The thermoelectric performance of carbon black/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) composite films

Carbon black/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (CB/PEDOT:PSS) composite films have been prepared by a spin-coating method. The morphology of the composite films was investigated by field emission scanning electron microscopy and atomic force microscopy. The thermoelectric properties of CB/PEDOT:PSS composite films were measured at room temperature. As the content of CB increased from 0 to 11.16 wt%, the electrical conductivity of the composite films first increased sharply and then decreased, while the Seebeck coefficient increased slowly. A highest power factor of 0.96 μWm^?1 K^?2 was obtained.     

Influence of ethylene glycol vapor annealing on structure and property of wet-spun PVA/PEDOT:PSS blend fiber

In this study, blend fibers composed of poly(vinyl alcohol) and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) were prepared via wet-spinning technology. Ethylene glycol (EG) vapor annealing was employed to improve the electrical conductivity and tensile properties of blend fibers. The effects of EG vapor annealing on structures and properties of blend fibers were investigated in detail by analyzing the changes in chemical constituent and structure, molecular structure, surface morphology, surface chemical composition, electrical conductivity, and tensile properties. FTIR spectroscopy indicates that EG vapor annealing does not change the chemical constituent and structure of blend fibers. Raman spectroscopy shows that vapor annealing leads to conformational changes of PEDOT chains from benzoid structure to quinoid structure. AFM and SEM images show that surface morphology of blend fibers become smoother after vapor annealing. XPS measurement shows that EG vapor annealing induces significant phase separation between PEDOT and PSS, forming an enriched PSS layer on the surface of blend fibers, thus leading to a thinner insulating PSS layer between PEDOT grains. This conformational change is beneficial to improve the electrical conductivity of blend fibers. The resultant blend fiber reached conductivity up to 20.4 S cm^?1. The mechanical properties of blend fibers were also improved by EG vapor annealing, with the Young’s modulus and tensile strength increasing from 3.6 GPa and 112 MPa to 4.4 GPa and 132.7 MPa, respectively.     

Efficiency enhancement of polymer solar cells with Ag nanoparticles incorporated into PEDOT:PSS layer

In this study, large-sized silver nanoparticles (Ag NPs) (average size: 80 nm) have been introduced into the anodic buffer poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer (thickness: about 55 nm) of poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester bulk heterojunction polymer solar cells. The results showed that the short-circuit current density can increase from 8.73 to 11.36 mA/cm², and power conversion efficiency increases from 2.28 to 2.65 % when 0.1 wt% Ag NPs was incorporated in PEDOT:PSS layer, corresponding to an efficiency improvement of 16.2 %. Absorption spectrums of the active layers indicate that large-sized Ag NPs have no clear contribution to optical absorption improvement. By measuring the conductivity of PEDOT:PSS films without and with Ag NPs and analyzing device structure of this polymer solar cell, it was founded that the improvements in power conversion efficiency was originated from higher conductivity of PEDOT:PSS layer incorporated with Ag NPs and the shorter routes for holes to travel to the anode.     

Significant vertical phase separation in solvent-vapor-annealed poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) composite films leading to better conductivity and work function for high-performance indium tin oxide-free optoelectronics

In the present study, a novel polar-solvent vapor annealing (PSVA) was used to induce a significant structural rearrangement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films in order to improve their electrical conductivity and work function. The effects of polar-solvent vapor annealing on PEDOT:PSS were systematically compared with those of a conventional solvent additive method (SAM) and investigated in detail by analyzing the changes in conductivity, morphology, top and bottom surface composition, conformational PEDOT chains, and work function. The results confirmed that PSVA induces significant phase separation between excess PSS and PEDOT chains and a spontaneous formation of a highly enriched PSS layer on the top surface of the PEDOT:PSS polymer blend, which in turn leads to better 3-dimensional connections between the conducting PEDOT chains and higher work function. The resultant PSVA-treated PEDOT:PSS anode films exhibited a significantly enhanced conductivity of up to 1057 S cm(-1) and a tunable high work function of up to 5.35 eV. The PSVA-treated PEDOT:PSS films were employed as transparent anodes in polymer light-emitting diodes (PLEDs) and polymer solar cells (PSCs). The cell performances of organic optoelectronic devices with the PSVA-treated PEDOT:PSS anodes were further improved due to the significant vertical phase separation and the self-organized PSS top surface in PSVA-treated PEDOT:PSS films, which can increase the anode conductivity and work function and allow the direct formation of a functional buffer layer between the active layer and the polymeric electrode. The results of the present study will allow better use and understanding of polymeric-blend materials and will further advance the realization of high-performance indium tin oxide (ITO)-free organic electronics.     

Improved thermoelectric performance of PEDOT:PSS films prepared by polar-solvent vapor annealing method

To improve thermoelectric performance, polar-solvent vapor annealing (PSVA) method was introduced into the preparation of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films. The solvent vapors included dimethyl sulfoxide, ethylene glycol, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and deionized water (H₂O). The PSVA-treated PEDOT:PSS films exhibited significantly enhanced electrical conductivity and the maximum value was up to 496 S cm^?1. Especially, utilizing the PSVA method, H₂O could also remarkably enhance the electrical conductivity of pristine PEDOT:PSS film from 0.2 to 57 S cm^?1. There was no distinct change for the Seebeck coefficient of PSVA-treated films with the significantly enhanced electrical conductivity, thereby a maximum power factor of 9.47 μW m^?1 K^?2 at room temperature was obtained. The effects of PSVA method on thermoelectric performance of PEDOT:PSS films were also investigated systematically by analyzing the changes in morphology, carrier mobility and carrier concentration. The results confirmed that PSVA-treated PEDOT:PSS films could obtain smoother morphologies and realize the simultaneous increase of carrier mobility and carrier concentration, which results in the improvement of the thermoelectric performance.     

Multiwall carbon nanotube and poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) composite films for transistor and inverter devices

Highly conductive multiwalled carbon nanotube (MWNT)/Poly(3,4-ethylenedioxythiophene) polymerized with poly(4-styrenesulfonate) (PEDOT:PSS) films were prepared by spin coating a mixture solution. The solution was prepared by dispersing MWNT in the PEDOT:PSS solution in water using ultrasonication without any oxidation process. The effect of the MWNT loading in the solution on the film properties such as surface roughness, work function, surface energy, optical transparency, and conductivity was studied. The conductivity of MWNT/PEDOT:PSS composite film was increased with higher MWNT loading and the high conductivity of MWNT/PEDOT:PSS films enabled them to be used as a source/drain electrode in organic thin film transistor (OTFT). The pentacene TFT with MWNT/PEDOT:PSS S/D electrode showed much higher performance with mobility about 0.2 cm2/(V s) and on/off ratio about 5 × 10? compared to that with PEDOT:PSS S/D electrode (～0.05 cm2/(V s), 1 × 10?). The complementary inverters exhibited excellent characteristics, including high gain value of about 30.     

Composite inks of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)/silver nanoparticles and electric/optical properties of inkjet-printed thin films

Poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)/silver nanoparticles composite inks have been prepared through in situ synthesis and ultrasonic dispersion. The developed inks were proved to be suitable for various inkjet printing trials to deposit the thin films which were subsequently characterized to assess their electric and optical properties. The results have indicated that the dedoping of PSS from PEDOT during the in situ synthesis can be detrimental to the conductivity of the deposited composite films. However, the addition of silver nanoparticles to pristine PEDOT:PSS has significantly enhanced the conductivity of the thin films, with an inevitable loss in transparency. The various factors that can influence the properties of the thin films have also been analyzed and discussed. This study provides an insight into the effect of silver nanoparticles on PEDOT:PSS thin films deposited using inkjet printing process, and their properties due to the methods of ink formulation.     

Polymeric anodes from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) for 3.5% efficient organic solar cells

We present highly efficient indium tin oxide free polymer solar cells based on poly-(3-hexylthiophene-2,5-diyl) and C₆₁-bis-butric-acid-methyl-ester (P3HT:bisPCBM) comprising a polymeric anode from highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) formulations. The film conductivity was optimized by various additives. We found conductivities of almost 600 S/cm upon the addition of dimethylsulfoxide. The wetting properties of different PEDOT:PSS formulations were investigated by contact angle measurements. The optimized high conductivity in combination with the good film forming properties allow for the fabrication of highly efficient organic solar cells with an external power conversion efficiency of 3.5% with PEDOT:PSS as polymeric anode.     

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.     

Properties of one-step synthesized Pt nanoparticle-doped poly(3,4-ethylenedioxy thiophen):poly(styrenesulfonate) hybrid films

Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) thin films incorporating Pt nanoparticles were synthesized by a simple method using H₂PtCl₆? xH₂O. The surface morphology, chain structure, bonding states, and electronic structure of the films were investigated. Unusual formation of a PEDOT-rich surface was accompanied with interactions between PEDOT:PSS and Pt nanoparticles due to agglomeration of PEDOT:PSS around Pt nanoparticles and destabilization of chain conformation. High doping of the PEDOT moiety occurred during the reduction of H₂PtCl₆·xH₂O so that an increased work function and a decreased energy gap between the edge of the highest occupied molecular orbital and the Fermi level were observed. Intermediate products including chlorine and [PtCl₆]⁻, and the ionic nature of the Pt nanoparticles were responsible for the resultant properties of Pt-PEDOT:PSS. Products generated during the formation of Pt nanoparticles served as a third anionic dopant like PSS and as an inhibitor of segregation.     

Parameter extraction applied to the de-doping of PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styenesulphonate)) thermoelectrics

A recent report suggested that de-doping (reducing the volume of the dopants) could improve the figure-of-merit of PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styenesulphonate)) thermoelectrics through a simultaneous decrease in the thermal conductivity and an increase in the electrical conductivity. While this had been shown to increase the values of ZT, better understanding on the physics would be desirable. This work analyzed the transport data reported by Kim et al. (Nat Mater 12:719–723, 2013) on PEDOT:PSS and evaluated the changes in the materials parameters during de-doping. Our results showed that moderate de-doping had the effect of increasing the carrier mobility while at the same time it decreased somewhat the carrier density. Matching the mobilities computed from the thermal and electrical conductivity data and from theory allowed us to evaluate the width of the density of states σ, the values of the site spacing a′ and the localization length L for a known value of the escape frequency ν_ph. As observed, both L and a′ increased moderately with de-doping while their ratio L/a′ also increased from 0.44 to 0.55 over the ethylene glycol treatment range (up to 200 min). This suggested that de-doping not only reduced the PSS volume and the film thickness but also brought about improvement in the charge transport. The computed value of σ was amazingly small (only ~3.8 meV) contributing to the better thermoelectric performance.     

Thermoelectric properties of graphite-PEDOT:PSS coated flexible polyester fabrics

Flexible thermoelectric (TE) fabrics were prepared by dip coating of a mixture solution of water base colloidal graphite and dimethyl sulfoxide doped poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) on polyester fabric. The phase composition and morphology of the TE fabrics were investigated by X-ray diffraction and field emission scanning electron microscopy. The TE properties of the graphite-PEDOT:PSS coated fabrics with different graphite loadings were measured in the temperature range from 298 to 398 K. As the content of graphite increased from 5 to 20 wt%, the electrical conductivity of the graphite-PEDOT:PSS coated polyester fabrics decreased, while the Seebeck coefficient increased in the measured temperature range from 298 to 398 K. A maximum power factor of ~0.025 μWm^?1K^?2 at 398 K was obtained for the graphite-PEDOT:PSS coated fabric with 15 wt% graphite loading.     

Fabrication of efficient polymer light-emitting diodes using water/alcohol soluble poly(vinyl alcohol) doped with alkali metal salts as electron-injection layer

An effective electron-injection layer (EIL) is crucial to efficient polymer light-emitting diodes (PLEDs) with high work-function metal as cathode. This work presents the use of water/alcohol soluble poly(vinyl alcohol) (PVA), especially doped with alkali metal salts, as a highly effective EIL to fabricate efficient multilayer PLEDs, allowing the use of stable aluminum as the cathode. Using neat PVA as EIL, the maximum brightness and maximum current efficiency of the device [ITO/PEDOT:PSS/SY/PVA/Al(90 nm)] were significantly enhanced to 5518 cd/m² and 2.64 cd/A (from 395 cd/m² and 0.06 cd/A without the EIL) due to promoted electron-injection and hole-blocking. The device performance is further enhanced by doping the PVA with alkali metal salts (M₂CO₃ or CH₃COOM; M: Na, K, Cs), and the enhancement is increased with increasing dopant concentration. Particularly, the PVA doped with 30 wt% alkali metal carbonates revealed the best performance (20214–25163 cd/m², 5.83–6.83 cd/A). This has been attributed to improved electron-injection from aluminum cathode, which has been confirmed by the corresponding increase in the open-circuit voltages (V _oc) obtained from photovoltaic measurements. Current results indicate that commercially available PVA are promising electron-injection layer for PLEDs when doped with appropriate alkali metal salts.     

Surface modification of poly(3,4-ethylene dioxthiophene):poly(styrene sulfonic acid) (PEDOT:PSS) films by atmospheric-pressure argon plasma for organic thin-film solar cells

Highly-conductive poly(3,4-ethylene dioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) films obtained by the addition of dimethylsulfoxide (DMSO) and the argon plasma exposure were used as a transparent conductive anode (TCA) for copper-phthalocyanine (CuPc)/C60 organic thin-film solar cells (OSCs). The CuPc/C60 OSCs on as-grown DMSO added PEDOT:PSS layer showed a power efficiency of 0.6%, whereas it was improved markedly to 1.34% after the atmospheric-pressure argon plasma exposure, which was comparable to that formed on indium-tin-oxide layer. Effects of the DMSO addition and the argon plasma exposure in the spin-coated PEDOT:PSS films is demonstrated in terms of the in-depth characterization of optical and electrical properties.     

Efficient TCO-free organic solar cells with modified poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) anodes

Organic photovoltaic cells (OPVs) with a highly conductive poly 3,4-ethylenedioxythiophene:poly styrenesulfonate (PEDOT:PSS) layer as an anode and that were modified with the addition of some organic solvents such as sorbitol (So), dimethyl sulfoxide (DMSO), N-methyl-pyrrolidone (NMP), dimethylformamide (DMF), and ethylene glycol (EG) were fabricated without the use of transparent conducting oxide (TCO). The conductivity of the PEDOT:PSS film that was modified with each additive was enhanced by three orders of magnitude. According to the atomic force microscopy (AFM) study, the conductivity enhancement might have been related to the better connections between the conducting PEDOT chains. The TCO-free solar cells with a modified PEDOT:PSS layer and an active layer composed of poly (3-hexylthiophene) (P3HT) and phenyl [6, 6] C61 butyric acid methyl ester (PCBM) performed as well as the indium-tin-oxide (ITO)-based organic solar cells. The power conversion efficiency (PCE) of the organic solar cells with a DMSO-, So + DMSO-, and EG-modified PEDOT:PSS layer reached 3.51, 3.64, and 3.77%, respectively, under an illumination of AM 1.5 (100 mW/cm2).     

An Efficiently Doped PEDOT:PSS Ink Formulation via Metastable Liquid−Liquid Contact for Capillary Flow-Driven,Hierarchically and Highly Conductive Films

With commercial electronics transitioning toward flexible devices, there is a growing demand for high-performance polymers such as poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS). Previous breakthroughs in promoting the conductivity of PEDOT:PSS, which mainly stem from solvent-treatment and transfer-printing strategies, remain as inevitable challenges due to the inefficient, unstable, and biologically incompatible process. Herein, a scalable fabrication of conducting PEDOT:PSS inks is reported via a metastable liquid−liquid contact (MLLC) method, realizing phase separation and removal of excess PSS simultaneously. MLLC-doped inks are further used to prepare ring-like films through a compromise between the coffee-ring effect and the Marangoni vortex during evaporation of droplets. The specific control over deposition conditions allows for tunable ring-like morphologies and preferentially interconnected networks of PEDOT:PSS nanofibrils, resulting in a high electrical conductivity of 6,616 S cm⁻¹ and excellent optical transparency of the film. The combination of excellent electrical properties and the special morphology enables it to serve as electrodes for touch sensors with gradient pressure sensitivity. These findings not only provide new insight into developing a simple and efficient doping method for commercial PEDOT:PSS ink, but also offer a promising self-assembled deposition pattern of organic semiconductor films, expanding the applications in flexible electronics, bioelectronics as well as photovoltaic devices.     

On the mechanism of conductivity enhancement in plasma treated poly(3,4-ethylenedioxythiophene) films

The conductive poly(3,4-ethylenedioxythiophene): p-toluene sulfonate (PEDOT : PTS) films were prepared by gas-phase polymerization using CVD technique. PEDOT : PTS films with better electrical performance were produced by the additional doping with O₂ plasma after vapor phase polymerization. The mechanism for this conductivity enhancement is studied through surface structural analyses using Raman and X-ray photoelectron spectroscopy (XPS). The increase in conductivity is likely to be due to the generation of new functional groups such as carboxyl and hydroxyl groups that are acted as a dopant and the removal of the impurities on PEDOT: PTS surface with plasma treatment.     

PEDOT:PSS as back contact for CdTe solar cells and the effect of PEDOT:PSS conductivity on device performance

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) was studied as the back contact of Cadmium telluride (CdTe) solar cells and was compared with conventional Cu-based back contact. A series of PEDOT:PSS aqueous solutions with different conductivities were spin coated onto the glass/SnO2:F/SnO2/CdS/CdTe structures as back contact, and the PEDOT:PSS conductivity dependence of device performance was studied. It was found that PEDOT:PSS back contact with higher conductivity produces devices with lower series resistance and higher shunt resistance, leading to higher fill factor and higher device efficiencies. As the conductivity of PEDOT:PSS increased from 0.03 to 0.24 S/cm, the efficiency of the solar cell increased from 2.7 to 5.1 %. Methanol cleaning also played an important role in increasing the device performance. The efficiency of our best device with PEDOT:PSS back contact has reached 9.1 %, approaching those with conventional Cu/Au back contact (12.5 %).     

溴掺杂对PEDOT/PSS薄膜性能的影响及机理研究

为改善聚乙撑二氧噻吩∶聚（对苯乙烯磺酸）根阴离子（PEDOT/PSS）薄膜的光学及电学性能,采用共混-旋涂法在石英玻片上制备出溴掺杂的PEDOT/PSS透明导电膜,并就其掺杂导电机理进行了探讨.结果表明：经微量溴掺杂后的PEDOT/PSS薄膜,其透光性能与导电性能均得到提高;质量分数6%溴掺杂条件下,薄膜透光率为95....     

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.