Investigation of the doping efficiency of poly(styrene sulfonic acid) in poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) dispersions by capillary electrophoresis

CE can efficiently separate poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS) complexes and free PSS in dispersions and can be used to estimate the degree of PSS doping. We investigated the doping efficiency of PSS on PEDOT in dispersions using CE and its effect on the conductivity of the resulting PEDOT/PSS films. Results of this study indicate that dispersions containing 1:2.5–3 EDOT:PSS feed ratio (by weight) exhibiting 72–73% PSS doping generate highly processable and highly conductive films. Conductivity can be optimized by limiting the time of reaction to 12 h. At this point of the reaction, the PEDOT/PSS segments, appearing as broad band in the electropherogram, could still exist in an extended coil conformation favoring charge transport resulting in high conductivity. Above a threshold PEDOT length formed at reaction times longer than 12 h, the PEDOT/PSS complex, appearing as spikes in the electropherogram, most likely have undergone a conformational change to coiled core‐shell structure restricting charge transport resulting in low conductivity. The optimal conductivity (5.2 S/cm) of films from dispersions synthesized for 12 h is significantly higher than those from its commercial equivalent Clevios P and other reported values obtained under similar conditions without the addition of codopants.     

Langmuir‐Blodgett Films of Alkanethiolate Gold Nanorods

Colloidal multilayers of octadecanethiol‐capped Au nanorods were prepared using the Langmuir‐Blodgett technique. Uniform growth of the films with increasing number of deposition has been observed. Vertical transfer efficiency indicates efficient transfer for immersion of hydrophobic substrates and poor transfer for emersion of such substrates. The vertically transferred film has an order parameter S = 0.027, which suggests that the orientation of the nanorods in the film is somewhat isotropic about the dipping direction. Horizontal transfer of the Langmuir monolayer on Formvar/carbon‐coated Cu grids, however, gave scattered domains of Au nanorods aligned in parallel stacks. Such behavior is probably related to the rigidity of the Langmuir monolayer.     

Rod‐Like Silicate‐Epoxy Nanocomposites

Summary: Epoxy nanocomposites containing rod‐like silicate (attapulgite) were prepared using a simple organic modification to the nanorods. The modification led to effective interfacial adhesion between the ceramic nanorods and the epoxy resin and hence good load transfer. Scanning electron microscopy examination revealed a uniform dispersion of nanorods in the epoxy resin. Compared to the neat resin, nanocomposites with 7.47 vol.‐% nanorods exhibited an increase in the (rubbery state) storage modulus of 122.5%. In addition, the nanocomposites exhibited improved dimensional stability both above and below the T_g.

Storage modulus of the neat resin and nanocomposites.     

Roll‐to‐Roll printed PEDOT/PSS/GO Plastic Film for Electrochemical Determination of Carbofuran

In this work, we developed a roll‐to‐roll printed poly(3,4‐ethylenedioxythiophene)/polystyrene sulphoanate without graphene oxide (GO) (PEDOT/PSS) and with graphene oxide (PEDOT/PSS/GO) plastic films for the electrochemical determination of carbofuran. Both the PEDOT/PSS and PEDOT/PSS/GO plastic films showed electroactivity towards the oxidation of carbofuran. Incorporation of graphene oxide (GO) improves the electrochemical activity of carbofuran and increased its sensitivity. The printed plastic films were characterized by cyclic voltammetry (CV), linear sweep voltammetry (LSV), surface profilometer, four point probe and atomic force microscopy (AFM). The effects of pH, deposition time, deposition potential and film thickness on the oxidation peak current of carbofuran were investigated. Under the optimized conditions, a dynamic linear range of 1 μM–90 μM with a detection limit of 1.0×10^?7 M (S/N=3) were obtained. The printed PEDOT/PSS/GO plastic electrode was applied for the determination of carbofuran in vegetable and fruit samples with recoveries between 94.4 and 101.8 %.     

Red to Blue High Electrochromic Contrast and Rapid Switching Poly(3,4‐ethylenedioxypyrrole)–Au/Ag Nanocomposite Devices for Smart Windows

Poly(3,4‐ethylenedioxypyrrole) (PEDOP)–Ag and PEDOP–Au nanocomposite films have been synthesized for the first time by electropolymerization of the conducting‐polymer precursor in a waterproof ionic liquid, 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, followed by Ag/Au nanoparticle incorporation. That the Ag/Au nanoparticles are not adventitious entities in the film is confirmed by a) X‐ray photoelectron spectroscopy, which provides evidence of Ag/Au–PEDOP interactions through chemical shifts of the Ag/Au core levels and new signals due to Ag–N(H) and Au–N(H) components, and b) electron microscopy, which reveals Au nanoparticles with a face‐centered‐cubic crystalline structure associated with the amorphous polymer. Spectroelectrochemistry of electrochromic devices based on PEDOP–Au show a large coloring efficiency (η_max=270 cm² C^?1, λ=458 nm) in the visible region, for an orange/red to blue reversible transition, followed by a second, remarkably high η_max of 490 cm² C^?1 (λ=1000 nm) in the near‐infrared region as compared to the much lower values achieved for the neat PEDOP analogue. Electrochemical impedance spectroscopy studies reveal that the metal nanoparticles lower charge‐transfer resistance and facilitate ion intercalation–deintercalation, which manifests in enhanced performance characteristics. In addition, significantly faster color–bleach kinetics (five times of that of neat PEDOP!) and a larger electrochemical ion insertion capacity unambiguously demonstrate the potential such conducting‐polymer nanocomposites have for smart window applications.     

Detection of layer‐by‐layer self‐assembly multilayer films by low‐temperature plasma mass spectrometry

The detection of layer‐by‐layer self‐assembly multilayer films was carried out using low‐temperature plasma (LTP) mass spectrometry (MS) under ambient conditions. These multilayer films have been prepared on quartz plates through the alternate assembling of oppositely charged 4‐aminothiophenol (4‐ATP) capped Au particles and thioglycolic acid (TGA) capped Ag particles. An LTP probe was used for direct desorption and ionization of chemical components on the films. Without the complicated sample preparation, the structure information of 4‐ATP and TGA on films was studied by LTP‐MS. Characteristic ions of 4‐ATP (M) and TGA (F), including [M]^+?, [M‐NH₂]⁺, [M‐HCN‐H]⁺, and [F + H]⁺, [F‐H]⁺, [F‐OH]⁺, [F‐COOH]⁺ were recorded by LTP‐MS on the films. However, [M‐CS‐H]⁺ and [F‐SH]⁺ could not be observed on the film, which were detected in the neat sample. In addition, the semi‐quantitative analysis of chemical components on monolayer film was carried out, and the amounts of 4‐ATP and TGA on monolayer surface were 45 ng/mm² and 54 ng/mm², respectively. This resulted the ionization efficiencies of 72% for 4‐ATP and 54% for TGA. In order to evaluate the reliability of present LTP‐MS, the correlations between this approach and some traditional methods, such as UV–vis spectroscopy, atomic force microscope and X‐ray photoelectron spectroscopy were studied, which resulted the correlation coefficients of higher than 0.9776. The results indicated that this technique can be used for analyzing the films without any pretreatment, which possesses great potential in the studies of self‐assembly multilayer films. Copyright © 2013 John Wiley & Sons, Ltd.     

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     

In Situ Chemical Oxidative Polymerization Preparation of Poly(3,4‐ethylenedioxythiophene)/Graphene Nanocomposites with Enhanced Thermoelectric Performance

Three different in situ chemical oxidative polymerization routes, that is, (A) spin‐coating and subsequent liquid layer polymerization, (B) spin‐coating followed by vapor phase polymerization, and (C) in situ polymerization and then post‐treatment by immersion in ethylene glycol (EG), have been developed to achieve poly(3,4‐ethylenedioxythiophene)/reduced graphene oxide (PEDOT/rGO) nanocomposites. As demonstrated by scanning electron microscopic and energy‐dispersive X‐ray spectroscopic techniques, PEDOT has been successfully coated on the surface of the rGO nanosheets by each of the three preparation routes. Importantly, all of the nanocomposites display a greatly enhanced thermoelectric performance (power factors) relative to those of the corresponding neat PEDOT.     

Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Transparent [90% transmittance at 550 nm at a sheet resistance (R_s) of 279 Ω sq^?1] poly(3,4‐ethylenedioxythiophene) (PEDOT) films with electrical conductivities up to 1354 S cm^?1 are prepared using base‐inhibited vapor phase polymerization at atmospheric pressure. The influence of reaction conditions, such as temperature and growth time, on the film formation is investigated. A simple and convenient two‐electrode method is used for the in situ measurement of resistance, enabling to investigate the growth mechanism of polymer films and the influence of different parameters (relative humidity and the amount of oxidant) on the film growth. Low humidity exerts a detrimental effect on film growth and conductivity. In situ R_s measurements suggest that a large structural change occurs upon washing the PEDOT‐oxidant film. © 2014 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2014 , 52, 561–571     

Improved Electrochromic Performance of Poly(3,4‐ethylenedioxythiophene) by Incorporating a Three‐Dimensionally Ordered Macroporous Structure

In this paper, three‐dimensionally ordered macroporous (3DOM) poly(3,4‐ethylenedioxythiophene) (PEDOT) films were electropolymerized from an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([Bmim]PF₆). The electrochromic performances of the 3DOM PEDOT films were studied. The 3DOM films exhibited high transmittance modulation (41.2 % at λ=580 nm), high ionic fast switching speeds (0.7 and 0.7 s for coloration and bleaching, respectively), and enhanced cycling stability relative to that exhibited by the dense PEDOT film. The relationship between the declining behavior of the transmittance modulation and the nanostructure of the film was investigated. A three‐period decay process was proposed to understand the declining behavior. The 3D interconnected macroporous nanostructure is beneficial for fast ion and electron transportation, high ion accessibility, and maintenance of structure integrity, which result in enhanced cycling stability and fast switching speeds.     

Free‐Standing Conducting Polymer Films for High‐Performance Energy Devices

Thick, uniform, easily processed, highly conductive polymer films are desirable as electrodes for solar cells as well as polymer capacitors. Here, a novel scalable strategy is developed to prepare highly conductive thick poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (HCT‐PEDOT:PSS) films with layered structure that display a conductivity of 1400 S cm^?1 and a low sheet resistance of 0.59 ohm sq^?1. Organic solar cells with laminated HCT‐PEDOT:PSS exhibit a performance comparable to the reference devices with vacuum‐deposited Ag top electrodes. More importantly, the HCT‐PEDOT:PSS film delivers a specific capacitance of 120 F g^?1 at a current density of 0.4 A g^?1. All‐solid‐state flexible symmetric supercapacitors with the HCT‐PEDOT:PSS films display a high volumetric energy density of 6.80 mWh cm^?3 at a power density of 100 mW cm^?3 and 3.15 mWh cm^?3 at a very high power density of 16160 mW cm^?3 that outperforms previous reported solid‐state supercapacitors based on PEDOT materials.     

Synthesis of highly conductive EDOT copolymer films via oxidative chemical in situ polymerization

Poly(3,4‐ethylenedioxythiophene)s (PEDOT) represent a class of conjugated polymers that can be potentially used as an electrode material for flexible organic electronics due to their superior conductivity and transparency. In this study, we demonstrate that the conductivity of a PEDOT containing copolymer film can be further enhanced by the oxidative chemical in situ copolymerization of a liquid film spun coated from monomer mixture (3,4‐ethylenedioxythiophene (EDOT) and 3‐thienyl ethoxybutanesulfonate (TEBS)), oxidant (iron(III) p‐toluenesulfonate (Fe(OTs)₃)), weak base (imidazole), and solvent (methanol). We investigated that the effect of the processing parameters such as the molar ratios TEBS/EDOT, IM/EDOT, and Fe(OTs)₃/EDOT on the surface morphology, optical property, and the conductivity of the resulting copolymer films. These parameters have been optimized to achieve conductivities for the copolymer films as high as 170 S/cm compared with a conductivity of 30 S/cm for the pure PEDOT film synthesized using the same fabrication method. This conductivity enhancement for the copolymer films was found to be resulted from the fact that the addition of TEBS monomer reduces the copolymerization rate, leading to the formation of much more uniform film surface without defects and copolymers of higher molecular weight which increase the conductivity of the resulting copolymer film. The composition of two monomers in the copolymer film is not related to the variation of conductivity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1662–1673, 2008     

Comparative study on the properties of poly(trimethylene terephthalate) ‐based nanocomposites containing multi‐walled carbon (MWCNT) and tungsten disulfide (INT‐WS2) nanotubes

Multi‐walled carbon (MWCNT) and tungsten disulfide (INT‐WS₂) nanotubes are materials with excellent mechanical properties, high electrical and thermal conductivity. These special properties make them excellent candidates for high strength and electrically conductive polymer nanocomposite applications. In this work, the possibility of the improvement of mechanical, thermal and electrical properties of poly(trimethylene terephthalate) (PTT) by the introduction of MWCNT and INT‐WS₂ nanotubes was investigated. The PTT nanocomposites with low loading of nanotubes were prepared by in situ polymerization method. Analysis of the nanocomposites' morphology carried out by SEM and TEM has confirmed that well‐dispersed nanotubes in the PTT matrix were obtained at low loading (<0.5 wt%). Thermal and thermo‐oxidative stability of nanocomposites was not affected by the presence of nanotubes in PTT matrix. Loading with INT‐WS₂ up to 0.5 wt% was insufficient to ensure electrical conductivity of PTT nanocomposite films. In the case of nanocomposites filled with MWCNT, it was found that nanotube incorporation leads to increase of electrical conductivity of PTT films by 10 orders of magnitude, approaching a value of 10^?3 S/cm at loading of 0.3 wt%. Tensile properties of amorphous and semicrystalline (annealed samples) nanocomposites were affected by the presence of nanotubes. Moreover, the increase in the brittleness of semicrystalline nanocomposites with the increase in MWCNT loading was observed, while the nanocomposites filled with INT‐WS₂ were less brittle than neat PTT. Copyright © 2016 John Wiley & Sons, Ltd.     

Highly Conductive PEDOT:PSS Films with 1,3‐Dimethyl‐2‐Imidazolidinone as Transparent Electrodes for Organic Light‐Emitting Diodes

Highly conductive poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films as transparent electrodes for organic light‐emitting diodes (OLEDs) are doped with a new solvent 1,3‐dimethyl‐2‐imidazolidinone (DMI) and are optimized using solvent post‐treatment. The DMI doped PEDOT:PSS films show significantly enhanced conductivities up to 812.1 S cm⁻¹. The sheet resistance of the PEDOT:PSS films doped with DMI is further reduced by various solvent post‐treatment. The effect of solvent post‐treatment on DMI doped PEDOT:PSS films is investigated and is shown to reduce insulating PSS in the conductive films. The solvent posttreated PEDOT:PSS films are successfully employed as transparent electrodes in white OLEDs. It is shown that the efficiency of OLEDs with the optimized DMI doped PEDOT:PSS films is higher than that of reference OLEDs doped with a conventional solvent (ethylene glycol). The results present that the optimized PEDOT:PSS films with the new solvent of DMI can be a promising transparent electrode for low‐cost, efficient ITO‐free white OLEDs.

     

Effects of additives and post‐treatment on the thermoelectric performance of vapor‐phase polymerized PEDOT films

Vapor‐phase polymerization (VPP) is an important method for the fabrication of high‐quality conducting polymers, especially poly(3,4‐ethylenedioxythiophene) (PEDOT). In this work, the effects of additives and post‐treatment solvents on the thermoelectric (TE) performance of VPP‐PEDOT films were systematically investigated. The use of 1‐butyl‐3‐menthylinidazolium tetrafluoroborate ([BMIm][BF₄], an ionic liquid) was shown to significantly enhance the electrical conductivity of VPP‐PEDOT films compared with other additives. The VPP‐PEDOT film post‐treated with mixed ethylene glycol (EG)/[BMIm][BF₄] solvent displayed the high power factor of 45.3 μW m^?1 K^?2 which is 122% higher than that prepared without any additive or post‐treatment solvent, along with enhanced electrical conductivity and Seebeck coefficient. This work highlighted the superior effect of the [BMIm][BF₄] additive and the EG/[BMIm][BF₄] solvent post‐treatment on the TE performance of the VPP‐PEDOT film. These results should help with developing the VPP method to fabricate high‐performance PEDOT films. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1738–1744     

Electrochemical Behavior and Amperometric Detection of 4‐Chlorophenol on Nano‐Au Thin Films Modified Glassy Carbon Electrode

An amperometric sensor based on nano‐Au thin films was fabricated, by means of which a fast response to 4‐chlorophenol (4‐CP) can be achieved in the range of mM concentrations. The nanostructured Au thin film was prepared on glassy carbon electrodes by a template‐free, double‐potential step electrodeposition technique. Its structural feature can be controlled well by adjusting the deposition time. The amperometric detection of 4‐CP was performed at +0.85 V with a linear detection range from 0.2 to 4.8 mM and a detection limit of 0.11 mM (S/N=3). Besides, the effect of concentrations on the electrochemical behavior of 4‐CP on the Au thin film was investigated by linear sweep voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy.     

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.     

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     

One‐step Synthesis and Enhanced Thermoelectric Properties of Polymer–Quantum Dot Composite Films

Conventional syntheses of polymer–inorganic composite thermoelectric materials suffer major problems such as inhomogeneity, large particle size, and oxidation that result in ineffective loading. Now a one‐step synthesis can be used to fabricate high‐quality small‐sized anions codoped poly(3,4‐ethylenedioxythiophene):dodecylbenzenesulfonate/Cl‐tellurium (PEDOT:DBSA/Cl‐Te) composite films using a series of novel Te^IV‐based oxidants. The synchronized production of PEDOT and Te results in thick and homogeneous films containing evenly distributed and well‐protected Te quantum dots. Owing to the heavily doped crystalline polymer matrix as well as the <5 nm unoxidized Te quantum dot loading, at low Te concentrations as 2.1–5.8 wt %, the films exhibits high power factors of about 100 μW m^?1 K^?2, which is 50 % higher compared to a pure PEDOT:DBSA film.     

Helical Carbon and Graphite Films Prepared from Helical Poly(3,4‐ethylenedioxythiophene) Films Synthesized by Electrochemical Polymerization in Chiral Nematic Liquid Crystals

Helical carbon and graphite films from helical poly(3,4‐ethylenedioxythiophene) (H‐PEDOT) films synthesized through electrochemical polymerization in a chiral nematic liquid‐crystal (N*‐LC) field are prepared. The microscope investigations showed that the H‐PEDOT film synthesized in the N*‐LC has large domains of one‐handed spiral morphology consisting of fibril bundles. The H‐PEDOT films exhibited distinct Cotton effects in circular dichroism spectra. The highly twisted N*‐LC with a helical pitch of smaller than 1 μm produced the H‐PEDOT film with a highly ordered morphology. The spiral morphologies with left‐ and right‐handed screws were observed for the carbon films prepared from the H‐PEDOT films at 800 °C and were well correlated with the textures and helical pitches of the N*‐LCs. The spiral morphologies of the precursors were also retained even in the graphite films prepared from the helical carbon films at 2600 °C.