A simple, low-cost approach to prepare flexible highly conductive polymer composites by in situ reduction of silver carboxylate for flexible electronic applications

In recent years, efforts to prepare flexible highly conductive polymer composites at low temperatures for flexible electronic applications have increased significantly. Here, we describe a novel approach for the preparation of flexible highly conductive polymer composites (resistivity: 2.5 × 10⁻⁵ Ω cm) at a low temperature (150 °C), enabling the wide use of low cost, flexible substrates such as paper and polyethylene terephthalate (PET). The approach involves (i) in situ reduction of silver carboxylate on the surface of silver flakes by a flexible epoxy (diglycidyl ether of polypropylene glycol) to form highly surface reactive nano/submicron-sized particles; (ii) the in situ formed nano/submicron-sized particles facilitate the sintering between silver flakes during curing. Morphology and Raman studies indicated that the improved electrical conductivity was the result of sintering and direct metal-metal contacts between silver flakes. This approach developed for the preparation of flexible highly conductive polymer composites offers significant advantages, including simple low temperature processing, low cost, low viscosity, suitability for low-cost jet dispensing technologies, flexibility while maintaining high conductivity, and tunable mechanical properties. The developed flexible highly conductive materials with these advantages are attractive for current and emerging flexible electronic applications.     

Fabrication of flexible conductive films derived from poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) (PEDOT:PSS) on the nonwoven fabrics substrate

In this research, conducting poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) (PEDOT:PSS) aqueous dispersion was synthesized at first via chemical oxidative polymerization and followed by mixing it with poly(styrene-r-butyl acrylate) P(St-BA) aqueous latex, creating a conductive material with outstanding stretchability. The elastic conductive composite were then film formed on the glass and poly(ethylene terephthalate) (PET) nonwoven fabric substrate by spin coating and dip coating, respectively. Composite films with various contents of PEDOT:PSS polymer (10–100 wt.%) had been prepared. From the conductivity measurements, the conductivity was still kept as high as 88 S cm⁻¹ even the PEDOT:PSS content was lowered to 10 wt.%. Furthermore, the elasticity of conductive films on the PET-nonwoven fabric substrate was evaluated by the 180° bending test repeating 100 times. With introducing soft P(St-BA) material in the PEDOT:PSS phase, the surface resistance increased merely 3–6 times after bending 100 times, while the surface resistance for pure PEDOT:PSS film could reach 18–20 times.     

Planar silver nanowire,carbon nanotube and PEDOT:PSS nanocomposite transparent electrodes

Highly conductive, transparent and flexible planar electrodes were fabricated using interwoven silver nanowires and single-walled carbon nanotubes (AgNW:SWCNT) in a PEDOT:PSS matrix via an epoxy transfer method from a silicon template. The planar electrodes achieved a sheet resistance of 6.6 ± 0.0 Ω/□ and an average transmission of 86% between 400 and 800 nm. A high figure of merit of 367 Ω⁻¹ is reported for the electrodes, which is much higher than that measured for indium tin oxide and reported for other AgNW composites. The AgNW:SWCNT:PEDOT:PSS electrode was used to fabricate low temperature (annealing free) devices demonstrating their potential to function with a range of organic semiconducting polymer:fullerene bulk heterojunction blend systems.     

Planar silver nanowire,carbon nanotube and PEDOT:PSS nanocomposite transparent electrodes

Abstract

Highly conductive, transparent and flexible planar electrodes were fabricated using interwoven silver nanowires and single-walled carbon nanotubes (AgNW:SWCNT) in a PEDOT:PSS matrix via an epoxy transfer method from a silicon template. The planar electrodes achieved a sheet resistance of 6.6 ± 0.0 Ω/□ and an average transmission of 86% between 400 and 800 nm. A high figure of merit of 367 Ω^?1 is reported for the electrodes, which is much higher than that measured for indium tin oxide and reported for other AgNW composites. The AgNW:SWCNT:PEDOT:PSS electrode was used to fabricate low temperature (annealing free) devices demonstrating their potential to function with a range of organic semiconducting polymer:fullerene bulk heterojunction blend systems.     

Preparation and characterization of poly(3,4-ethylenedioxythiophene)–poly(styrene sulfonate) composite thin films highly loaded with platinum nanoparticles

In this work, we propose a simple and efficient, low-temperature (∼120 °C) process to prepare transparent thin films of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS) loaded with high concentration (up to 22.5 wt%) of platinum (Pt) nanoparticles. Firstly, an improved polyol method was modified to synthesize nano-sized (∼5 nm) and mono-dispersed Pt particles. These nanoparticles were incorporated into the matrix of PEDOT:PSS thin films via a spin coating/drying procedure. The electrochemical activities of the PEDOT:PSS thin film modified electrodes with respect to the I⁻/I₃⁻ redox reactions were investigated. It was found that the modified electrode of PEDOT:PSS thin film containing 22.5 wt% Pt exhibited the electrochemical activity comparable to the conventional Pt thin film electrode, suggesting that this electrode has good potential to serve as a counter electrode in dye-sensitized solar cells.     

PEDOT:PSS nano-gels for highly electrically conductive silver/epoxy composite adhesives

In this work, we report a methanol-facilitated approach to directly use aqueous Poly(3,4-ethylenedioxythiophene):Poly(styrene sulfonate) (PEDOT:PSS) in the silver/epoxy composites for preparation of highly electrically conductive adhesives (ECAs) and an investigation of the interaction between PEDOT:PSS nano-gels and silver microflakes. PEDOT:PSS nano-gel (18?<?d?<?30 nm) aqueous dispersion is immiscible with epoxy resin and difficult to incorporate into the conventional silver-filled ECAs. To overcome this challenge, we used methanol to facilitate the dispersion of PEDOT:PSS and silver microflake in epoxy resin. The synergetic interactions between PEDOT:PSS and silver and the effect of methanol were investigated using dynamic light scattering (DLS), atomic force microscopy, Kelvin probe force microscopy, and scanning electron microscope. When PEDOT:PSS was exposed to methanol, its morphology changed from coil to coil/linear structure; the contact potential difference between silver microflake and PEDOT:PSS increased from 9.47 to 22.56 mV, showing an increased conductivity between PEDOT:PSS and silver microflake. It was found that the introduction of a small amount of PEDOT:PSS (0.1 wt%) to the conventional ECA with 60 wt% silver microflake remarkably improved the electrical conductivity from 104 to 386 S/cm. A significantly high conductivity of 2526 S/cm was achieved by further increasing the PEDOT:PSS concentration to 1 wt%. The impact of PEDOT:PSS on the adhesive bonding strength towards copper substrate was also examined; the bonding strength slightly decreased when <?1 wt% PEDOT:PSS was used, but abruptly dropped when PEDOT:PSS content was further increased beyond 1 wt%. The incorporation of the optimal 1 wt% PEDOT:PSS into conventional ECAs with 60% silver microflake greatly increased the electrical conductivities by 25 times with limited impact on the shear strength. The results provide insights to the synergetic interplay of conductive polymer and metallic fillers, and might have profound technical implications on the development of advanced conductive composites.     

Conductive polymer PEDOT:PSS back contact for CdTe solar cell

Two types of superstrate glass/ITO/CdS/CdTe PV structures were prepared by high vacuum evaporation technique with (i) activation of CdS layer and CdS/CdTe bi-layer structure step-by-step and (ii) activation of CdS/CdTe bi-layer structure. The activation was performed by annealing the structures with CdCl₂ in air at 400 °C for 15 min. Main conditions for CdS and CdTe thin films deposition and following treatment were selected from the literature data with the purpose to prepare and compare complete CdTe solar cells with standard p + Cu_xTe back contact and conductive polymer poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonic acid (PEDOT:PSS) back contact. Obtained layers and structures were characterized using the XRD, SEM and I-V methods. Both the methods of activation treatment give comparable results from the point of view PV properties of complete solar cells. It was found that highly conductive PEDOT:PSS intermediate layer can significantly improve the back contact characteristics of CdTe. However these hybrid structures need to be further optimized to compete successfully with conventional inorganic back contacts in complete CdTe solar cells.     

An Electrochemical Gelation Method for Patterning Conductive PEDOT:PSS Hydrogels

Due to their high water content and macroscopic connectivity, hydrogels made from the conducting polymer PEDOT:PSS are a promising platform from which to fabricate a wide range of porous conductive materials that are increasingly of interest in applications as varied as bioelectronics, regenerative medicine, and energy storage. Despite the promising properties of PEDOT:PSS‐based porous materials, the ability to pattern PEDOT:PSS hydrogels is still required to enable their integration with multifunctional and multichannel electronic devices. In this work, a novel electrochemical gelation (“electrogelation”) method is presented for rapidly patterning PEDOT:PSS hydrogels on any conductive template, including curved and 3D surfaces. High spatial resolution is achieved through use of a sacrificial metal layer to generate the hydrogel pattern, thereby enabling high‐performance conducting hydrogels and aerogels with desirable material properties to be introduced into increasingly complex device architectures.     

Assessment of electromechanical properties of screen printed polymer nanopastes

Printed electronics has provided different printing techniques as environmentally friendly and cost-effective manufacturing methods of electronic components. The printed items can be produced on low cost, different types of flexible substrates, even when their surface is corrugated. This opens a new application range of printed electronics and makes them competitive with traditionally manufactured electronics. However, it is necessary to investigate new materials to continue the rapid progress in printed electronics. In our study, the electromechanical properties of polymer nanopastes consisted of carbon nanotubes and graphite platelet nanofibers mixed with a conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) were investigated. Their microstructure and the layer morphology were observed using a scanning electron microscope and an optical microscope. The thickness and average roughness of the layers printed on the foil and paper were determined with a contact profilometer. The mechanical durability of the screen printed layers was verified in a cyclic bending test. The highest mechanical durability was exhibited by the polymer pastes containing carbon nanotubes.     

Synergetic effect of hybrid boron nitride and multi-walled carbon nanotubes on the thermal conductivity of epoxy composites

This study investigates the synergistic effect of combining multi-walled carbon nanotubes (MWCNTs) and boron nitride (BN) flakes on thermally conductive epoxy composite. The surface of the two fillers was functionalized to form covalent bonds between the epoxy and filler, thereby reducing thermal interfacial resistance. The hybrid filler provided significant enhancement of thermal conductivity, adding 30 vol% modified BN and 1 vol% functionalized MWCNTs achieving a 743% increase in thermal conductivity (1.913 W mK⁻¹, compared to 0.2267 W mK⁻¹ of neat epoxy).     

Conductivity enhancement of conjugated polymer after HCl-methanol treatment

Polymer conductivity is key factor to improve the performance of the electronic and photonic devices. Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) films were soaked into 0.03, 0.14, 0.41, and 1.13 M concentrations of HCl-methanol solution for 10, 20, 30, 40, 50, 60, and 70 min. The resulting films were investigated using Fourier transform infrared (FTIR) spectrometry, conductivity measurements, and field emission scanning electron microscopy. The characteristic FTIR absorption peaks of poly(4-styrenesulfonate) (PSS) of the films decreased as the soaking time increased. While PSS absorption peaks appeared in the HCl-methanol soaking solution and increased with the soaking time. The conductivity of PEDOT:PSS film was approximately 1.20 × 10^− 6 S/cm before soaking in the HCl-methanol solution. The conductivity of PEDOT:PSS was enhanced nearly three orders of magnitude after soaking the films into the HCl-methanol solvent. The surface of PEDOT:PSS film was initially very smooth. However, numerous humps appeared on the surface of the films after soaking PEDOT:PSS film into the HCl-methanol solution for 10, 20, and 30 min. The number of humps was reduced and disappeared thereafter.     

Study of the effect of the doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) polymeric anode on the organic light-emitting diode performances

Bottom-emitting organic diode devices with polymeric anode were fabricated and their performances were compared to devices with different anodes. The highly transparent (transmittance ≈ 90%) and conductive (700 S/cm) anode was poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) processed from aqueous solution and modified by addition of dimethyl sulfoxide (DMSO). The electro-optical characteristics of the DMSO-doped PEDOT:PSS based device and devices with architectures based on undoped PEDOT:PSS and/or indium tin oxide (ITO) were investigated and the effects of the different anodes were analyzed by means of electrical responses in static and dynamic regimes. The efficiency of the device with the proposed polymeric anode was comparable to that of ITO based device but reduced with respect to the device including PEDOT:PSS as hole-injection layer. These results were correlated to the film morphological properties and discussed in terms of interfacial state density modification.     

Organic thin film transistor using silver electrodes by the ink-jet printing technology

We have developed a conductive ink containing silver nanoparticles from which the electrodes for organic thin film transistor were directly patterned by ink-jet printing. Nano-sized silver particles having ∼ 20 nm diameter was used for a direct metal printing. Silver conductive ink was printed on the heavily doped n-type silicon wafer with 200-nm thick thermal SiO₂ layer as a substrate. To achieve a high line resolution and smooth conductive path, the printing conditions such as the inter-drop distance, stage moving velocity and temperature of the pre-heated substrates were optimized. After the heat-treatment at temperatures of 200 °C for 30 min, the printed silver patterns exhibit metal-like appearance and the conductivity. To fabricate a coplanar type TFTs, an active material of semiconducting oligomer, α,ω-dihexylquaterthiophene (DH4T) in a chlorobenzene was deposited between the ink-jet printed silver electrodes by drop casting. The OTFT with the ink-jetted source/drain electrodes shows general performance characteristics with good saturation behavior and no significant contact resistance as compared to the one with vacuum deposited electrodes. The electrical characteristic parameters of OTFT show the mobility of 1.3 × 10^− 3 cm² V^− 1 s^− 1 in the saturation regime, on/off current ratio over 10³, and threshold voltage of about − 13 V.     

Low temperature processing of hybrid nanoparticulate Indium Tin Oxide (ITO) polymer layers and application in large scale lighting devices

We report on transparent conductive indium tin oxide (In₂O₃:Sn; ITO) nanoparticle films processed at a low temperature of 130 °C for the application in lighting devices using spin coating and doctor blading techniques. Major emphasis is put on the beneficial application of the particular transparent electrode material for the fabrication of patterned large area electroluminescence lamps. In order to improve film properties like adhesion and conductivity, hybrid nanoparticle-polymer blends out of ITO particles and organic film-forming agent polyvinylpyrrolidone (PVP) and the organofunctional coupling agent 3-methacryloxypropyltrimethoxysilane (MPTS) have been developed. The layers were cured by UV-irradiation, which was also used for lateral structuring of the transparent, conductive electrode. Additional low-temperature heat treatment (T = 130 °C) in air and forming gas improved the electronic properties. While pure ITO nanoparticulate layers processed at 130 °C exhibited conductance of up to 3.1 Ω^− 1 cm^− 1, the nanocomposite coatings showed a conductance of up to 9.8 Ω^− 1 cm^− 1. Corresponding layers with a sheet resistance of 750 Ω/□ were applied in electroluminescent lamps.     

Large-scale fabrication and electrical properties of an anisotropic conductive polymer composite utilizing preferable location of carbon nanotubes in a polymer blend

An anisotropically conductive polymer composite (ACPC) based on carbon nanotubes (CNTs) and polycarbonate (PC)/polyethylene (PE) blend was fabricated via a slit die extrusion-hot stretch process. Under the influence of the shear flow and hot stretch, the PC phase is in situ deformed into aligned conductive fibrils in the PE matrix, whose surface region holds the majority of CNTs. When the stretch ratio rises to a certain level, the resistivity of the ACPC shows a strong anisotropy of three orders of magnitude difference between the perpendicular and parallel stretch directions. The fibrillar ACPC shows a weak positive temperature coefficient (PTC) effect, and two-process negative temperature coefficient (NTC) effect caused by the reorganization of PC fibrils below but near 230 °C, and the transformation from anisotropy to isotropy beyond 230 °C. The obtained ACPC allows it to have such potential applications as switch and sensor materials.     

A novel heteroleptic iridium complex with multifunctional ligands used for polymeric light-emitting diodes

A novel iridium complex using 3-(5-(4-(pyridin-2-yl)phenyl)-1,3,4-oxadiazol-2-yl)-9-hexyl-9H-carbazole containing both hole-transporting group and electron-transporting group as main ligand and 2-(5-p-tolyl-2H-1,2,4-triazol-3-yl)pyridine as ancillary ligand was synthesized and investigated in this paper. The iridium complex possesses high solubility, high thermal stability with 5% weight-reduction temperature (ΔT_5%) of 390 °C and glass-transition temperature (T_g) of 218 °C. Polymeric light-emitting diodes (PLEDs) based on structure of ITO/PEDOT: PSS/PVK: PBD: iridium complex/TPBI/CsF/Al fabricated by solution-processed technology were measured. The PLED using the iridium complex as phosphorescent dopant at 4 wt.% doping concentration is optimal which shows the maximum luminance of 7746 cd·cm⁻², maximum current efficiency of 14.0 cd A⁻¹ and maximum external quantum efficiency of 5.8% with CIE coordinates of (0.48, 0.50). The EL emission originates from both monomers and exciplexes formed from the iridium complex and PVK.     

Enhancement of poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonate) properties by poly(vinyl alcohol) and doping agent as conductive nano-thin film for electronic application

In this work, the integration of the useful concepts of polymer blending and doping agent to simultaneously improve various properties of poly(3,4-ethylene dioxy thiophene) poly(styrene sulfonate) (PEDOT:PSS) nano-thin films was shown. According to the polymer-blending concept, insulating poly(vinyl alcohol) (PVA) has a good deal of potential to be utilized as a filler to improve the critical properties of the PEDOT:PSS matrix, especially conductivity, wettability, and thermal and mechanical properties. At the appropriate amount of PVA, 0.08 wt%, it acts as a binder to improve the connection network between PEDOT:PSS chains, leading to a maximum conductivity of 1.18 S/cm, and also providing a good contact angle of 8.8°. The transmission of the films decreased with increasing PVA content; however, all specimens still showed excellent transmittance values of more than 80 %. The thermal stability and the resistance to abrasion of the nano-thin conductive films were improved by strong covalent bonds between PVA and PSS, which were verified by TGA and a scratching test, respectively. In addition, the relationship of PEDOT:PSS properties versus various amounts of insulating PVA for practical usage for specific electronic fields were shown. Use of the doping agent quinoxaline was aimed to particularly enhance the conductivity of PEDOT:PSS. The highest conductivity (2.75 S/cm) was achieved when 0.5 wt% quinoxaline was added into 0.08 wt% PVA/PEDOT:PSS while the other properties were not significantly altered.     

Low-temperature processing of transparent conductive indium tin oxide nanocomposites using polyvinyl derivatives

We report on the influence of additives on the electrical, optical, morphological and mechanical properties of transparent conductive indium tin oxide (In₂O₃:Sn; ITO) nanoparticle films by the use of polymers as matrix material. Key issues to fabricate layers suitable for use in electronic device applications are presented. Polyvinyl derivatives polyvinyl acetate, polyvinyl alcohol (PVA) and polyvinyl butyral were applied and their suitability to form transparent conductive ITO nanocomposite coatings at a maximum process temperature of 130 °C was investigated. A low-temperature treatment with UV-light has been developed to provide the possibility of curing ITO thin films deposited on substrates which do not withstand high process temperatures. Compared to best pure ITO layers (0.2 Ω^− 1 cm^− 1), the ITO-PVA nanocomposite coatings show a conductance value of 4.1 Ω^− 1 cm^− 1 and 5.9 Ω^− 1 cm^− 1 after reducing in forming gas. Sheet resistance of ca. 1200 Ω/□ with coexistent transmittance of 85% at 550 nm for a layer thickness of about 1.45 μm was achieved. The conductance enhancement is a consequence of nanoparticulate ITO network densification due to the acting shrinkage forces caused by the polymer matrix during film drying and additionally UV-induced crosslinking of PVA.     

Synthesis of conductive semi-transparent silver films deposited by a Pneumatically-Assisted Ultrasonic Spray Pyrolysis Technique

The synthesis and characterization of nanostructured silver films deposited on corning glass by a deposition technique called Pneumatically-Assisted Ultrasonic Spray Pyrolysis are reported. Silver nitrate and triethanolamine were used as silver precursor and reducer agent, respectively. The substrate temperatures during deposition were in the range of 300–450 °C and the deposition times from 30 to 240 s. The deposited films are polycrystalline with cubic face-centered structure, and crystalline grain size less than 30 nm. Deposition rates up to 600 Å min⁻¹ were obtained at substrate temperature as low as 300 °C. The electrical, optical, and morphological properties of these films are also reported. Semi-transparent conductive silver films were obtained at 350 °C with a deposition time of 45 s.     

Removal of acid orange 7 by guava seed carbon: A four parameter optimization study

The preparation of carbon from waste materials is a recent and economic alternative for the removal of dyes. In this study four samples of carbon were obtained by thermal treatment at 1000 °C using as precursor the guava seed with different particle sizes. The Taguchi method was applied as an experimental design to establish the optimum conditions for the removal of acid orange 7 in batch experiments. The chosen experimental factors and their ranges were: pH (2–12), temperature (15–35 °C), specific surface area (50–600 m² g⁻¹) and adsorbent dosage (16–50 mg ml⁻¹). The orthogonal array L₉ and the larger the better response category were selected to determine the optimum removal conditions: pH 2, temperature 15 °C, S_esp 600 m² g⁻¹ and dosage 30 mg ml⁻¹. Under these conditions a total removal of acid orange 7 was achieved. Moreover, the most significant factors were the carbon specific surface area and the pH. The influence of the different factors on the adsorption of acid orange 7 from solution is explained in terms of electrostatic interactions by considering the dye species and the character of the surface.