while maintaining a cleaner environment and a strong socioeconomic growth, is going to be one of the biggest challenges faced by mankind in the 21st century. The first step in overcoming the challenge for a sustainable future is to use energy more efficiently so that the demand for fossil fuels can be reduced drastically. The second step is a transition from the use of fossil fuels to renewable energy sources. In this sense, organic electrode materials are becoming increasingly attractive compared to inorganic electrode materials which have reached a plateau regarding performance and have severe drawbacks in terms of cost, safety and environmental friendliness. Using organic composites based on conducting polymers, such as polypyrrole, and abundant, cheap and naturally occurring biopolymers rich in quinones, such as lignin, has recently emerged as an interesting alternative. These materials, which exhibit electronic and ionic conductivity, provide challenging opportunities in the development of new charge storage materials. This review presents an overview of recent developments in organic biopolymer composite electrodes as renewable electroactive materials towards sustainable, cheap and scalable energy storage devices.
A ternary composite supercapacitor electrode consisting of phosphomolybdic acid (HMA), a renewable biopolymer, lignin, and polypyrrole was synthesized by a simple one-step simultaneous electrochemical deposition and characterized by electrochemical methods. It was found that the addition of HMA increased the specific capacitance of the polypyrrole-lignin composite from 477 to 682 F g(-1) ( at a discharge current of 1 A g(-1)) and also significantly improved the charge storage capacity from 6(to 128 mA h g(-1).
The electrochemical and optical properties of a series of alternating polyfluorene copolymers with low band gaps were determined. These polymers incorporated fluorene units alternating with groups including electron-withdrawing (A) and electron-donating (D) groups in donor-acceptor-donor (DAD) sequence to achieve the lowering of band gaps. The polymers were solvent-casted on platinum disk electrode and the band gaps were estimated from cyclic voltammetry (CV). These values were compared with values obtained from optical absorption measurements. Although the electrochemically determined band gaps were found to be slightly higher than the optical band gap in most cases, values are well correlated. The values of the band gaps determined range from 2.1 to 1.3 eV. © 2006 Elsevier B.V. All rights reserved.
Developing sustainable organic electrode materials for energy storage applications is an urgent task. We present a promising candidate based on the use of lignin, the second most abundant biopolymer in nature. This polymer is combined with a conducting polymer, where lignin as a polyanion can behave both as a dopant and surfactant. The synthesis of PEDOT/Lig biocomposites by both oxidative chemical and electrochemical polymerization of EDOT in the presence of lignin sulfonate is presented. The characterization of PEDOT/Lig was performed by UV-Vis-NIR spectroscopy, FTIR infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry and galvanostatic charge-discharge. PEDOT doped with lignin doubles the specific capacitance (170.4 F g(-1)) compared to reference PEDOT electrodes (80.4 F g(-1)). The enhanced energy storage performance is a consequence of the additional pseudocapacitance generated by the quinone moieties in lignin, which give rise to faradaic reactions. Furthermore PEDOT/Lig is a highly stable biocomposite, retaining about 83% of its electroactivity after 1000 charge/discharge cycles. These results illustrate that the redox doping strategy is a facile and straightforward approach to improve the electroactive performance of PEDOT.
We report spectroelectrochemical studies to investigate the charge storage mechanism of composite polypyrrole/lignin electrodes. Renewable bioorganic electrode materials were produced by electropolymerization of pyrrole in the presence of a water-soluble lignin derivative acting as a dopant. The resulting composite exhibited enhanced charge storage abilities due to a lignin-based faradaic process, which was expressed after repeated electrochemical redox of the material. The in situ FTIR spectroelectrochemistry results show the formation of quinone groups, and reversible oxidation-reduction of these groups during charge-discharge experiments in the electrode materials. The most significant IR bands include carbonyl absorption near 1705 cm(-1), which is attributed to the creation of quinone moieties during oxidation, and absorption at 1045 cm(-1) which is due to hydroquinone moieties.
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.
The charge carrier dynamics of a new polymer-fullerene blend are examined on the femtosecond to the millisecond time scale. The full time range is globally fitted using a chemical reaction rate model that includes all key processes, charge generation, energy transfer, charge separation, and recombination, over the full 12 orders of magnitude in time and a factor of 33 in light intensity. Particular attention is paid to the charge recombination processes and it is found that they are highly material specific. Comparison of the dynamics to those of a previously studied polymer: fullerene blend reveals that while for one blend the recombination dynamics are mainly controlled by geminate recombination, the charge recombination in the presently studied polymer: fullerene blend are entirely controlled by non-geminate electron-hole recombination. Carrier density dependence of the non-geminate recombination rate is analyzed and a correlated disorder model of site energies is proposed to explain the observed dependency.
Hole mobility in polyfluorene/fullerene blends has been studied with field effect transistors. Two different C60 derivatives and one C70 derivative have been investigated together with two different polyfluorenes. Mobility is presented as a function of acceptor loading at ratios suitable for photovoltaics and varies between 10–3 and 10–5 cm2 V–1 s–1 depending on the polymer/acceptor combination. The hole mobility is increased in blends with the commonly used acceptor [6-6]-phenyl-C61-butyric acid methylester (PCBM). With related C60 and C70 derivatives the hole mobility is decreased under the same circumstances.
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.
Both electron and hole mobilities have been simultaneously measured through charge extraction by linearly increasing voltage on polymer heterojunction solar cells with varying stoichiometry of polymer and acceptor. The polymer is a low band gap copolymer of fluorene, thiophene, and electron accepting groups named APFO-Green 5, and the acceptor is [6,6]-phenyl-C61-butyric acid methylester. Results are correlated to field effect transistor measurements on the same material system. A monotonous increase in mobility for both carrier types is observed with increased acceptor loading.
Bipolar transport in blends of a copolymer of fluorene, thiophene and electron accepting groups, and the substituted fullerene [6,6]-phenyl-C61-butyric acid methylester have been studied through charge extraction by linearly increasing voltage on solar cells and with field effect transistors. Between 10% and 90% polymer has been used and the results show a clear correlation to solar cell performance. Optimal solar cells comprise 20% polymer and have a power conversion efficiency of 3.5%. The electron mobility is increasing strongly with fullerene content, but is always lower than the hole mobility, thus explaining the low amount of polymer in optimized devices.
We have demonstrated a general way to tune the emission of poly(alkylthiophenes) by using steric interaction between the repeating units. Light-emitting diodes prepared of the polymers have blue to near-infrared emission.
We report a systematic approach to the control of the conjugation length along the poly(thiophene) backbone. The planarity of the main chain can be permanently modified by altering the pattern of substitution and character of the substituents on the poly(thiophene) chain, and the conjugation length is thus modified. We obtain blue, green, orange, red, and near-infrared electroluminescence from four chemically distinct poly(thiophenes). The external quantum efficiencies are in the range of 0.01-0.6%.
We have demonstrated two general ways to increase the photoluminescence efficiency of films from conjugated polymers. One is to disperse the conjugated polymer on a molecular level by using attractive forces between the conjugated polymer and the matrix. The other method is to substitute the conjugated polymer with side chains which separates the conjugated backbones. Using this idea a new poly(thiophene) with a photoluminescence efficiency of 16% in films has been prepared. LEDs from this polymer exhibit an external efficiency of 0.1% for single layer and 0.7% for double layer diodes.
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We have shown that it is possible to regioselectively polymerize 3-(4-octylphenyl) thiophene with FeCl3. Adding FeCl3 slowly to the monomer leads to a soft and therefore regioselective polymerization. The head-to-tail content was determined by H-1 NMR to be 94 +/- 2%. Thin films of the polymer treated with chloroform vapor have an absorption maximum at 602 nm (2.06 eV) with clear vibronic fine structure. Free standing films have a conductivity of 4 S/cm, which is 100 times higher than for earlier prepared poly(3-(4-octylphenyl)thiophene). A mechanism for the regioregular polymerization is also proposed.
Different mixtures of identically substituted C60 and C70 based fullerens have been used as acceptors in three polymer: fullerene systems that strongly express various performance limiting aspects of bulk heterojunction solar cells. Results are correlated with, and discussed in terms of e.g. morphology, charge separation, and charge transport. In these systems, there appears to be no relevant differences in either mobility or energy level positions between the identically substituted C60 and C70 based fullerenes tested. Examples of how fullerene mixtures influence the nano-morphology of the active layer are given. An upper limit to the open circuit voltage that can be obtained with fullerenes is also suggested.
We combine results from transient optical absorption in a bulk heterojunction polymer donor/fullerene acceptor material, obtained in the optical range as well as in the THz range, with results from electrical transients after a short light pulse, to present a unified interpretation of the transport of charge after the very first act of photoinduced charge transfer. We find that the mobility of charges is initially very high, but dramatically reduced with time, to arrive at values three orders of magnitude lower. We show that this can be understood as a consequence of the transport of hot charges by hopping through the density of states, from higher to lower energies.
Recombination in the well-performing bulk heterojunction solar cell blend between the conjugated polymer TQ-1 and the substituted fullerene PCBM has been investigated with pump-probe transient absorption and charge extraction of photo-generated carriers (photo-CELIV). Both methods are shown to generate identical and overlapping data under appropriate experimental conditions. The dominant type of recombination is bimolecular with a rate constant of 7 x 10(-12) cm(-3) s(-1). This recombination rate is shown to be fully consistent with solar cell performance. Deviations from an ideal bimolecular recombination process, in this material system only observable at high pump fluences, are explained with a time-dependent charge-carrier mobility, and the implications of such a behavior for device development are discussed.
Empirical data for the fill factor as a function of charge carrier mobility for two different polymer: fullerene systems is presented and analyzed. The results indicate that charge extraction depth limitations and space charge effects are inconsistent with the observed behavior, and the decrease in the fill factor is, instead, attributed to the field-dependent charge separation and geminate recombination. A solar cell photocurrent limited by the Onsager-Braun charge transfer exciton dissociation is shown to be able to accommodate the experimental observations. Charge dissociation limited solar cells always benefit from increased mobilities, and the negative contribution from the reduced charge separation is shown to be much more important for the fill factor in these material systems than any adverse effects from charge carrier extraction depth limitations or space charge effects due to unbalanced mobilities. The logarithmic dependence of the fill factor on the mobility for such a process is also shown to imply that simply increasing the mobilities is an impractical way to reach very high fill factors under these conditions since unrealistically high mobilities are required. A more controlled morphology is, instead, argued to be necessary for high performance.
The temperature dependence of charge carrier mobility in conjugated polymers and their blends with fullerenes is investigated with different electrical methods, through field effect transistor (FET), space charge limited current (SCLC) and charge extraction (CELIV) measurements. Simple models, such as the Gaussian disorder model (GDM), are shown to accurately predict the temperature behavior, and a good correlation between the different measurement methods is obtained. Inconsistent charge carrier concentrations in the modeling are explained through intrinsic non-equilibrium effects, and are responsible for the limited applicability of existing numerical models. A severe extrinsic influence from water in FETs with a hydrophilic insulator interface is also demonstrated. The presence of water leads to a significant overestimate of the disorder in the materials from measurements close to room temperature and erratic behavior in the 150-350 K range. To circumvent this problem it is shown to be necessary to measure under ultra high vacuum (UHV) conditions. © 2008 Elsevier B.V. All rights reserved.
We present the synthesis and characterisation of poly(2-(2',5'-bis(2?-ethylhexyloxy)phenyl)-1, 4-phenylenevinylene) (BEHP-PPV) polymerised under different conditions. The photoluminescence efficiencies (?PL) in the solid state of BEHP-PPV obtained at 144°C and 0°C are 28% and 60%, respectively. Polymerisation temperatures below 0°C decreases the molecular weight without changing the photoluminescence efficiency to any large extent.
Electron tomography has been used for analyzing the active layer in a polymer solar cell, a bulk heterojunction of an alternating copolymer of fluorene and a derivative of fullerene. The method supplies a three-dimensional representation of the morphology of the film, where domains with different scattering properties may be distinguished. The reconstruction shows good contrast between the two phases included in the film and demonstrates that electron tomography is an adequate tool for investigations of the three-dimensional nanostructure of the amorphous materials used in polymer solar cells.
The role of an optical spacer layer has been examined by optical simulations of organic solar cells with various bandgaps. The simulations have been performed with the transfer matrix method and the finite element method. The results show that no beneficial effect can be expected by adding an optical spacer to a solar cell with an already optimized active layer thickness.
Several organic materials and blends have been studied with the use of electron tomography. Tomography reconstructions of active layers of organic solar cells, where various preparation techniques have been used, have been analysed and compared to device behaviour. In addition, materials with predefined structures, including contrast enhancing features, have been studied and double tilt data collection has been employed to improve reconstructions. Small changes in preparation procedures may lead to large differences in morphology and device performance, and the results also indicate a complex relation between these.
Optical modeling of one folded tandem solar cell and four types of stacked tandem solar cells has been performed using the finite element method and the transfer matrix method for the folded cell and the stacked cells, respectively. The results are analyzed by comparing upper limits for short circuit currents and power conversion efficiencies. In the case of serial connected tandems all of the five cell types may be compared, and we find that the folded cells are comparable to stacked tandem cells in terms of currents and power conversion efficiencies.
The optical behavior of a reflective tandem solar cell (V cell) is modeled by means of finite element method (FEM) simulations. The absorption of solar light in the active material as well as in both electrode layers is calculated. The FEM solves the electromagnetic wave equation on the entire defined geometry, resulting in the consideration of interference effects, as well as effects of refraction and reflection. Both single cells and tandem cells are modeled and confirmed to be in accordance with reflectance measurements. Energy dissipation in the active layers is studied as a function of layer thickness and folding angle, and the simulations clearly display the advantage of the light trapping feature of folded cells. This is especially prominent in cells with thinner active layers, where folding induces absorption in the active layer equivalent to that of much thicker cells.
Folded and planar solar cells are examined with optical simulations, with the finite element method. The maximum photocurrent densities during the full day are compared between cells of different geometries and tilting angles. The change of incident angle and spectrum over time are handled in this analysis. The results show that the light trapping effect of the folded cell makes these cells show higher maximum photocurrent densities than the planar cells during all hours of the day. This is the case for both single and tandem cells. The results also indicate that balancing the currents in the tandem cells by adjusting the active layer thickness may be more cumbersome with the folded tandem cells than the stacked planar cells.
A mesoscopic network in the form of a hydrogel of the highly conductive polymer PEDOT/PSS hydrogel was used in an enzyme electrode setup. Osmium was used both as a crosslink point in the hydrogel network and as a mediator between the prosthetic group of the enzyme and the conductive polymer matrix. Both biostability and high conductivity is important aspects when building nerve- or cell- electrodes. Diffusion of analytes surrounding the cells into the matrix electrode is feasible due to the open hydrogel structure. The high water content in these structures is important when buffering them to a pH of choice.
Electrodes coated with the conducting polymer poly(3,4-ethylene dioxythiophene) (PEDOT) possess attractive electrochemical properties for stimulation or recording in the nervous system. Biomolecules, added as counter ions in electropolymerization, could further improve the biomaterial properties, eliminating the need for surfactant counter ions in the process. Such PEDOT/biomolecular composites, using heparin or hyaluronic acid, have previously been investigated electrochemically. In the present study, their biocompatibility is evaluated. An agarose overlay assay using L929 fibroblasts, and elution and direct contact tests on human neuroblastoma SH-SY5Y cells are applied to investigate cytotoxicity in vitro. PEDOT: heparin was further evaluated in vivo through polymer-coated implants in rodent cortex. No cytotoxic response was seen to any of the PEDOT materials tested. The examination of cortical tissue exposed to polymer-coated implants showed extensive glial scarring irrespective of implant material (Pt:polymer or Pt). However, quantification of immunological response, through distance measurements from implant site to closest neuron and counting of ED1+ cell density around implant, was comparable to those of platinum controls. These results indicate that PEDOT: heparin surfaces were non-cytotoxic and show no marked difference in immunological response in cortical tissue compared to pure platinum controls.
New strategies to improve neuron coupling to neuroelectronic implants are needed. In particular, tomaintain functional coupling between implant and neurons, foreign body response like encapsulation must meminimized. Apart from modifying materials to mitigate encapsulation it has been shown that with extremely thinstructures, encapsulation will be less pronounced. We here utilize wire electrochemical transistors (WECTs) usingconducting polymer coated fibers. Monofilaments down to 10 μm can be successfully coated and weaved intocomplex networks with built in logic functions, so called textile logic. Such systems can control signal patterns at alarge number of electrode terminals from a few addressing fibres. Not only is fibre size in the range where lessencapsulation is expected but textiles are known to make successful implants because of their soft and flexiblemechanical properties. Further, textile fabrication provides versatility and even three dimensional networks arepossible. Three possible architectures for neuroelectronic systems are discussed. WECTs are sensitive to dehydrationand materials for better durability or improved encapsulation is needed for stable performance in biologicalenvironments.
Development of electroactive conjugated polymers, for the purpose of recording and eliciting signals in the neural systems in humans, can be used to fashion the interfaces between the two signalling systems of electronics and neural systems. The design of desirable chemical, mechanical and electrical properties in the electroactive polymer electrodes, and the means of integration of these into biological systems, are here reviewed.
Electrodes intended for neural communication must be designed to meet both the electrochemical and biological requirements essential for long term functionality. Metallic electrode materials have been found inadequate to meet these requirements and therefore conducting polymers for neural electrodes have emerged as a field of interest. One clear advantage with polymer electrodes is the possibility to tailor the material to have optimal biomechanical and chemical properties for certain applications. To identify and evaluate new materials for neural communication electrodes, three charged biomolecules, fibrinogen, hyaluronic acid (HA), and heparin are used as counterions in the electrochemical polymerization of poly (3,4-ethylenedioxythiophene) (PEDOT). The resulting material is evaluated electrochemically and the amount of exposed biomolecule on the surface is quantified. PEDOT: biomolecule surfaces are also studied with static contact angle measurements as well as scanning electron microscopy and compared to surfaces of PEDOT electrochemically deposited with surfactant counterion polystyrene sulphonate (PSS). Electrochemical measurements show that PEDOT: heparin and PEDOT: HA, both have the electrochemical properties required for neural electrodes, and PEDOT: heparin also compares well to PEDOT: PSS. PEDOT: fibrinogen is found less suitable as neural electrode material.
Conducting polymers appear very attractive as sensor materials either as the gas-sensitive component or as a matrix for easy immobilization of a specific substrate. The planar Schottky barrier diode with poly(3-octylthiophene), P3OT, as the semiconductor is used as a sensor for the detection of different gas species. The shifts in the current-voltage (C-V) characteristics as well as the C-V characteristics of the diodes due to water and ethanol vapour, ammonia gas and nitric oxide gases are studied. Nitric oxide and ammonia give the largest and most specific changes of the C-V characteristics. Nitric oxide has a doping effect, which increases the reverse current, while ammonia is the only gas that causes a negative change in the forward bias current of the I-V curve. The planar configuration of the Schottky barrier diode facilitates the absorption of gaseous species in the environment, and provides a simple method for production of gas sensors.
Charge separation and recombination are key processes determining the performance of organic optoelectronic devices. Here we combine photoluminescence and photovoltaic characterization of organic solar cell devices with ultrafast multipulse photocurrent spectroscopy to investigate charge generation mechanisms in the organic photovoltaic devices based on a blend of an alternating polyquinoxaline copolymer with fullerene. The combined use of these techniques enables the determination of the contributions of geminate and bimolecular processes to the solar cell performance. We observe that charge separation is not a temperature-activated process in the studied materials. At the same time, the generation of free charges shows a dear external field and morphology dependence. This indicates that the critical step of charge separation involves the nonequilibrium state that is formed at early times after photoexcitation, when the polaronic localization is not yet complete. This work reveals new aspects of molecular level charge dynamics in the organic light-conversion systems.
Thin films of conducting polypyrrole doped with large polymeric anions of polystyrene-sulphonate are electrochemically prepared to study the metal/polymer junctions. Aluminium and gold contacts are vacuum deposited to form metal/polymer/gold sandwich structures for current-voltage characterization. Photoelectron spectroscopy, using UV and X-ray photons, is carried out to investigate the possible causes of current limitation in the Al/PPy(PSS) junction.
The nature of polymer/metal interfaces is decisive for the operation of polymer based electronic devices. At such interfaces charge transport may be affected by barrier formation, or by formation of insulating interfaces of various types. We have prepared thin films of conducting polypyrrole doped with large polymeric anions of polystyrenesulphonate for studies in metal/polymer junctions. Aluminium and gold contacts are vacuum deposited to form metal/polymer/gold sandwich structures. The current-voltage characteristics show that the interface between polypyrrole and gold is ohmic with no current limitation. However, the aluminium/polypyrrole interface forms highly resistive and nonohmic contacts. Photoelectron spectroscopy using UV and X-ray photons reveals a decrease of the work function upon Al deposition, reactions between Al and the sulphonate anions, and immediate oxidation of the aluminium upon exposure to oxygen. These observations corroborate the interpretation that the current limitation found at Al/polypyrrole junctions is due to formation of insulating aluminium oxide, not excluding reactions between the metal and dopant. It is also pointed out that interfaces between reactive metals and polymers are prone to such oxide interface formation, considering the high diffusivity of oxygen in many polymers.
Control of the nanoscale morphology of the donor-acceptor material blends inorganic solar Cells is critical for optimizing the photovoltaic performances. The influence of intrinsic (acceptor materials) and extrinsic (donor:acceptor weight ratio, substrate, solvent) parameters was investigated, by atomic force microscopy (AFM) and electron tomography (ET), on the nanoscale phase separation of blends of a low-band-gap alternating polyfluorene copolymers (APFO-Green9) with [6,6]-phenyl-C-71-butyric acid methyl ester ([70]PCBM). The photovoltaic performances display an optimal efficiency for the device elaborated with a 1:3 APFO-Green polymer:[70][PCBM weight ratio and spin-coated from chloroform solution. The associated active layer morphology presents small phase-separated domains which is a good balance between as a large interfacial donor-acceptor area and Continuous paths of the donor and acceptor phases to the electrodes.
The decay of photoexcitations in polythiophene chains has been studied in solid solutions of the polymer from room temperature to 4 K. A strong blue shift of the emission spectrum is observed in the polymer blend, as compared to the homopolymer. Dispersion of the polythiophene suppresses the non-radiative processes, which are suggested to be correlated to close contacts of polymer chains. Quantum chemistry modeling of the excited state distributed on two chains corroborate this conclusion.
The extension of the emission region for organic LEDs into the ultraviolet region is reported. Emission at 394 nm is achieved by modifying the geometry of a device based on poly(octylphenyl)bithiophene (PTOPT) and poly(octylphenyl)oxadiazole (PBD) which had previously been shown to emit white light. Through changing the geometry the red and green emission peaks have been suppressed and the UV band (from the PBD) enhanced.
We report on an electroluminescent diode emitting red, green, and blue light simultaneously. The device is based on a thin polymer layer, poly[3‐(4‐octylphenyl)‐2,2′‐bithiophene] and a thick molecular layer, 2‐(4‐biphenylyl)‐5‐(4‐tertbutyl‐phenyl)1,3,5‐oxadiazole. The quantum efficiency for light conversion is 0.3% and the turn‐on voltage for light emission is 7 V. In this article we present electric and spectroscopic characterizations. A mechanism for the light emission, based on electron and hole recombination between the two organic layers, is proposed