Formation of transparent conducting films based on core‐shell latices: Influence of the polypyrrole shell thickness

Transparent conducting latex films have been prepared from core‐shell latices. The latex particles have a poly(butyl methacrylate) (PBMA) core of about 700 nm and a very thin polypyrrole (PPy) shell. We have studied the film formation of latices with 1, 2, and 4 wt % PPy and compared this with the film formation of the pure PBMA latex. The film formation process was studied by transparency measurements, atomic force microscopy surface flattening, and transmission electron microscopy on ultrathin sections of films after various annealing times at 120°C. It is demonstrated that highly transparent (>90%) and antistatic films can be produced using these latices. The presence of a polypyrrole shell around the PBMA latex particle seriously hinders the deformation of the particles. The amount of polypyrrole, and thus the shell thickness, is the determining factor for the speed of film formation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 900–909, 2001     

Film formation, surface character, and relative density for electrochromic PEI/(PSS:PEDOT) multilayered thin films

Thin films of alternating layer composition were constructed from the polyelectrolyte complex PEDOT:PSS and the polycation PEI, using ionic self assembly (ISA). The PEI/PEDOT:PSS system displays a consistent trend in film growth, as evidenced by UV-visible spectroscopy and ellipsometry. We find that the overall density of PEDOT increases with increasing number of layers. The density of PSS during multilayer deposition differs from PEDOT, with a sharp drop in density between the 3rd and 6th bilayers. Combining film deposition estimates with contact angle measurement, we distinguish three regions of growth, separated by the 3rd and 6th layers. We ascertain that a constant level of interpenetration between PEI and PEDOT:PSS is reached by the 6th layer. Results from kinetics experiments and pH variation reveal a local increase in pH for the PEDOT species as it comes into contact with the PEI surface. Electrochemical characterization indicates that our films have an interpenetrated PEDOT network and a relatively hydrophilic surface. We demonstrate that ISA can be used to generate robust thin films, stable over a large pH range, whose coloration and conductivity may be manipulated on a large scale using applied voltage, and may be fine-tuned by changing the pH. The films exhibit electrochromic properties similar to other PEDOT derivatives, with a change in transmittance of 51% for 16 bilayers at 643 nm.     

Electro-synthesis of novel nanostructured PEDOT films and their application as catalyst support

Poly(3,4-ethylenedioxythiophene) (PEDOT) films doped with nitric and chlorine ions have been electrochemically deposited simply by a one-step electrochemical method in an aqueous media in the absence of any surfactant. The fabricated PEDOT films were characterized by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The results indicate that the hierarchical structured PEDOT film doped with nitric ions displays a 'lunar craters' porous morphology consisting of PEDOT nano-sheets with a thickness of less than 2 nm. The effect of counter ions on the electro-polymerization, the electrochemistry, and the morphology of the polymer film was studied. Compared with PEDOT film doped with nitric acid, PEDOT film deposited in the presence of chlorine ions shows irregular morphology and less electrochemical activity. The specific nanostructure of the polymer was further studied as catalyst support for platinum nanoparticles to methanol electro-oxidation.     

Humido-sensitive conducting polymer films and applications to linear actuators

Free-standing films made of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT/PSS) with various PSS contents were newly prepared by casting water dispersion of the PEDOT/PSS colloidal particles in the presence of an extra PSS. Electrical conductivity, morphology, water vapor sorption, and electro-active polymer actuating behavior of the resulting films were investigated by means of four-point method, atomic force microscope (AFM), sorption isotherm, and electromechanical analyses. The maximum contraction of the film by application of an electric field increased with increasing both PSS content and relative humidity (RH), where the value attained 7% at 70% RH for the film with 93% of PSS. Since the isothermal sorption curve of the film was less dependent on the PSS content, the significant increase of the film contraction was explained by two mechanisms: (i) the extra PSS prevented from hydrogen bonding between adjacent PEDOT/PSS particles that suppressed dimensional changes of the film; and (ii) the higher the RH, the larger the degree of water vapor sorption, which led to the large film contraction by desorption of water vapor via Joule heating. On the basis of this phenomenon linear actuators utilizing PEDOT/PSS films were successfully developed and applied to leverage actuator and Braille cell.     

Conductive composite particles synthesized via pickering emulsion polymerization using conductive latex of poly(3,4-ethylenedioxythiophene) (PEDOT) as stabilizer

In this research, poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles less than 100 nm were synthesized first and applied as the solid stabilizer for producing PEDOT-polystyrene (PEDOT-PSt) composite latex by Pickering emulsion polymerization. The results showed that most PEDOT nanoparticles adhered to the PSt core particles having the size from 100 to 250 nm. By casting the latex, the obtained PEDOT-PSt film had a surface resistance of 4–5 kΩ/□, almost the same as the pure PEDOT film, though its PEDOT content was only 6.2 wt%. Those PEDOT nanoparticles in the outer layer could contact with one another, forming a continuous network as the conductive passageway. Furthermore, soft latex particles of poly(styrene-co-butyl acrylate), P(St-BA), were synthesized and mixed with the conducting rigid PEDOT-PSt latex for improving the toughness and transparency of the casting film. A critical point at about 2 wt% of PEDOT content in the PEDOT-PSt/P(St-BA) film was observed in the surface resistance measurement.     

导电聚合物PEDOT/PSS-MPEG的制备及性能

引言导电高分子既有导体材料的光电学特性,又有良好的力学性能和可加工性[1],这使得导电高分子材料具有广泛的应用前景。聚噻吩类有机导电材料[2]就是这类材料中的一种。聚噻吩的室温电导率     

Improving the hydrophobic,water barrier and crystallization properties of poly(ethylene terephthalate) by incorporating monodisperse SiO2 particles

This paper details an improvement in the properties of poly(ethylene terephthalate) (PET) with respect to its use in petroleum engineering by incorporating uniform (monodisperse; 35 to 380 nm) silica (SiO₂) particles and polystyrene? SiO₂ core–shell particles by melt mixing. The resulting high‐performance nanocomposite (SNPET) films are presented. The results of contact angle and water absorption tests showed that the contact angle of the amorphous SNPET films increased from 72° to 118.5° as the core–shell particle load increased from 0 to 6.0 wt%. The contact angle reached 128.0° when the films were annealed. Decreasing the SiO₂ particle size demonstrably improved the SNPET film hydrophobicity and lowered the water diffusion coefficient, i.e. SiO₂ particles of 35 nm in size gave the greatest enhancement of water barrier properties. Results of transmission electron microscopy, scanning electron microscopy, atomic force microscopy and optical measurements showed the homogeneous particle dispersion and nanostructure in the SNPET films. Their transparency and haziness increased as the particle size decreased. Use of such core–shell structures meant that the uniform (monodisperse) SiO₂ particles could be dispersed homogeneously in PET, and effectively improved the surface, thermal and crystallization behavior of SNPET films to produce materials with high barrier stability against water. Copyright © 2010 Society of Chemical Industry     

Hole transport in conducting ultrathin films of PEDOT/PSS prepared by layer-by-layer deposition technique

Multilayered ultrathin films of a conductive polymer, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) were prepared by layer-by-layer deposition technique. These films were characterized by absorption spectroscopy, atomic force microscopy, cyclic voltammetry and potential step chronoamperometry. The PEDOT/PSS films were layered up with a bilayer thickness of 5 nm and the surface roughness of the films was improved after the ultrasonicated pretreatment of a PEDOT/PSS aqueous dispersion prior to the deposition. The ultrathin films thus obtained kept excellent diffusion constant of hole carriers, 5×10⁻¹⁰ cm² s⁻¹, as high as that of spin-cast films of PEDOT/PSS, indicating that the conducting polymer films are fabricated with nanometer-scale precision and act as a junction layer between the electrode and electrochemically active organic materials.     

热敏乳液薄膜的制备及性能

本文介绍了一种可以通过三步法制得的具有亲油的核和亲水的壳的高分子微胶粒。首先,通过乳液聚合得到甲基丙烯酸正丁酯与甲基丙酸甲酯的共聚物乳液(p-(BMA-MMA));利用(p-(BMA-MMA)乳液作为种子,用一种氧化还原引发体系引发反应,通过控制反应条件,在乳胶粒表面包覆一层均匀的聚甲基丙烯酸缩水甘油酯(p-GMA)外壳,壳层聚合物的含量为5~15wt.%之间;最后,壳层表面的环氧基团与三乙醇胺盐酸盐反应,环氧基团转变为季铵盐,使外壳成为极性的亲水表面。核-壳型固体微胶粒可以在水中较好地分散并形成稳定的乳液。通过旋涂法将固体乳液颗粒和PVA的混合水溶液涂在铝版基上,室温下干燥,可得到乳液薄膜。实验发现,室温下核-壳乳液薄膜与水的接触角在16.1°-27.5°范围内,可经过150℃短时间的烤版处理后,接触角将超过87,°表明乳液薄膜通过加热后完全由亲水性转为亲油性。同时,该乳液薄膜在烤版前很容易用中性水由版基上冲洗掉,但烤版后不再能够被洗掉。当在乳液薄膜中加入一种红外染料(最大吸收波长在830nm)后,该薄膜变得对830nm的LD激光敏感,并通过LD激光曝光和中性水显影后,得到阴图型图像。     

Electrical conductivity of polymer blends of poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate): N-methyl-2-pyrrolidinone and polyvinyl alcohol

The goal of this study is to determine the electrically conductivity of the polymers poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate): N-methyl-2-pyrrolidinone (PEDOT: PSS: NMP) and PEDOT: PSS when blended with polyvinyl alcohol (PVA). While the conducting polymers have high conductivity when not blended with PVA, they are brittle and difficult to spin-coat. Thus, the motivation for this study is to develop blends of these two conducting polymers with PVA to produce a material with optimized mechanical properties and that can also be spin-coated. The blends are produced using aqueous preparations of these materials. Mixtures of various weight percentages (wt %) of PEDOT: PSS: NMP and PEDOT: PSS are prepared and spin-coated on glass slides to form thin films. In the blends, the film conductivity increases with increasing content of either PEDOT: PSS: NMP or PEDOT: PSS. For example, 100 wt % of PEDOT: PSS: NMP and 60 wt % of PEDOT: PSS: NMP blended with PVA exhibit conductivities of, respectively, 10 and 4.02 S/cm. In contrast, conductivities of only 0.0525 and 0.000506 S/cm are observed, respectively, for 100 wt % of PEDOT: PSS and 60 wt % of PEDOT: PSS content in the PEDOT: PSS/PVA blends (No NMP). The addition of the NMP enhances the electrical conductivity by two to five orders of magnitude (depending on the amount of PVA in the blend) due to conformational change of PEDOT chains. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A PSS‐Free PEDOT Conductive Film Supported by a Hierarchical Nanoporous Layer Glass

The importance of transparent conductive film is increasing due to its use in applications such as touch‐panel devices. Although indium tin oxide is widely used because of its high conductivity and transparency, conductive polymers are being studied as alternative materials that avoid the use of rare metals and the brittleness associated with existing systems. Polyethylene dioxythiophene (PEDOT)/polyethylene sulfonic acid (PSS) is drawing a lot of attention due to its well‐balanced conductivity, transparency, film formability, and chemical stability. The nonconductive PSS reportedly covers the conductive PEDOT. The PSS shell provides carrier and film‐formability to PEDOT but is also a barrier that hinders electrical conductivity. Therefore, the PEDOT film formability is explored supported by a substrate without the addition of PSS. The “hierarchical nanoporous layer glass” holds the PSS‐free PEDOT with its nanopores to form a homogeneous, transparent film. The PSS‐free PEDOT film thus achieves transparency of over 85% and resistivity of below 500 Ω sq^?1.     

Composite polypyrrole-containing particles and electrical properties of thin films prepared therefrom

Preparation of core-shell particles consisting of polystyrene-poly(ethylene glycol) monomethacrylate (PS-PEGMA) core covered with polypyrrole (PPy) shell is described. The thickness of PPy shell, which strongly influences electrical properties of the films prepared from the particles, can be varied by changing pyrrole load, controlling the overall template surface area in the system and by influencing the pyrrole polymerization kinetics in the presence of different oxidants. The type of anions and PPy loading strongly influence the electrical conductivity. Typical value of the resistivity of thin film consisting of core-shell particles was 34 Ωm (PPy oxidized by FeCl₃, shell thickness 3 nm). Current-voltage dependences of low conductivity samples (thin PPy shell layer) are characteristic of contact-limited currents. The conductivity of the particles changes with humidity, which can be utilized in humidity sensors.     

Effects of solvents on thermoelectric performance of PANi/PEDOT/PSS composite films

Organic thermoelectric materials based on conducting polymers, especially for polyaniline (PANi) and poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), have attracted great concern due to their tunable electron transport properties by controlling doping level. Here, the solvent effects of deionized H₂O and NH₃·H₂O were investigated on the electrical conductivity and Seebeck coefficient of PANi/PEDOT/PSS composite films. The introduction of PEDOT/PSS can not only effectively improve the quality of pure PANi film, but also enhance the electrical conductivity of PANi film. The different volumes of deionized H₂O as dilution have a great influence on the electrical conductivity of PANi/PEDOT/PSS composite thin film with a maximum electrical conductivity value of 63.5 S cm^?1, which is much higher than pure PANi and pristine PEDOT/PSS. The introduction of NH₃·H₂O shows a positive effect on Seebeck coefficient with a large decline on electrical conductivity of PANi/PEDOT/PSS. The Raman spectroscopy, scanning electron microscopy (SEM), and UV-vis spectroscopy were used to obtain the morphology and structure information of PANi/PEDOT/PSS.     

Stress development and film formation in multiphase composite latexes

Designed appropriately, multiphase soft-core/hard-shell latex particles can achieve film formation without the addition of a coalescing aid, while preserving sufficient film hardness. Achieving optimal performance in these materials requires an understanding of how particle morphology affects film formation and stress development in the film. In this study, soft-core/hard-shell latex particles with different shell ratios, core and shell glass transition temperatures (T _gs), and particle sizes (63–177 nm) were synthesized using a two-stage emulsion polymerization. The film formation behavior of the composite particles was investigated with cryogenic scanning electron microscopy, atomic force microscopy, and measurements of the minimum film formation temperature (MFFT). Results show that film formation was enhanced for particles with thinner hard shells, smaller particle size, and a smaller difference in T _g between the core and shell polymers. For example, the MFFT decreased and the particle deformation increased for particles with thinner shells and smaller particle sizes. Stress development during drying was characterized using a cantilever beam bending technique. A walled cantilever design was used to monitor stress development without the complication of a lateral drying front. The film formation behavior and stress development correlated well with practical paint properties like scrub resistance and gloss.     

Dip Coating of Water-Resistant PEDOT:PSS Films Based on Physical Crosslinking

Water-resistant poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films are valuable in biomedical applications; however, they typically require crosslinkers to stabilize the films, which can introduce undesired aggregation or phase separation reactions. Herein, a dipping-based process to prepare PEDOT:PSS films on nonplanar surfaces without crosslinker is developed. Sequential soaking of a dip-coated PEDOT:PSS film in ethanol and water imparts water resistance to the film. Microscopic and spectroscopic techniques are used to monitor the process and confirm that the ethanol soaking elutes the excess PSS from the film bulk, which stabilizes the film prior to the water-soaking process. The obtained films act as conductors and semiconductors on curved surfaces, including 3D-printed objects. A film deposited on a curved surface is successfully applied as the channel layer in a neuromorphic organic electrochemical transistor. This approach can enable integrated bioelectronic and neuromorphic applications that can be readily deployed for facile prototyping.     

Preparation and surface properties of core‐shell polyacrylate latex containing fluorine and silicon in the shell

The core‐shell polyacrylate latex particles containing fluorine and silicon in the shell were successfully synthesized by a seed emulsion polymerization, using methyl methacrylate (MMA) and butyl acrylate (BA) as main monomers, dodecafluoroheptyl methacrylate (DFMA), and γ‐(methacryloxy) propyltrimethoxy silane (KH‐570) as functional monomers. The influence of the amount of fluorine and silicon monomers on the emulsion polymerization process and the surface properties of the latex films were discussed, and the surface free energy of latex films were estimated using two different theoretical models. The emulsion and its films were characterized by particle size distribution (PSD) analysis, transmission electron microscopy (TEM), Fourier transform infrared spectrum (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹⁹F‐NMR) spectrometry, contact angle (CA) and X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. The results indicate that the average particle size of the latex particles is about 160 nm and the PSD is narrow, the synthesized latex particles exist with core‐shell structure, and a gradient distribution of fluorine and silicon exist in the latex films. In addition, both the hydrophobicity and thermal stability of the latex films are greatly improved because of the enrichment of fluorine and silicon at the film‐air interface, and the surface free energy is as low as 15.4 mN/m, which is comparable to that of polytetrafluoroethylene (PTFE). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrochemical and spectroelectrochemical study on bilayer films composed of C60 and poly(3,4-ethylenedioxythiophene) PEDOT

Bilayers of drop casted C₆₀ fullerene films and electrochemically synthesized poly(3,4-ethylenedioxythiophene) (PEDOT) films have been studied. The PEDOT film was polymerised by cyclic voltammetry on top of the drop casted C₆₀ fullerene film. The bilayer films were produced and characterized in three different electrolytes; tetrabutylammoniumhexafluorophosphate (TBAPF₆) and lithium hexafluorophosphate (LiPF₆) in acetonitrile (ACN) and in the ionic liquid 1-butyl-3-methyl-imidazolium tetrafluoroborate (BMIMBF₄). The bilayers were studied by cyclic voltammetry and in situ Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy. Both p- and n-doping of the bilayer films were studied and compared with PEDOT films prepared in organic media.     

Structural, chemical and electrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) prepared with various counter-ions and heat treatments

Electrochemical deposition of the conjugated polymer poly(3,4-ethylenedioxythiophene) (PEDOT) forms thin, conductive films that are especially suitable for charge transfer at the tissue-electrode interface of neural implants. For this study, the effects of counter-ion choice and annealing parameters on the electrical and structural properties of PEDOT were investigated. Films were polymerized with various organic and inorganic counter-ions. Studies of crystalline order were conducted via X-ray diffraction (XRD). Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to investigate the electrical properties of these films. X-ray photoelectron spectroscopy (XPS) was used to investigate surface chemistry of PEDOT films. The results of XRD experiments showed that films polymerized with certain small counter-ions have a regular structure with strong (100) edge-to-edge correlations of PEDOT chains at ∼1.3 nm. After annealing at 170 °C for 1 h, the XRD peaks attributed to PEDOT disappeared. PEDOT polymerized with LiClO₄ as a counter-ion showed improved impedance and charge storage capacity after annealing at 160 °C.     

Fluorene-based narrow-band-gap copolymers for red light-emitting diodes and bulk heterojunction photovoltaic cells

A series of narrow band-gap conjugated copolymers (PFO-DDQ) derived from 9,9-dioctylfluorene (DOF) and 2,3-dimethyl-5,8-dithien-2-yl-quinoxalines (DDQ) is prepared by the palladium-catalyzed Suzuki coupling reaction with the molar feed ratio of DDQ at around 1%, 5%, 15%, 30% and 50%, respectively. The obtained polymers are readily soluble in common organic solvents. The solutions and the thin solid films of the copolymers absorb light from 300–590 nm with two absorbance peaks at around 380 and 490 nm. The intensity of 490 nm peak increases with the increasing DDQ content in the polymers. Efficient energy transfer due to exciton trapping on narrow-band-gap DDQ sites has been observed. The PL emission consists exclusively of DDQ unit emission at around 591–643 nm depending on the DDQ content in solid film. The EL emission peaks are red-shifted from 580 nm for PFO-DDQ1 to 635 nm for PFO-DDQ50. The highest external quantum efficiency achieved with the device configuration ITO/PEDOT/PVK/PFO-DDQ15/Ba/Al is 1.33% with a luminous efficiency 1.54 cd/A. Bulk heterojunction photovoltaic cells fabricated from composite films of PFO-DDQ30 copolymer and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) as electron donor and electron acceptor, respectively in device configuration: ITO/PEDOT:PSS/PFO-DDQ30:PCBM/PFPNBr/Al shows power conversion efficiencies of 1.18% with open-circuit voltage (V_oc) of 0.90 V and short-circuit current density (J_sc) of 2.66 mA/cm² under an AM1.5 solar simulator (100 mW/cm²). The photocurrent response wavelengths of the PVCs based on PFO-DDQ30/PCBM blends covers 300–700 nm. This indicates that these kinds of low band-gap polymers are promising candidates for polymeric solar cells and red light-emitting diodes.     

Small angle neutron scattering studies of composite latex film structure

The mechanical properties and structure of composite films made of high T_g polystyrene (PS) nodules dispersed in a low T_g polybutylacrylate (PBuA) matrix were studied by means of dynamic mechanical spectrometry and small angle neutron scattering. For films cast from mixtures of PS and PBuA latexes, film mechanical reinforcement was obtained above a percolation threshold of about 30% PS volume fraction. A segregation of PS particles into dense clusters in the PBuA continuous matrix, reminiscent of a phase separation, was observed. For films cast from core-shell particles, this segregation phenomenon may be prevented, depending on the coverage of the PS core by the PBuA shell. An efficient core encapsulation in the core-shell morphology leads to poor contact between PS cores, and the elastic moduli are then close to that of the PBuA matrix. Upon annealing the films above the T_g of PS, extensive coalescence of PS particles occurred when large contacts were already present in the dry film at room temperature, and a percolating network of coalesced PS domains provides large elastic moduli at temperatures between the T_g of PBuA and PS. The coalescence was prevented when PS particles were taken apart by the PBuA shell.