Influence of imidazole‐based acidity control of PEDOT:PSS on its electrical properties and environmental stability

Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been studied for a wide range of applications due to its potential as a transparent electrode. Herein, the use of imidazole and its derivatives as a neutralizing additive for PEDOT:PSS dispersion and in‐depth studies of their effects in terms of electrical properties and stability is reported. Although the neutralization in general reduces the electrical conductivity of PEDOT:PSS, the conductivity after imidazole treatment (685.2 S cm^?1) is higher than that after treatment of other derivatives. Spectroscopic and thermoelectric studies show that the de‐doping effect resulted in the conductivity reduction. As a trade‐off of the conductivity reduction, greatly enhanced long‐term stability and noncorrosive characteristics are obtained after neutralization. The change in sheet resistance of imidazole‐treated PEDOT:PSS after 500 h under harsh conditions (85 °C and 85% humidity) is half that of the untreated samples, demonstrating the great enhancement of the stability. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1530–1536     

Transparent conductive films based on polymer composites containing the mixed‐valence tetrathiafulvalene nanofibers

We report the facile preparation of the conductive polymer composites containing the mixed‐valence tetrathiafulvalene (TTF) nanofibers and their applications as all‐organic transparent conductive materials. TTF can be used as a nanofiller for transforming conventional polymers to conductive materials. Self‐assemble nanofibers of the neutral and radical cation of TTF can be formed in the polymer solutions during the film deposition, and the resulting composite films with several micron thickness can serve as the conductive material with high transparency. Several kinds of conventional polymers, such as polystyrene, poly(methyl methacrylate) (PMMA), and poly(vinylpyrrolidone), can be used as a polymer matrix of the composites. The conductivities of the PMMA film containing 35 mol % of the mixed‐valence TTF and the PEDOT–PSS film showed similar values (2.8 × 10^–2 and 5.4 × 10^–1 S/cm, respectively). In contrast, the normalized transmittance of the PMMA film by 1‐μm thickness greatly increased (96%/μm) when compared with that of the PEDOT–PSS film (10%/μm). In addition, the degradation of the conductivity of the nanofibers by heating and aging was effectively suppressed in the composite samples. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6441–6450, 2009     

Effect of (3‐glycidyloxypropyl)trimethoxysilane (GOPS) on the electrical properties of PEDOT:PSS films

Poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) has been reported as a successful functional material in a broad variety of applications. One of the most important advantages of PEDOT:PSS is its water‐solubility, which enables simple and environmental friendly manufacturing processes. Unfortunately, this also implies that pristine PEDOT:PSS films are unsuitable for applications in aqueous environments. To reach stability in polar solvents, (3‐glycidyloxypropyl)trimethoxysilane (GOPS) is typically used to cross‐link PEDOT:PSS. Although this strategy is widely used, its mechanism and effect on PEDOT:PSS performance have not been articulated yet. Here, we present a broad study that provides a better understanding of the effect of GOPS on the electrical and electronic properties of PEDOT:PSS. We show that the GOPS reacts with the sulfonic acid group of the excess PSS, causing a change in the PEDOT:PSS film morphology, while the oxidation level of PEDOT remains unaffected. This is at the origin of the observed conductivity changes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 814–820     

Polymer Optoelectronic Devices with High‐Conductivity Poly(3,4‐Ethylenedioxythiophene) Anodes

Abstract

The conductivity of poly(3,4‐ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) film can be enhanced by more than two orders in magnitude by adding a compound with two or more polar groups, such as ethylene glycol (EG), meso‐erythritol (IUPAC name: 1,2,3,4‐tetrahydroxybutane), or 2‐nitroethanol, into the PEDOT:PSS aqueous solution. The mechanism of the increase in conductivity for PEDOT:PSS has been studied using Raman spectroscopy and atomic force microscope (AFM). Here we propose that the change in conductivity is due to the conformational change of PEDOT chains in the film. In untreated PEDOT:PSS films, coil, linear, or expanded‐coil conformations of the PEDOT chains may be present. In treated PEDOT:PSS films, the linear or expanded‐coil conformations may becomes the dominant form for PEDOT chains. This conformational change results in the enhancement of charge‐carrier mobility in the film and leads to enhanced conductivity. The high‐conductivity PEDOT:PSS film is ideal as the electrode for polymer optoelectronic devices. In this article, we report on the fabrication of polymer light‐emitting diodes (PLEDs) and photovoltaic cells (PVs) made using a highly conductive form of PEDOT:PSS as anode, and we demonstrate its performance relative to that of similar device using indium‐tin oxide (ITO) as the anode.     

Fast,Direct, Low‐Cost Route to Scalable,Conductive, and Multipurpose Poly(3,4‐ethylenedixoythiophene)‐Coated Plastic Electrodes

Poly(3,4‐ethylenedioxythiophene) (PEDOT) films are deposited, using an electroless method, onto flexible plastic poly(ethylene terephthalate) (PET) substrates of approximately 20×6 cm². The sheet resistance of a PEDOT–PET film is approximately 600 Ω per square, and the nanoscale conductivity is 0.103 S cm^?1. A plastic electrochromic PEDOT–Prussian blue device is constructed. The device undergoes a color change of pale blue to deep violet–blue reversibly over 1000 cycles, thus demonstrating its use as a light‐modulating smart window. The PEDOT–PET film is also used in a quantum dot solar cell, and the resulting photoelectrochemical performance and work function indicate that it is also promising for photovoltaic cells. The high homogeneity of the PEDOT deposit on PET, the optimal balance between conductivity and optical transparency, and the demonstration of its use in an electro‐optical device and a solar cell, offer the opportunity to use this electrode material in a variety of low‐cost optoelectronic devices.     

From superhydrophobic‐ to superhydrophilic‐patterned poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) architectures as a novel platform for biotechnological applications

The manufacture of three‐dimensional patterned electroactive poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) microstructures with tailored architecture, morphology, and wettability is presented. The patterned microstructures are fabricated using a simple, effective, low cost, and reproducible technique based on microfluidic technology. These novel structures can represent innovative platforms for advanced strategies in a wide range of biotechnological applications, including tissue engineering, drug delivery, microfluidic, and sensors and actuators devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1802–1810     

Biosensor employing screen‐printed PEDOT:PSS for sensitive detection of phenolic compounds in water

Poly(3,4‐ethylenedioxythiophene) (PEDOT) and its derivatives are relatively new, and unique members of conducting‐polymers family. In this article, we present an approach for simple, reliable and cost‐efficient electrochemical biosensor for real‐time detection and quantification of phenolic compounds (PhCs). The PEDOT:poly(styrene sulfonate) (PSS) polymer, directly screen‐printed on the surface of the working electrode, was shown to act as an effective electrical conductor but also as an efficient redox mediator. It has also been found suitable for the reduction of quinone ions at low reducing potentials, close to 0 V versus Ag/AgCl, thus minimizing interferences due to other electroactive species present in real samples. Based on these properties, a biosensor based on tyrosinase immobilized on PEDOT:PSS‐modified electrodes was developed allowing the detection of PhCs in surface waters. The biosensor displayed very good performance in terms of sensitivity, detection limit and linear range. Assays using surface water previously spiked with bisphenol A showed that the biosensor was able to detect PhCs in real conditions with no matrix effect. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Novel electroluminescent cationic polyelectrolyte based on poly[(fluorene‐2,7‐diylvinylene)‐alt‐(1,4‐phenylenevinylene)] and its precursor

A novel conjugated poly[(fluorene‐2,7‐vinylene)‐alt‐(1,4‐phenylenevinylene)] derivative 2 with quaternizable tertiary amino groups was synthesized by Heck coupling of a substituted 2,7‐dibromofluorene and 1,4‐dialkoxy‐2,5‐divinylbenzene. The corresponding quaternary ammonium cationic polyelectrolyte 3 was obtained by the treatment of 2 with bromoethane. Both polymers were soluble in common organic solvents, like tetrahydrofuran, chloroform, and dichloromethane. Polymer 3 showed a limited solubility in alcohols and was insoluble in water. Photophysical and electrochemical properties of the resulting polymers were fully investigated. An intensive green photoluminescence (PL) with maxima at 550 and 545 nm was observed from thin films of 2 and 3 polymers, respectively, red‐shifted compared with the PL emission spectra measured in the solution. The electrochemical band gaps were 2.38–2.45 eV. Single‐layer and double‐layer (with poly[3,4‐(ethylenedioxy)thiophene]/poly (styrenesulfonate) (PEDOT:PSS)) light‐emitting devices (LEDs) with ITO and Al electrodes were prepared and studied. They emitted a green light and their electroluminescence (EL) spectra were similar to those of PL thin films. The external EL efficiency was determined to be 0.43 and 0.32% for ITO/PEDOT:PSS/ 2 /Al and ITO/PEDOT:PSS/ 3 /Al LEDs, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1016–1027, 2007     

Photolithographic patterning of highly conductive PEDOT:PSS and its application in organic light‐emitting diodes

Photolithographically patterned highly conductive (～1400 S/cm) poly(3,4‐ethylenedioxythio‐phene):poly(styrenesulfonate) (PEDOT:PSS) films are demonstrated as electrodes for organic light emitting diodes (OLEDs). With the assistance of hydrofluoroether (HFE) solvents and fluorinated photoresists, high‐resolution passive‐matrix OLEDs with PEDOT:PSS electrodes are fabricated, in which the OLEDs show comparable performance to those devices prepared on the indium tin oxide (ITO) electrodes. This photolithographic patterning process for PEDTO:PSS has great potential for applications which require flexible electrodes. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1221–1226     

Solution‐processable and thermally cross‐linkable fluorene‐cored triple‐triphenylamines with terminal vinyl groups to enhance electroluminescence of MEH‐PPV: Synthesis,curing, and optoelectronic properties

This study reports the synthesis, curing, and optoelectronic properties of a solution‐processable, thermally cross‐linkable electron‐ and hole‐blocking material containing fluorene‐core and three periphery N‐phenyl‐N‐(4‐vinylphenyl)benzeneamine ( FTV ). The FTV exhibited good thermal stability with T_d above 478 °C in nitrogen atmosphere. The FTV is readily cross‐linked via terminal vinyl groups by heating at 160 °C for 30 min to obtain homogeneous film with excellent solvent resistance. Multilayer PLED device [ITO/PEDOT:PSS/cured‐ FTV /MEH‐PPV/Ca (50 nm)/Al (100 nm)] was successfully fabricated using solution processed. Inserting cured‐ FTV is between PEDOT:PSS and MEH‐PPV results in simultaneous reduction in hole injection from PEDOT:PSS to MEH‐PPV and blocking in electron transport from MEH‐PPV to anode. The maximum luminance and maximum current efficiency were enhanced from 1810 and 0.27 to 4640 cd/m² and 1.08 cd/A, respectively, after inserting cured‐ FTV layer. Current results demonstrate that the thermally cross‐linkable FTV enhances not only device efficiency but also film homogeneity after thermal curing. FTV is a promising electron‐ and hole‐blocking material applicable for the fabrication of multilayer PLEDs based on PPV derivatives. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 000: 000–000, 2012     

Tuning of PEDOT:PSS Properties Through Covalent Surface Modification

Conductive polymer (poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS) is an attractive platform for the design of flexible electronic, optoelectronic, and (bio)sensor devices. Practical application of PEDOT:PSS often requires an incorporation of specific molecules or moieties for tailoring of its physical–chemical properties. In this article, a method for covalent modification of PEDOT:PSS using arenediazonium tosylates was proposed. The procedure includes two steps: chemisorption of diazo‐cations on the PEDOT:PSS surface followed by thermal decomposition of the diazonium salt and the covalent bond formation. Structural and surface properties of the samples were evaluated by XPS, SEM‐EDX, AFM, goniometry, and a range of electric and optical measurements. The developed modification procedure enables tuning of the PEDOT:PSS surface properties such as conductivity and optical absorption. The possibility to introduce various organic functional groups (from hydrophilic to hydrophobic) and to create new groups for further functionalization makes the developed procedure multipurpose. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 378–387     

Thermoresponsive conductive polymer composite thin film and fiber mat: Crosslinked PEDOT:PSS and P(NIPAAm‐co‐NMA) composite

The thermoresponsive conductive composite (TCC) thin films and fiber mats, whose electrical property changed with temperature, were fabricated successfully. The thermocrosslinkable and thermoresponsive copolymer, poly(N‐isopropyl acrylamide‐co‐N‐methylolacrylamide) (PNN), was synthesized. The TCC thin film and fiber mat were fabricated by spin coating and electrospinning process of PEDOT:PSS/PNN solutions, respectively. After thermocrosslinking and doping by DMSO, the composite thin films and fiber mats were obtained. Fibrous structures of TCC fiber mats were observed by SEM. The surface resistance and conductivity of composites were measured. The thermoresponsivity and swelling ratio of TCCs were also studied. The thermoresponsive conductive property was analyzed by measuring the surface resistance of TCCs in water bath under various temperatures from 20 to 50 °C. With the increase of temperature, the TCCs shrank to be dense structure and showed lower surface resistance. The TCC fibers mat exhibited greater sensitivity to temperature than thin film owing to its fibrous structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1078–1087     

Hole‐buffer polymer composed of alternating p‐terphenyl and tetraethylene glycol ether moieties: Synthesis and application in polymer light‐emitting diodes

Carrier balance is essential to obtain efficient emission in polymer light‐emitting diodes (PLEDs). A new polymer 3P5O composed of alternating p‐terphenyl and tetraethylene glycol ether segments is designed and synthesized by the Suzuki coupling reaction and successfully employed as hole‐buffer layer to improve carrier balance. Multilayer PLEDs [ITO/PEDOT:PSS/ 3P5O /SY/LiF/Al], with Super Yellow (SY) as the emitting layer and 3P5O as the hole‐buffer layer, reveal maximum luminance (17,050 cd/m²) and maximum current efficiency (6.6 cd/A) superior to that without the hole‐buffer layer (10,017 cd/m², 3.0 cd/A). Moreover, it also shows better performance than that using conventional BCP as hole‐blocking layer [ITO/PEDOT:PSS/SY/BCP/LiF/Al (80 nm): 13,639 cd/m², 4.1 cd/A]. The performance enhancement has been attributed to hole‐buffering characteristics of 3P5O that results in improved carrier recombination ratio and wider carrier recombination region. Current results indicate that the 3P5O is a promising hole‐buffer polymer to enhance the performance of optoelectronic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 785–794     

Control of doctor‐blade coated poly (3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) electrodes shape on prepatterned substrates via microflow control in a drying droplet

We demonstrated a simple patterning method for the deposition of polymer electrodes such as poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS). We made use of the difference in wettability between hydrophobic surfaces and hydrophilic surfaces to make the patterns. However, the patterns made with our patterning method created undesirable ring‐like stains, which were caused by the outward flow of the solute within the PEDOT/PSS solution drop. To achieve homogenous device performance, we proposed a simple process for removing this ring‐like stain by making the surface tension gradient with dual solvent system in the PEDOT/PSS solution drop. Because this surface tension gradient causes the inward flow of the solute within the PEDOT/PSS solution drop, the ring‐like stain is removed. Finally, we confirmed the potential of our patterning method for polymer electrodes such as the PEDOT/PSS by fabricating pentacene thin‐film transistors (TFTs) and measuring the electrical properties of the pentacene TFTs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1590–1596, 2011     

Efficient enhancement of the thermoelectric performance of vapor phase polymerized poly(3,4‐ethylenedioxythiophene) films with poly(ethyleneimine)

Tuning the molecular rearrangement and oxidation level has been proven to be effective strategies for optimizing the thermoelectric (TE) performance of PEDOT. It is difficult to achieve these effects simultaneously via a one‐step process, however. In this work, we combined vapor phase polymerization (VPP) and H₂SO₄ post‐treatment to obtain a highly conductive PEDOT film. A novel strategy using polyethylenemine (PEI) as an effective reducing agent was employed to enhance the thermopower of the PEDOT film. Grazing‐Incidence Wide‐Angle X‐ray Scattering analysis and the changes in the oxidation level allow us to elucidate the role of PEI and its transport mechanism. It is demonstrated that the thermopower of well‐ordered crystallites in the PEDOT film significantly increases more than five times (from 11 to 59 μV K^?1) by the PEI‐DMF solution immersion process, while the electrical conductivity is maintained at 100 S cm^?1. The promising method connecting VPP, H₂SO₄, and PEI shows great potential for effectively tuning the thermopower of organic TE materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 257–265     

Random terpolymers for electroluminescent devices: Synthesis and characterization of new cyano‐containing poly(fluorenylene‐vinylene)s

The synthesis of new random poly(2,7‐fluorenylene‐vinylene)s was achieved by a Suzuki–Heck cascade polymerization reaction. The poly(fluorenylene‐vinylene) base structure was modified by the regio‐random incorporation of 1‐cyano‐2,5‐phenylene as electron withdrawing unit ( CN‐PFV1 ) and its properties were compared with terpolymers also embodying 1,4‐dioctyloxy‐2,5‐phenylene ( CN‐PFV2 ) or 3,6‐N‐octylcarbazole ( CN‐PFV3 ) as electron‐donating moieties. Thermal analysis revealed a high thermal stability (T_d > 389 °C) and the absence of glass transitions for all polymers. Cyclic voltammetry indicated a high electron affinity of the materials (2.96–3.21 eV) attributed to the presence of the cyano‐containing comonomer. In dilute solutions, the copolymers showed a broad green fluorescence with quantum yields ranging from 0.42 to 0.79, while in the solid state, a relatively narrow emission centered at ～ 560 nm, governed by the low‐energy segments within the π‐conjugated backbone, was observed. The electroluminescence properties of the materials were tested in OLED devices of ITO/PEDOT‐PSS/ CN‐PFV1‐3 /Ca/Al or ITO/PEDOT‐PSS/ CN‐PFV1‐3 /Alq₃/Ca/Al configurations, showing a bright green‐yellow emission that, in the case of CN‐PFV2 , reached 1403 cd/m² with efficiencies as high as 0.13 cd/A. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6051–6063, 2008     

Flexible conducting polymer transistors with supercapacitor function

Planar organic electrochemical transistors (OECTs) using PEDOT:PSS as the channel material and nanostructured carbon (nsC) as the gate electrode material and poly(sodium 4‐styrenesulfonate (PSSNa) gel as the electrolyte were fabricated on flexible polyethylene terephthalate (Mylar^®) substrates. The nsC was deposited at room‐temperature by supersonic cluster beam deposition (SCBD). Interestingly, the OECT acts as a hybrid supercapacitor (to give a device that we indicate as transcap). The energy storage ability of transcaps has been studied with two cell configurations: one featuring PEDOT:PSS as the positive electrode and nsC as the negative electrode and another configuration with reversed electrode polarity. Potentiostatic charge/discharge studies show that both supercapacitors show good performance in terms of voltage retention, in particular, when PEDOT:PSS is used as the positive electrode. Galvanostatic charge–discharge characteristics show typical symmetric triangular shape, indicating a nearly ideal capacitive behavior with a high columbic efficiency (close to 100%). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 96–103     

Enhanced dielectric properties of polymer composite films induced by encapsulated MWCNTs with a one core‐two shell structure

Multiwalled carbon nanotubes (MWCNTs) can endow high dielectric constant to polymer‐based composites. However, the accompanying poor dispersion of MWCNTs and high dielectric loss for composites severely limit their application in dielectric field. Herein, a modified acid‐treated MWCNTs encapsulated by the polyaniline/poly(sodium 4‐styrenesulfonate) layers (aMWCNTs@PANI‐PSS) with a one core‐two shell structure was fabricated by in situ polymerization followed by electrostatic self‐assembly technique. Furthermore, the composite films based on aMWCNTs@PANI‐PSS/poly(vinylidenefluoride‐hexaflouropropylene) (PVDF‐HFP) were fabricated by a solution‐casting method. An ultrathin insulating PSS shell is wrapped onto aMWCNTs@PANI, resulting in the improvement of dispersibility for aMWCNTs@PANI and the decrease of dielectric loss for composite films. When the content of aMWCNTs@PANI‐PSS is 5.0 wt %, the dielectric constant of aMWCNTs@PANI‐PSS/PVDF‐HFP reaches 430 (100 Hz), which is about 55 times of pure PVDF‐HFP and 1.7 times of aMWCNTs@PANI/PVDF‐HFP (247). Besides, the responding dielectric loss of aMWCNTs@PANI‐PSS/PVDF‐HFP composite film is only 0.67, much lower than that of aMWCNTs@PANI/PVDF‐HFP (25) and aMWCNTs/PVDF‐HFP (3185). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 948–956     

Improved efficiency of organic solar cells with modified hole‐extraction layers

The aim of this work has been to study the influence of modified hole‐extraction layers on the performance of organic solar cells (OSCs) based on blends of poly (3‐hexylthiophene) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester. The hole‐extraction layers consist of poly (3,4‐ethylene dioxythiophene):polystyrene sulfonic acid (PEDOT:PSS) doped with different concentrations of bromine. Compared with pristine OSC without adding bromine to the hole‐extraction layer, the bromine‐doped OSCs show a 49% increase in the power conversion efficiency (from 2.12 to 3.16%), which could be attributed to the increase of electrical and optical properties of PEDOT:PSS films after the addition of bromine. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 125–128, 2012     

Layer‐by‐layer assembly of readily detachable chitosan and poly(acrylic acid) polyelectrolyte multilayer films

Free‐standing layer‐by‐layer (LbL) assembled thin films have recently found utility in a broad range of applications. Previously reported free‐standing LbL films have generally required covalent modifications to improve aqueous stability and render these films suitable for biomedical applications. Here, we engineered chitosan and poly(acrylic acid) containing polyelectrolyte multilayer films, which are readily detached from hydrophilic silicon in aqueous conditions. These films demonstrate remarkable stability over 28 days in simulated in vivo conditions (pH 7.4, phosphate buffered saline at 37 °C) without the incorporation of any covalent crosslinking modifications. These films exhibit moduli (27–420 kPa) resembling that of many biological tissues including tendon, show high visible light transmittance of greater than 50%, and prevent fibronectin adsorption. The properties of this new detachable LbL film architecture indicate its promise for use in a variety of applications, particularly in medicine and biotechnology. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 127–131