Explaining the effects of processing on the electrical properties of PEDOT:PSS

By simultaneously measuring the Seebeck coefficient and the conductivity in differently processed PEDOT:PSS films, fundamental understanding is gained on how commonly used processing methods improve the conductivity of PEDOT:PSS. Use of a high boiling solvent (HBS) enhances the conductivity by 3 orders of magnitude, as is well-known. Simultaneously, the Seebeck coefficient S remains largely unaffected, which is shown to imply that the conductivity is improved by enhanced connectivity between PEDOT-rich filaments within the film, rather than by improved conductivity of the separate PEDOT filaments. Post-treatment of PEDOT:PSS films by washing with H₂SO₄ leads to a similarly enhanced conductivity and a significant reduction in the layer thickness. This reduction strikingly corresponds to the initial PSS ratio in the PEDOT:PSS films, which suggests removal and replacement of PSS in PEDOT:PSS by HSO₄⁻ or SO₄²⁻ after washing. Like for the HBS treatment, this improves the connectivity between PEDOT filaments. Depending on whether the H₂SO₄ treatment is or is not preceded by an HBS treatment also the intra-filament transport is affected. We show that by characterization of S and σ it is possible to obtain more fundamental understanding of the effects of processing on the (thermo)electrical characteristics of PEDOT:PSS.     

退火及掺杂对空穴传输层PEDOT:PSS电学特性的影响

采用匀胶机旋转涂成膜的方法,在手套箱中制备PEDOT聚对苯乙烯磺酸(PSS)薄膜。详细研究了退火和掺杂对薄膜电学特性的影响,结果发现,在本实验范围内,薄膜的电导率随退火的温度和时间增加均呈现出最大值,这与薄膜的表面形貌是密切相关的;并且,由于材料的亲水性,导致真空下比N2和空气条件下退火薄膜的电导率要高;通过掺杂N,N-二甲基甲酰胺(DMF)和乙二醇,使薄膜的电导率提高了近3个量级。     

Surface plasmon spectroscopy of thin composite films of Au nanoparticles and PEDOT:PSS conjugated polymer

We studied the effect of Au nanoparticles (NPs) on optical properties of composite films of poly(3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) mixed with Au NPs of 20, 40 and 60 nm in diameter by surface plasmon resonance (SPR) spectroscopy. The excitation wavelength of SPR redshifts with increasing the concentration of Au NPs in the Au/PEDOT:PSS composite films. The SPR spectra were simulated by using transfer matrix method (TMM) and effective medium approximation (EMA). The SPR wavelength redshift was ascribed to the film thickness increase of Au/PEDOT:PSS composites rather than effective permittivity variation of the composite films induced with Au NPs inclusion.     

Preparation and thermoelectric properties of PEDOT:PSS coated Te nanorod/PEDOT:PSS composite films

PEDOT:PSS coated Te (PCTe) nanorod/PEDOT:PSS composite films were prepared by a drop-casting technique. H₂SO₄ treatment was employed to enhance thermoelectric (TE) properties of the composite films. The addition of PCTe nanorods increased both the electrical conductivity and the Seebeck coefficient of the composite films. An optimized power factor of 141.9 μW/mK² was obtained for the film containing 90 wt% PCTe nanorods treated with 12 M H₂SO₄ at room temperature, which was 2.75 times as high as that of the untreated composite film, corresponding to the electrical conductivity and Seebeck coefficient of 204.6 S/cm and 83.27 μV/K, respectively. XPS and GIWAXS analysis revealed the removal of insulating PSS units and the rearrangement of PEDOT chains after the H₂SO₄ treatment. Finally, a 9-leg TE generator prototype was fabricated using the optimized composite film. The maximum output power and area output power density produced from the prototype were 47.7 nW and 57.2 μW/cm², respectively, at the temperature difference of 40 K.     

Piezoresistive properties of PEDOT:PSS

Recent market studies mention the necessity to include sensors in the design of organic electronic devices in order to broaden the range of applications. It is therefore essential to identify potential organic mechanical sensor materials and to develop processes and methods to structure them and characterize their piezoresistive properties. Furthermore, it is also essential for organic electronic devices to know the change of resistance upon bending of flexible substrates. A material widely used in organic electronics is the complex of the intrinsically conductive polymer poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate acid (PEDOT/PSS). In this paper first the fabrication of a polyimide (PI) membrane with integrated PEDOT/PSS strain gauges is presented. Upon a pressure difference the membrane is deflected and the resulting changes in resistance of the sensor elements are recorded. By applying a membrane mechanics model the resistance changes can be linked to the strain in the membrane and then the plane strain gauge factor k_PS for PEDOT/PSS of 0.48±0.07 at 36.6±3% rH can be determined.     

Solution processable PEDOT:PSS based hybrid electrodes for organic field effect transistors

We report high performance solution processed conductive inks used as contact electrodes for printed organic field effect transistors (OFETs). Poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) electrodes show highly improved very low sheet resistance of 65.8 ± 6.5 Ω/square (Ω/□) by addition of dimethyl sulfoxide (DMSO) and post treatment with methanol (MeOH) solvent. Sheet resistance was further improved to 33.8 ± 8.6 Ω/□ by blending silver nanowire (AgNW) with DMSO doped PEDOT:PSS. Printed OFETs with state of the art diketopyrrolopyrrole-thieno[3,2-b]thiophene (DPPT-TT) semiconducting polymer were demonstrated with various solution processable conductive inks, including bare, MeOH treated PEDOT:PSS, single wall carbon nanotubes, and hybrid PEDOT:PSS-AgNW, as the source and drain (S/D) electrode by spray printing using a metal shadow mask. The highest field effect mobility, 0.49 ± 0.03 cm² V⁻¹ s⁻¹ for DPPT-TT OFETs, was obtained using blended AgNW with DMSO doped PEDOT:PSS S/D electrode.     

Modeling thin film formation by Ultrasonic Spray method: A case of PEDOT:PSS thin films

Recent improvements in electronic and optoelectronic devices based on solution processable polymers have motivated development of scalable processing techniques like Ultrasonic Spray technique. Including potential for roll to roll fabrication, it has many other strengths. However, with spray coating it can be difficult to prepare films with a smooth surface. Here, we present model for Ultrasonic Spray deposition of thin films, which establish a clear correlation between process parameters and the film formation process, which ultimately decide the structural features of the thin films. Based on the time to cover the spray deposition area by the sprayed droplets and the time for droplet evaporation, a balance parameter has been defined. It provides a mean to determine suitable process parameters for uniform film formation by Ultrasonic Spray method. The model is further modified for the region of higher solution flow rates, where non-uniformity in droplet distribution is introduced. The predictions based on the model have been experimentally verified with thin films of poly(3,4-ethylene dioxythiophene) doped with polystyrene sulphonic acid (PEDOT:PSS). The method presented here can be used to predict proper deposition parameters for smooth film deposition by Ultrasonic Spray technique. Finally, the effect of film morphology on the sheet resistance of thin films of PEDOT:PSS is also presented.     

The enhancement of electrical and optical properties of PEDOT:PSS using one-step dynamic etching for flexible application

The conductivity enhancement of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by dynamic etching process was investigated to introduce the outstanding and simplest method for soft electronics. Four different samples which were pristine PEDOT:PSS, PEDOT:PSS doped with 5 wt.% DMSO, PEDOT:PSS with dipping process, and PEDOT:PSS with dynamic etching process were prepared to compare the properties such as conductivity, morphology, relative atomic percentage, and topography. All samples were characterized by four point probe, current atomic force microscopy (C-AFM), X-ray photoelectron spectroscopy (XPS), and UV–visible spectroscopy. The conductivity of the sample with dynamic etching process showed the highest value as 1299 S/cm among four samples. We proved that the dynamic etching process is superior to remove PSS phase from PEDOT:PSS film, to flow strong current through entire surface of PEDOT:PSS, and to show the smoothest surface (RMS 2.28 nm). XPS analysis was conducted for accurate chemical and structural surface environments of four samples and the relative atomic percentage of PEDOT in the sample with dynamic etching was the highest as 29.5%. The device performance of the sample with the dynamic etching process was outstanding as 10.31 mA/cm² of J_sc, 0.75 eV of V_oc, 0.46 of FF, and 3.53% of PCE. All properties and the device performance for PEDOT:PSS film by dynamic etching process were the most excellent among the samples.     

Hybrid photovoltaic structures based on amorphous silicon and P3HT:PCBM/PEDOT:PSS polymer semiconductors

Hybrid thin film photovoltaic structures, based on hydrogenated silicon (Si:H), organic poly(3-hexythiophene):methano-fullerenephenyl-C61-butyric-acid-methyl-ester (P3HT:PCBM) and poly(3,4ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) films, have been fabricated. Organic semiconductor thin films were deposited by spin-coating technique and were exposed to radio frequency plasma enhanced chemical vapor deposition (RF PECVD) of Si:H films at deposition temperature T_d = 160 °C. Different types of structures have been investigated: H1) ITO/(p)SiC:H /P3HT:PCBM/(n) Si:H, H2) ITO/PEDOT:PSS/(i)Si:H/(n) Si:H and H3) ITO/PEDOT:PSS/P3HT:PCBM/(i)Si:H/(n)Si:H. Short circuit current density spectral response and current-voltage characteristics were measured for diagnostic of the photovoltaic performance. The current density spectral dependence of hybrid structures which contains organic layers showed improved response (50–80%) in high photon energy range (hν ≈ 3.1–3.5 eV) in comparison with Si:H reference structure. An adjustment in the absorbing layer thickness and in the contact material for ITO/PEDOT:PSS/(i)Si:H/(n)Si:H structure, resulted in a remarkably high short circuit current density (as large as 17.74 mA/cm²), an open circuit voltage of 640 mV and an efficiency of 3.75%.     

Improvement of electrical conductivity of PEDOT:PSS films by 2-Methylimidazole post treatment

The electrical conductivity of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films was significantly improved without losing the optical transparency by treating the films with solution of 2-Methylimidazole in ethanol. The maximum electrical conductivity of such a thin film reached 930 S cm⁻¹, more than 1150 order of magnitude higher than that of pure PEDOT:PSS film. The mechanism of conductivity enhancement of treated thin PEDOT:PSS films was explored by atomic force microscopy (AFM) and UV/VIS spectrophotometer. The AFM scans show that the surface of the 2-Methylimidazole treated PEDOT:PSS layer is smoother than that of the pristine PEDOT:PSS thin film. Improvement in the morphology, electrical and optical properties of PEDOT:PSS films makes them highly suitable for numerous applications in optoelectronic devices.     

Highly conductive PEDOT:PSS film by doping p-toluenesulfonic acid and post-treatment with dimethyl sulfoxide for ITO-free polymer dispersed liquid crystal device

In this paper, the highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film realized by applying the doping technique and the post-treatment process is demonstrated. The conductivity of the spin coated PEDOT:PSS film enhanced greatly from 0.7 S/cm to 736 S/cm after 1.25% of p-toluenesulfonic acid solution (50 wt%) was doped into the PEDOT:PSS aqueous dispersion. The post-treatment using dimethyl sulfoxide further improved the conductivity to 1549 S/cm. The highly conductive PEDOT:PSS film was used as transparent electrode to fabricate ITO-free polymer dispersed liquid crystal (PDLC) cell. The experimental results showed that the electro-optical properties of the PDLC cell fabricated by the highly conductive PEDOT:PSS film were comparable to those of the PDLC cell constructed by ITO. This study reveals that the highly conductive PEDOT:PSS film is a prospective material for manufacturing ITO-free liquid crystal devices.     

Enhanced flexibility and stability of PEDOT:PSS electrodes through interfacial crosslinking for flexible organic light-emitting diodes

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films have drawn extensive attention as one of the most promising flexible transparent conductive electrodes to replace traditional indium tin oxide. However, some critical issues, such as weak adhesion, vulnerability to moisture and detrimental acidic property, need to be addressed before the practical application and industrialization. Here, we propose a facile and effective strategy of interfacial crosslinking to further improve the flexibility and stability of PEDOT:PSS electrodes with high transparency and conductivity by introducing polyethyleneimine ethoxylated (PEIE) on the surface. The flexibility and stability of PEDOT:PSS electrodes with PEIE overcoating layer are significantly improved, which can be attributed to the interfacial crosslinking reaction between PEIE and PSS. Finally, flexible organic light-emitting didoes (OLEDs) are constructed based on the PEDOT:PSS electrodes modified by PEIE, and current efficiency is enhanced from 20.5 to 76.4 cd/A with a 2.7-fold enhancement, owning to the improved carrier balance. This study confirms that PEIE is effective in protecting the PEDOT:PSS films from mechanical damage and moisture attack, while maintaining the high conductive and transmittance, and illustrates a promising future in low-cost flexible optoelectronic devices employing PEDOT:PSS electrodes.     

Scaling Effects on the Electrochemical Stimulation Performance of Au,Pt, and PEDOT:PSS Electrocorticography Arrays

The efficacy of electrical brain stimulation in combatting neurodegenerative diseases and initiating function is expected to be significantly enhanced with the development of smaller scale microstimulation electrodes and refined stimulation protocols. These benefits cannot be realized without a thorough understanding of scaling effects on electrochemical charge injection characteristics. This study fabricates and characterizes the electrochemical stimulation capabilities of Au, Pt, poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS/Au), and PEDOT:PSS/Pt electrode arrays in the 20–2000 µm diameter range. This study observes substantial enhancement in charge injection capacity up to 9.5× for PEDOT:PSS microelectrodes compared to metal ones, and 88% lower required power for injecting the same charge density. These significant benefits are strongest for electrode diameters below 200 µm. Detailed quantitative analyses are provided, enabling optimization of charge injection capacity with potential bias and symmetric and asymmetric pulse width engineering for all diameters. These systematic analyses inform the optimal design for acute and potentially chronic implants in regards to safety and clinically effective stimulation protocols, ensure the longevity of the electrodes below critical electrochemical limits of stimulation, and demonstrate that the material choice and pulse design can lead to more energy efficiency stimulation protocols that are of critical importance for fully implanted devices.     

Interplay Between Doping,Morphology, and Lattice Thermal Conductivity in PEDOT:PSS

Organic materials for thermoelectric (TE) applications have attracted a fair amount of attention in recent years due to remarkable advances achieved in terms of their figure of merit, ZT: a value of 0.42 has been reported by for poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) films treated with dimethyl sulfoxide, while 0.25 has been obtained for PEDOT:Tosylate. In this study various PEDOT morphologies are investigated, considering both neutral and doped (bipolaronic) samples, by means of classical molecular dynamics, by taking advantage of a recently developed all-atom force field. In the case of bare PEDOT, it is found that changing the distribution of chain lengths affects the thermal conductivity of neutral and doped samples in a different way: longer chain lengths result in higher conductivities in the neutral scenario, whereas an intermediate chain length gives the highest value in the bipolaronic case. The role of PSS in the bipolaronic state, as compared to the simpler case where the counterion is Cl⁻, is discussed.     

A highly conductive PEDOT:PSS film with the dipping treatment by hydroiodic acid as anode for organic light emitting diode

A highly conductive, transparent and uniform poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) film has been developed by dipping treatment with hydriodic acid (HI) solution. The HI-treated PEDOT:PSS film can reach a sheet resistance of 68 Ω per square and a transmittance of 87% at 550 nm. The conductivity enhancement for the HI-treated film is ascribed to the permeation of proton and iodine anion of HI into PEDOT:PSS film, resulting in the separation of PSS and PEDOT chains. The phase separation of PSS and PEDOT can provide more conductive pathways for carriers to improve conductivity of the film. Using the optimized HI-treated PEDOT:PSS film as anode, we have fabricated indium tin oxide (ITO)-free organic light emitting diode (OLED), which shows better performance than the device with ITO as anode. This proves that such PEDOT:PSS film with the dipping treatment by HI solution is a promising alternative to ITO for low cost, transparent and flexible OLED application.     

The effect of solvent treatment on the buried PEDOT:PSS layer

Solvent treatment has been widely used to improve the device performance of both Organic Light Emitting Diodes (OLEDs) and Polymer Solar Cells (PSCs). One of the proposed mechanisms is the modification of the buried PEDOT:PSS layer underneath the organic active layer by the permeating solvent. By measuring the lateral electric conductivity of the PEDOT:PSS layer, the 3 orders of magnitude's enhancement on the conductivity after solvent treatment confirms that the solvent permeates through the top organic active layer and modifies the PEDOT:PSS layer. Using a “peel-off” method, the buried PEDOT:PSS layer is fully exposed and studied by UV–vis spectra, XPS spectra, and c-AFM images. The data suggest that the permeating solvent dissolves PSS, changes PEDOT:PSS′ core-shell structure into a linear/coiled structure, and moves PSS from the bulk to the surface. As a result, PEDOT becomes more continuous in the bulk. The continuous conducting PEDOT-rich domains create percolating pathways for the current which significantly improve electric conductivity.     

Supported Lipid Bilayer Assembly on PEDOT:PSS Films and Transistors

Lipid bilayers are widely employed as a model system to investigate interactions between cells and their environment. Supported lipid bilayers (SLB) with integrated transmembrane proteins are emerging as a preferred platform for sensing applications. Challenges lie in the generation of SLB on surfaces which allow transduction of signals for characterization of lipid bilayer and incorporated transmembrane proteins. For the first time, the formation of SLBs is shown on films of the conducting polymer, poly(3,4‐ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS), using traditional methods for characterizing lipid bilayer quality and function (QCM‐D, FRAP) combined with impedance spectroscopy. Further, partial formation of SLBs on PEDOT:PSS based organic electrochemical transistors (OECTs) is successfully demonstrated, as well as the ability to integrate and sense the ion pore α‐hemolysin, confirming the sensitivity of the OECT as a transducer of biological membrane function. This work represents a highly promising first step toward the use of such OECTs for functional readout of transmembrane proteins in their native environment.     

Design of highly stable and solution-processable electrochromic devices based on PEDOT:PSS

This study aimed to improve the repeatability of electrochromic devices(ECD) based on Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS); therefore, ferrocene was introduced as an anodic species. When 0.05 wt% ferrocene as compared to that of the electrolyte was contained in the electrolyte layer, the bleaching time significantly reduced from 110 s to 25 s without changing ΔT; consequently, repeatability markedly improved. However, ferrocenium cations, generated when ferrocene undergoes a reversible redox reaction, have high reactivity with oxygen, and hence, the stability of ECD is lowered over time. To overcome this problem, l-ascorbic acid, commonly known as vitamin C, was introduced as an antioxidant in the electrolyte layer. The repeatability of the ECD and the storage stability of the electrolyte solution were improved without side effects at an l-ascorbic acid ratio of 0.025 wt% as compared to that of the electrolyte. In addition, using cyclic voltammetry, it was confirmed that l-ascorbic acid did not affect the electrochemical properties of the ECD, and played only the role of an antioxidant for ferrocene. Furthermore, regarding encapsulated ECD, high repeatability could be maintained by preventing solvent evaporation and oxygen penetration into the electrolyte layer. When ECD of size 4 cm × 5 cm was glass encapsulated, there was no change in ΔT even after 5000 cycles for 139 h. We observed day-to-day changes in the response time and ΔT for 30 d; it maintained almost constant values from the beginning. Repeatability tests of 15 cm × 15 cm size large-area ECD for applications, such as smart windows, were conducted.     

A highly conductive and smooth AgNW/PEDOT:PSS film treated by hot-pressing as electrode for organic light emitting diode

A highly conductive, smooth and transparent electrode is developed by coating poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) over silver nanowires (AgNWs) followed by a hot-pressing method. The hot-pressed AgNW/PEDOT:PSS film shows a low sheet resistance of 12 Ω/square, a transmittance of 83% at 550 nm and a smooth surface. The improvement of the conductivity and smoothness are ascribed to the fusion of nanowires resulted from the mechanical hot-pressing. The AgNW/PEDOT:PSS film on polyethylene naphthalate (PEN) substrate exhibits higher conductive stability against the bending test than commonly used indium tin oxide (ITO). Using the hot-pressed AgNW/PEDOT:PSS film as the anode, we have fabricated ITO-free organic light emitting diode with a maximum current efficiency of 58.2 cd/A, which is higher than the device with ITO anode. This proves that such AgNW/PEDOT:PSS film treated by hot-pressing is a promising candidate for flexible optoelectronic devices.