Ultrafast-laser-treated poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) electrodes with enhanced conductivity and transparency for semitransparent perovskite solar cells

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is an important organic electrode for solution-processed low-cost electronic devices. However, it requires doping and post-solvent treatment to improve its conductivity, and the chemicals used for such treatments may affect the device fabrication process. In this study, we developed a novel route for exploiting ultrafast lasers (femtosecond and picosecond laser) to simultaneously enhance the conductivity and transparency of PEDOT:PSS films and fabricate patterned solution-processed electrodes for electronic devices. The conductivity of the PEDOT:PSS film was improved by three orders of magnitude (from 3.1 to 1024 S·cm^–1), and high transparency of up to 88.5% (average visible transmittance, AVT) was achieved. Raman and depth-profiling X-ray photoelectron spectroscopy revealed that the oxidation level of PEDOT was enhanced, thereby increasing the carrier concentration. The surface PSS content also decreased, which is beneficial to the carrier mobility, resulting in significantly enhanced electrical conductivity. Further, we fabricated semitransparent perovskite solar cells using the as-made PEDOT:PSS as the transparent top electrodes, and a power conversion efficiency of 7.39% was achieved with 22.63% AVT. Thus, the proposed route for synthesizing conductive and transparent electrodes is promising for vacuum and doping-free electronics.     

Ag mesh network framework based nano composite for transparent conductive functional electrodes for capacitive touch sensor and thin film heater

We report on the development of a highly conductive, transparent and flexible Ag mesh-like network covered by an ITO/PEDOT:PSS nanocomposite for flexible conductive electronics. The electrode was deposited completely via solution-based deposition. A lower R_s value, from 7.21 Ω/□ to 5.05 Ω/□, was achieved by annealing the substrate via low-temperature plasma annealing. The low-temperature annealing was used to achieve crystallinity of the materials without deformation and degradation of PEDOT:PSS and the PET substrate. The low-cost deposition-based Ag NW-ITO/PEDOT:PSS electrode substantially decreased sheet resistance and provides the transmittance of 85.17%. The chemical stability and mechanical stability of the product were examined, and morphological studies were performed; in all of these, the substrate exhibited excellent behavior. Finally, a transparent flexible electrical heater and capacitive touch screen panel were fabricated using the Ag NW-ITO/PEDOT:PSS electrode to demonstrate the performance of the electrode and its potential applications.     

On the mechanism of conductivity enhancement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film through solvent treatment

The conductivity of a poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film is enhanced by more than 100-folds on adding some organic compounds into PEDOT:PSS aqueous solutions or by treating the PEDOT:PSS film with organic solvents, such as ethylene glycol (EG), 2-nitroethanol, methyl sulfoxide or 1-methyl-2-pyrrolidinone. The mechanism for this conductivity enhancement was studied through various chemical and physical characterizations. The PEDOT:PSS film which is soluble in water becomes insoluble after treatment with EG. This strongly suggests an increased interchain interaction among the PEDOT chains. Raman spectroscopy indicates that this increased interchain interaction results from conformational changes of the PEDOT chains, which change from a coil to linear or expanded-coil structure. The increased interchain interaction and conformation changes are further confirmed by the temperature dependence of conductivity and the electron spin resonance (ESR). It is found that EG treatment lowers the energy barrier for charge hopping among the PEDOT chains, lowers the polaron concentration in the PEDOT:PSS film by ∼50%, and increases the electrochemical activity of the PEDOT:PSS film in NaCl aqueous solution by ∼100%. Atomic force microscopy (AFM) and contact angle measurements show that the surface morphology of the PEDOT:PSS film changes as well after the EG treatment. Conductivity enhancement was also observed when other organic compounds were used, but it was strongly dependent on the chemical structure of the organic compounds, and observed only with organic compound with two or more polar groups. These experimental results support our proposal that the conductivity enhancement is due to the conformational change of the PEDOT chains and the driving force is the interaction between the dipoles of the organic compound and dipoles or charges on the PEDOT chains.     

Preparation of polyaniline-poly (p-styrenesulfonic acid) composite by post-polymerization and application as positive active material for a rechargeable lithium battery

Polyaniline (PANI)-poly (p-styrenesulfonic acid) (PSS) composite was prepared by thermal post-polymerization of PANI-p-styrenesulfonic acid (SSA) composite. A PANI–SSA composite was prepared by mixing PANI/N-methyl-2-pyrrolidinone solution with SSA aqueous solution. The PANI–SSA composite film was prepared by casting the composite onto an ITO glass plate. The cast film was converted to PANI-PSS film by heating at 100°C for 3h (post-polymerization process). The PANI–PSS modified ITO electrode showed electrochemical responses based on the redox reaction of PANI–PSS composite in the organic electrolyte solution, for example, propylene carbonate containing 1moldm–3 LiClO4. The PANI–PSS composite was a cation -doping polymer composite. The composite was also modified on a porous carbon material (Reticulated Vitreous CarbonTM, RVC, Energy Research and Generation, Inc.). The PANI–PSS modified RVC electrode showed similar electrochemical behaviour as the PANI–PSS modified ITO electrode. Model secondary lithium cells, Li|1moldm–3 LiClO4-propylene carbonate|PANI–PSS modified RVC electrode, were constructed and charge–discharge cycling tests were carried out. The cell showed about 60% coulombic efficiency under high current density cycling conditions (3.8Ag–1, per gram of PANI–PSS modified RVC electrode).     

Transparent and flexible electrodes and supercapacitors using polyaniline/single-walled carbon nanotube composite thin films

Large-scale transparent and flexible electronic devices have been pursued for potential applications such as those in touch sensors and display technologies. These applications require that the power source of these devices must also comply with transparent and flexible features. Here we present transparent and flexible supercapacitors assembled from polyaniline (PANI)/single-walled carbon nanotube (SWNT) composite thin film electrodes. The ultrathin, optically homogeneous and transparent, electrically conducting films of the PANI/SWNT composite show a large specific capacitance due to combined double-layer capacitance and pseudo-capacitance mechanisms. A supercapacitor assembled using electrodes with a SWNT density of 10.0 μg cm(-2) and 59 wt% PANI gives a specific capacitance of 55.0 F g(-1) at a current density of 2.6 A g(-1), showing its possibility for transparent and flexible energy storage.     

Reactive processing and evaluation of butadiene–styrene copolymer/polyaniline conductive blends

Blending is an important way to obtain materials based on intrinsically conductive polymers and conventional plastics and rubber materials. Much research has been carried out to determine the best performance of materials be used for electrostatic dissipation and electromagnetic interference shielding. Mechanical mixing, codissolution, and in situ polymerization have been used to prepare these materials. The method used depends on the host polymer and its thermal stability and acid attack resistance. Homogeneity and miscibility are properties that should be controlled during blend preparation. In this study, we prepared a conductive thermoplastic elastomer material based on butadiene–styrene copolymer (SBR) and polyaniline (PANI) doped with dodecylbenzene sulfonic acid (DBSA) and poly(styrene sulfonic acid) (PSS). PSS also acted as compatibilizer between PANI and SBR. PANI was doped by reactive processing with DBSA and PSS to produce the conductive complex PANI–DBSA–PSS. This complex was mixed with 90, 70, and 50% (w/w) SBR in a counterrotatory internal mixer. Conductivity tests, swelling studies, thermal analysis, and mechanical property and reflectivity testing were done, and the results show a strong dependence on PANI concentration and the ratio between PANI–DBSA and PSS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 681–685, 2006     

Anticorrosion efficiency of organic coatings depending on the pigment volume concentration of polyaniline phosphate

Polyaniline (PANI) was synthesized by reaction in an aqueous solution of ammonium peroxodisulfate and phosphoric acid. PANI was characterized by means of scanning electron microscopy and its physical–chemical properties were determined. Simultaneously with the synthesized PANI epoxy-ester coatings containing 3, 5, 10, 15, 20 and 24 vol.% of PANI as a corrosion inhibitor were formulated. The coatings were tested for their mechanical properties, film hardness and corrosion resistance. The testing of the anticorrosion efficiency of PANI as corrosion inhibitor was based on accelerated corrosion tests: in condensed water, NaCl mist, and condensing water and SO₂. The prepared PANI displayed inhibition effects in corrosion reactions progressing on a steel base under the organic coating. The synthesized PANI provides good anticorrosion efficiency in an epoxy-ester coating. The studied system does not contain any heavy metals harmful to the environment.     

Fabrication of flexible transparent electrodes using PEDOT:PSS and application to resistive touch screen panels

The flexible transparent electrodes were fabricated by line patterning of conductive inks consisting of poly(3,4‐ethylenedioxythiophene) doped with poly(4‐styrenesulfonic acid) (PEDOT:PSS) water dispersion, ethylene glycol, isopropyl alcohol, and tetraethoxysilane (TEOS) on polyethylene terephthalate (PET) films. The values of sheet resistance (R_s), total light transmittance, haze, figure‐of‐merit, and pencil hardness of the PEDOT:PSS‐TEOS/PET film were found to be 301 Ω/sq., 85.0%, 2.4%, 41, and 2H, respectively. Furthermore, a resistive touch screen panel was fabricated using the PEDOT:PSS‐TEOS/PET film as the top electrode. It was found that the drawing on the resistive touch screen panel was successfully displayed on the PC screen with good in‐plane uniformity and maximum linearity of 0.8%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45972.     

Morphological and electrochemical properties of “polyelectrolyte multilayer films” made from polyaniline and ZnO nanoparticles: Deposition as films or as clusters?

Deposits made by the alternated deposition of polyaniline (PANI) and ZnO nanoparticles may offer interesting applications as nonvolatile memory devices owing to the specific properties of each constituent. The rectifying ratio of such devices may strongly depend on the PANI/ZnO interface and on the morphology of the (PANI/ZnO)_n or (PANI/ZnO)_n‐PANI films. In this article we show that even if the morphology of the PEI/PSS‐(PANI/ZnO)_n or of the PEI/PSS‐(PANI/ZnO)_n‐PANI films seems very heterogeneous on the basis of scanning electron micrographs, the deposits consist of clusters deposited on a continuous film. In addition, the deposits become impermeable to ferrocyanide anions after the deposition of n = 10 alternated deposition cycles, confirming the existence of a continuous and impermeable film below the observed clusters. Such deposits may find interesting properties as a nonvolatile memory device. POLYM. COMPOS. 34:1333–1341, 2013. © 2013 Society of Plastics Engineers     

Effect of secondary dopants on electrochemical and spectroelectrochemical properties of polyaniline

Polyaniline (PANI) was doped with poly(styrene sulfonic acid) (PSS) via doping-dedoping-redoping procedure. Incorporation of PSS in PANI resulted modifications in electrochemical and electrochromic properties, morphology and polymer structure of the polymer film as evidenced by the results of cyclic voltammetry, in situ UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis and conductivity measurements. PANI doped with PSS was found to have a cross-link/branched structure with a minimum degradation product. The absence of degradation products improves the electrochemical, electrochromic properties and thermal stability of the PANI layer for electrochromic applications.     

Conductive poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonate) polymer glue as an ohmic and rectifying electrical contact for H‐terminated n‐Si and p‐Si wafers

An organic conductive glue based on a blend of poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and d ‐sorbitol was examined for laminating conductors to crystalline silicon. The PEDOT:PSS glue functions as a high‐work‐function solution processable conductor and exhibits an ohmic contact on p‐type silicon and a rectifying contact on n‐type silicon. Under illumination, the n‐Si/PEDOT:PSS:d ‐sorbitol junctions exhibit current–voltage characteristics suggesting minority carrier trap states, leading to charge recombination at the silicon/polymer interface. Conductive glue for laminating to crystalline silicon is desirable for making electrical contacts to flexible materials such as molecular semiconductors, graphene or transparent conductive oxides. These materials could eliminate the need for metal contacts to the front face of silicon solar cells. Conductive glue could prove especially useful for laminating to textured silicon or novel micro‐ or nanostructured silicon materials. © 2018 Society of Chemical Industry     

Dendrimer‐encapsulated Pt nanoparticles/polyaniline nanofibers for glucose detection

A novel amperometric glucose biosensor based on self‐assembling glucose oxidase (GOx) and dendrimer‐encapsulated Pt nanoparticles (Pt‐DENs) on nanofibrous polyaniline (PANI) was described. PANI nanofibers were synthesized via an interfacial polymerization method. A sulfonated polyelectrolytes‐poly(sodium 4‐styrenesulfonate) (PSS) was used to form the negative PANI/sulfonated polyelectrolyte complex, which had good disperse in aqueous solution. GOx was immobilized on the PANI/PSS surface by alternatively assembling a cationic Pt‐DENs layer and an anionic GOx layer. The unique sandwich‐like layer structure (Pt‐DENs/GOx/Pt‐DENs/PANI/PSS) formed by self‐assembling provides a favorable microenvironment to keep the bioactivity of GOx and to prevent enzyme molecule leakage. The fabricated Pt‐DENs/GOx/Pt‐DENs/PANI/PSS electrode exhibited excellent response performance to glucose with a detection limit of 0.5 μM, wide linear range from 10 μM to 4.5 mM, short response time within 5 s, improved sensitivity of 39.63 μA/(mM cm²), and good stability (85% remains after 20 days). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Flexible polymer thermoelectric device based on PEDOT:PSS and surface treated pyromellitic dianhydride-oxydianiline polyimide substrate

Flexible polymer thermoelectric devices based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and pyromellitic dianhydride-oxydianiline polyimide polyimide (PI) were fabricated and investigated in this work. PI was selected as a substrate for PEDOT:PSS to secure from repeated bending cycles of flexible device. To enhance the interfacial adhesion between PEDOT:PSS and PI, oxygen plasma treatment was used on the surface of PI substrate. The effect of the surface treatment with oxygen plasma on the synthesized PI substrate was significant. The polar component of surface free energy of PI was increased from 2.8 to 31.8 mJ/m². The power factor of PEDOT:PSS on the PI substrate was increased from 25.86 to 43.78 μW m⁻¹ K⁻². Also, as a result of 10 k times of bending test, the electrical performance consistency and the mechanical stability of the fabricated devices were confirmed. This verified fabricated flexible polymer thermoelectric devices based on PEDOT:PSS and PI are suitable for the various applications.     

Transparent Conducting Electrodes from Conducting Polymer Nanofibers and Their Application as Thin‐Film Heaters

Transparent conducting electrodes attract attention in relation to solar cells, touch panels, displays, e‐readers, and transparent heaters. In many cases, rarefied metal nets with optical transmittance of ≈90% and with minimal sheet resistance are sought after. Here, a mesh of conducting polymer nanofibers is developed as a transparent conducting electrode. A sheet resistance of 8.4 kΩ sq⁻¹ with 84% optical transmittance is achieved with polyethylene oxide/poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEO/PEDOT:PSS) blended polymer nanofibers. This study also demonstrates that such nanofiber being deposited on a glass substrate can be used as a transparent film heater in relevant applications such as window heating or displays at harsh environments. Such a transparent heater is rated at 0.41 W in.⁻² for 120 V. It is also capable of heating a substrate up to ≈70 °C in 4 min at 60 V from room temperature without any degeneration of nanofiber network, rendering itself as a practically useful transparent heater. The performance of the PEO/PEDOT:PSS nanofiber‐coated transparent glass heater is comparable to that of the relatively expensive indium tin oxide thin‐film heaters.     

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.     

Facile preparation of conductive paint made with polyaniline/dodecylbenzenesulfonic acid dispersion and poly(methyl methacrylate)

We investigated an easy way to prepare industrially a conductive paint made with polyaniline (PANI)/dodecylbenzenesulfonic acid (DBSA) dispersion and poly(methyl methacrylate) (PMMA) in organic media. First, water‐dispersible PANI doped with DBSA was chemically synthesized with aniline sulfate using ammonium persulfate in water, and the resulting PANI/DBSA was readily extracted from the reaction medium with a mixture of toluene and methyl ethyl ketone (MEK) (toluene:MEK = 1:1 (v/v)), which is useful for industrial applications. The obtained PANI/DBSA organic dispersion was mixed with PMMA organic solution to give the corresponding PANI/DBSA conductive paint containing PMMA. A film prepared with the resulting PANI/DBSA conductive paint was found to possess relatively good conductivity and low surface resistivity for a conductive paint utilized for an electrostatic discharge even at low PANI/DBSA content in the PANI/DBSA–PMMA composite film (the conductivity and the surface resistivity were 9.48 × 10^?4 S cm^?1 and 3.14 × 10⁶ Ω cm^?2, respectively, when the feed ratio of PANI/DBSA:PMMA was 1:39 (w/w)). Furthermore, it was found that the conductivity of the film composed of PANI/DBSA–PMMA composite can be readily and widely controlled by the PANI/DBSA content of the composite or by the amount of DBSA used during the PANI/DBSA synthesis. The highest conductivity of PANI/DBSA–PMMA composite film (7.84 × 10^?1 S cm^?1) was obtained when the feed ratio of PANI/DBSA:PMMA was 1:4 (w/w). Copyright © 2007 Society of Chemical Industry     

High dielectric constant polyaniline/sulfonated poly(aryl ether ketone) composite membranes with good thermal and mechanical properties

All‐organic polyaniline (PANI)/sulfonated poly(aryl ether ketone) (SPAEK) composite membranes consisting of a PANI (conducting) filler evenly distributed in an SPAEK (insulating) matrix were prepared with a solution‐blending technique. The dielectric properties, electrical conductivity, and thermal and mechanical performances of the all‐organic PANI/SPAEK composite membranes were investigated as a function of different PANI loading levels. The composite membrane containing 30 wt % PANI exhibited a high dielectric constant of about 600, a low dielectric loss tangent of about 0.6 (at 1 kHz), and good thermal properties (temperature for 5% weight loss > 250°C) and mechanical properties (tensile strength ≈ 35 MPa). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1990–1995, 2013     

Interfacial polymerization of polyaniline and its layer‐by‐layer assembly into polyelectrolytes multilayer thin‐films

The layer‐by‐layer (LbL) self assembly deposition technique was used to prepare multilayer thin films of anionic polyaniline‐blend‐poly(sodium 4‐styrenesulfonate) (PANI‐PSS) and cationic poly(diallydimethylammonium chloride) (PDADMAC). Anionic polyaniline was prepared by the interfacial polymerization of aniline monomer in the presence of PSS which acted as template to provide water solubility. The PSS to PANI concentration ratios used in the synthesis step was found to have a major effect on the final PANI‐PSS synthesis, its self assembly and the electrical properties of the prepared films. The optical and electrical properties of the films were measured by ultraviolet‐visible spectroscopy (UV‐Vis) and a 4‐point probe setup, respectively while the thickness of the films was measured by atomic force microscopy (AFM). Results showed that the optimum condition for the film growth and optimal conductivity were obtained with different synthesis conditions. These results suggest that the PSS concentration used for interfacial synthesis of PANI must be finely tuned depending on the type of application aimed by the user. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A red-to-gray poly(3-methylthiophene) electrochromic device using a zinc hexacyanoferrate/PEDOT:PSS composite counter electrode

In this paper, we describe a novel red-to-gray poly(3-methylthiophene) (PMeT) electrochromic device (ECD) with the aid of a zinc hexacyanoferrate (ZnHCF)/PEDOT:PSS counter electrode. The application of ZnHCF to an ECD is first reported. ZnHCF has long suffered from poor deposition yield problem, but we demonstrate that a robust ZnHCF film can be prepared by spin coating of a liquid suspension composed of ZnHCF nanoparticles and PEDOT:PSS ink on ITO. It was found that the ZnHCF/PEDOT:PSS composite worked much better with PMeT than pure ZnHCF or pure PEDOT:PSS from both electrochemical and optical aspects. With a LiClO₄/PC electrolyte, the PMeT ECD having ZnHCF/PEDOT:PSS as its counter electrode could be reversibly switched between its red state (>0.8 V) and its gray state (<0 V). For a 2 cm × 2 cm prototype device, the response time for coloration was less than 1 s. The maximum transmittance modulation of the device could attain 45.3% at 750 nm, which resulted in a corresponding coloration efficiency of 336.8 cm²/C. The maximum contrast ratio was 5.45 at 720 nm. In addition, the charge capacity of the ECD could retain 95% of its original value after 10,000 cycles of cyclic voltammetry aging test, although an electrodeposited PMeT film alone could be cycled several hundred times only. To sum up, this work proposes a new, cost-effective transparent counter electrode and brings a stable, high visual-contrast PMeT ECD prototype for further development of a red-color bistable display.     

Freeze-drying and mechanical redispersion of aqueous PEDOT:PSS

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films are attracting famous applications in antistatic coating, energy storage and conversion, printed electronics, and biomedical fields due to their conductivity, optical transparency and flexibility. However, PEDOT:PSS has poor dispersion stability during long-term storage and transport. Moreover, the dried PEDOT:PSS films are insoluble in any solvent and cannot be redispersed again. In comparison to bake drying, here, a feasible strategy to achieve mechanically redispersed PEDOT:PSS with the help of freeze-drying process was reported. The redispersed PEDOT:PSS can recover not only the initial characters such as pH, chemical composition, viscosity, and particle size under similar solid contents, but also conductivity and surface morphology of treated films. In addition, the treated film exhibits self-healing properties similar to pristine film in terms of mechanical and electrical properties. This technology enables reuse and overcomes the technical problems of PEDOT:PSS dispersion, realizing real-time processing to meet variable applications.