Control of doctor‐blade coated poly (3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) electrodes shape on prepatterned substrates via microflow control in a drying droplet

We demonstrated a simple patterning method for the deposition of polymer electrodes such as poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS). We made use of the difference in wettability between hydrophobic surfaces and hydrophilic surfaces to make the patterns. However, the patterns made with our patterning method created undesirable ring‐like stains, which were caused by the outward flow of the solute within the PEDOT/PSS solution drop. To achieve homogenous device performance, we proposed a simple process for removing this ring‐like stain by making the surface tension gradient with dual solvent system in the PEDOT/PSS solution drop. Because this surface tension gradient causes the inward flow of the solute within the PEDOT/PSS solution drop, the ring‐like stain is removed. Finally, we confirmed the potential of our patterning method for polymer electrodes such as the PEDOT/PSS by fabricating pentacene thin‐film transistors (TFTs) and measuring the electrical properties of the pentacene TFTs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1590–1596, 2011     

Preparation and Characterization of Carbon Nano‐Onion/PEDOT:PSS Composites

Composites of unmodified or oxidized carbon nano‐onions (CNOs/ox‐CNOs) with poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) are prepared with different compositions. By varying the ratio of PEDOT:PSS relative to CNOs, CNO/PEDOT:PSS composites with various PEDOT:PSS loadings are obtained and the corresponding film properties are studied as a function of the polymer. X‐ray photoelectron spectroscopy characterization is performed for pristine and ox‐CNO samples. The composites are characterized by scanning and transmission electron microscopy and differential scanning calorimetry studies. The electrochemical properties of the nanocomposites are determined and compared. Doping the composites with carbon nanostructures significantly increases their mechanical and electrochemical stabilities. A comparison of the results shows that CNOs dispersed in the polymer matrices increase the capacitance of the CNO/PEDOT:PSS and ox‐CNO/PEDOT:PSS composites.     

氧化石墨烯掺杂PEDOT:PSS作为空穴注入层对有机发光二极管发光性能的影响

研究了氧化石墨烯(GO)掺杂聚(3,4-亚乙二氧基噻吩):聚(苯乙烯磺酸) (PEDOT:PSS)作为空穴注入层对有机发光二极管发光性能的影响. 在PEDOT:PSS水溶液中掺入GO, 经过湿法旋涂和退火成膜后, 不仅提高了空穴注入层的空穴注入能力和导电率, 透光率也得到了相应的提高, 从而使得有机发光二极管(OLED)器件的发光性能得到了提升. 通过优化GO掺杂量发现, 当GO掺杂量为0.8%(质量分数)时, 空穴注入层的透光率达到最大值(96.8%), 此时获得的OLED器件性能最佳, 其最大发光亮度和最大发光效率分别达到17939 cd·m^-2和3.74 cd·A^-1. 与PEDOT:PSS 作为空穴注入层的器件相比, 掺杂GO后器件的最大发光亮度和最大发光效率分别提高了46.6%和67.6%.     

Conductivity enhancement of PEDOT:PSS film via sulfonic acid modification: application as transparent electrode for ITO-free polymer solar cells

3-Hydroxy-1-propanesulfonic acid(HPSA)was applied as a modification layer on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)film via spin-coating,resulting in a massive boost of the conductivity of PEDOT:PSS film,and thus the as-formed PEDOT:PSS/HPSA bilayer film was successfully used as a transparent electrode for ITO-free polymer solar cells(PSCs).Under the optimized concentration of HPSA(0.2 mol L~(-1)),the PEDOT:PSS/HPSA bilayer film has a conductivity of 1020 S cm~(-1),which is improved by about 1400 times of the pristine PEDOT:PSS film(0.7 S cm~(-1)).The sheet resistance of the PEDOT:PSS/HPSA bilayer film was 98Ωsq~(-1),and its transparency in the visible range was over 80%.Both parameters are comparable to those of ITO,enabling its suitability as the transparent electrode.According to atomic force microscopy(AFM),UV-Vis and Raman spectroscopic measurements,the conductivity enhancement was resulted from the removal of PSS moiety by methanol solvent and HPSA-induced segregation of insulating PSS chains along with the conformation transition of the conductive PEDOT chains within PEDOT:PSS.Upon applying PEDOT:PSS/HPSA bilayer film as the transparent electrode substituting ITO,the ITO-free polymer solar cells(PSCs)based on poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)]:[6,6]-phenyl C71-butyric acid methyl ester(PC_(71)BM)(PCDTBT:PC_(71)BM)active layer exhibited a power conversion efficiency(PCE)of 5.52%,which is comparable to that of the traditional ITO-based devices.     

Fast Visible-Light 3D Printing of Conductive PEDOT:PSS Hydrogels

Functional inks for light-based 3D printing are actively being searched for being able to exploit all the potentialities of additive manufacturing. Herein, a fast visible-light photopolymerization process is showed of conductive PEDOT:PSS hydrogels. For this purpose, a new Type II photoinitiator system (PIS) based on riboflavin (Rf), triethanolamine (TEA), and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is investigated for the visible light photopolymerization of acrylic monomers. PEDOT:PSS has a dual role by accelerating the photoinitiation process and providing conductivity to the obtained hydrogels. Using this PIS, full monomer conversion is achieved in less than 2 min using visible light. First, the PIS mechanism is studied, proposing that electron transfer between the triplet excited state of the dye (³Rf*) and the amine (TEA) is catalyzed by PEDOT:PSS. Second, a series of poly(2-hydroxyethyl acrylate)/PEDOT:PSS hydrogels with different compositions are obtained by photopolymerization. The presence of PEDOT:PSS negatively influences the swelling properties of hydrogels, but significantly increases its mechanical modulus and electrical properties. The new PIS is also tested for 3D printing in a commercially available Digital Light Processing (DLP) 3D printer (405 nm wavelength), obtaining high resolution and 500 µm hole size conductive scaffolds.     

Flexible ITO-free organic solar cells over 10% by employing drop-coated conductive PEDOT:PSS transparent anodes

Highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonic acid)(PEDOT:PSS) has been explored to fabricate flexible and stretchable conductors. Generally, PEDOT:PSS transparent anodes are prepared by spin-coating method. In this article, we adopt a method by dropping PEDOT:PSS aqueous solution on the PET plastic substrate to fabricate flexible electrodes. Compared with spin coating, drop-coating is simple and cost-effective with large-area fabrications. Through this method, we fabricated highly transparent conductive electrodes and systematically studied their electrical, optical, morphological and mechanical properties. With dimethyl sulfoxide/methanesulfonic acid(DMSO/MSA) treated PEDOT:PSS electrode,bendable devices based on non-fullerene system displayed an open-circuit voltage of 0.925 V, a fill factor of 70.74%, and a high power conversion efficiency(PCE) of 10.23% under 100 mW cm~(-2) illumination, which retained over 80% of the initial PCE value after 1000 bending cycles. Based on the findings, drop-coated PEDOT:PSS electrodes exhibited high suitability for the development of large-area and high-efficiency printed solar cell modules in the future.     

Thermoelectric properties of nanocomposite thin films prepared with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) and graphene

Carbon nanotubes (CNTs), either single wall carbon nanotubes (SWNTs) or multiwall carbon nanotubes (MWNTs), can improve the thermoelectric properties of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT?:?PSS), but it requires addition of 30-40 wt% CNTs. We report that the figure of merit (ZT) value of PEDOT?:?PSS thin film for thermoelectric property is increased about 10 times by incorporating 2 wt% of graphene. PEDOT?:?PSS thin films containing 1, 2, 3 wt% graphene are prepared by solution spin coating method. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses identified the strong π-π interactions which facilitated the dispersion between graphene and PEDOT?:?PSS. The uniformly distributed graphene increased the interfacial area by 2-10 times as compared with CNT based on the same weight. The power factor and ZT value of PEDOT?:?PSS thin film containing 2 wt% graphene was 11.09 μW mK(-2) and 2.1 × 10(-2), respectively. This enhancement arises from the facilitated carrier transfer between PEDOT?:?PSS and graphene as well as the high electron mobility of graphene (200,000 cm(2) V(-1) s(-1)). Furthermore the porous structure of the thin film decreases the thermal conductivity resulting in a high ZT value, which is higher by 20% than that for a PEDOT?:?PSS thin film containing 35 wt% SWNTs.     

Role of humidity on indium and tin migration in organic photovoltaic devices

The stability of a common interface used in organic photovoltaic cells, between the transparent electrode of Indium Tin Oxide (ITO) and a buffer layer of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) is strongly influenced by the presence of humidity during processing, leading to significant migration of indium and tin species into the PEDOT:PSS layer. The interface was studied using neutral impact collision ion scattering spectroscopy (NICISS) and X-ray photoelectron spectroscopy (XPS), to determine migration of indium and tin into the polymer layer. It was found that the migration starts almost instantly after spin coating of the aqueous PEDOT:PSS solution and it reaches a saturation level within twenty four hours. The indium and tin were found always uniformly distributed over the sampling depth of almost one-third of the thickness of the PEDOT:PSS layer. Exposure to humidity following annealing resulted in the highest concentration (1.8 × 10(-3) mol cm(-3)) of indium or tin species, corresponding to about one indium or tin moiety per 4.7 monomer units in the PEDOT:PSS. The maximum bulk concentration of indium is about two orders of magnitude higher after exposure to humid conditions compared to vacuum dried conditions. XPS measurements confirm the presence of both indium and tin in the PEDOT:PSS and the formation of salts with the metal ions as cations.     

Influence of a water rinse on the structure and properties of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) films

Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) films exhibit a complex structure of interconnected conductive PEDOT domains in an insulating PSS matrix that controls their electrical properties. This structure is modified by a water rinse, which removes PSS with negligible PEDOT loss. Upon PSS removal, film thickness is reduced by 35%, conductivity is increased by 50%, and a prominent dielectric relaxation is eliminated. These results suggest that the removed PSS is not associated with PEDOT and that the conductive domain network is not substantially altered by the removal of a significant fraction of insulator. The removal of PSS may benefit organic light emitting diode fabrication by reducing acid attack on indium tin oxide electrodes and lead to more robust performance in switching circuits by extending the working frequency range.     

Investigation of the doping efficiency of poly(styrene sulfonic acid) in poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) dispersions by capillary electrophoresis

CE can efficiently separate poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS) complexes and free PSS in dispersions and can be used to estimate the degree of PSS doping. We investigated the doping efficiency of PSS on PEDOT in dispersions using CE and its effect on the conductivity of the resulting PEDOT/PSS films. Results of this study indicate that dispersions containing 1:2.5–3 EDOT:PSS feed ratio (by weight) exhibiting 72–73% PSS doping generate highly processable and highly conductive films. Conductivity can be optimized by limiting the time of reaction to 12 h. At this point of the reaction, the PEDOT/PSS segments, appearing as broad band in the electropherogram, could still exist in an extended coil conformation favoring charge transport resulting in high conductivity. Above a threshold PEDOT length formed at reaction times longer than 12 h, the PEDOT/PSS complex, appearing as spikes in the electropherogram, most likely have undergone a conformational change to coiled core‐shell structure restricting charge transport resulting in low conductivity. The optimal conductivity (5.2 S/cm) of films from dispersions synthesized for 12 h is significantly higher than those from its commercial equivalent Clevios P and other reported values obtained under similar conditions without the addition of codopants.     

Water soluble amino grafted silicon nanoparticles and their use in polymer solar cells

Stable aqueous amino-grafted silicon nanoparticles(SiNPs-NH2) were prepared via one-pot solution method. By grafting amino groups on the particle surface, the dispersion of SiNPs in water became very stable and clear aqueous solutions could be obtained. By incorporating SiNPs-NH2 into the hole transport layer of poly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid(PEDOT:PSS), the performance of polymer solar cells composed of poly[2-methoxy,5-(2'-ethylhexyloxy)-1,4-phenylene vinylene](MEH-PPV):[6,6]-phenyl-C61-butyric acid methyl ester(PCBM) as active layer can be improved. SiNPs-NH2 are dispersed uniformly in the PEDOT:PSS solution and help form morphologies with small-sized domains in the PEDOT:PSS film. SiNPs-NH2 serve as screens between conducting polymer PEDOT and ionomer PSS to improve the phase separation and charge transport of the hole transport layer. As a result, the sheet resistance of PEDOT:PSS thin films is decreased from(93 ± 5) × 105 to(13 ± 3) × 105 ?/□. The power conversion efficiency(PCE) of polymer solar cells was thus improved by 9.8% for devices fabricated with PEDOT:PSS containing 1 wt% of SiNPs-NH2, compared with the devices fabricated by original PEDOT:PSS.     

Effect of (3‐glycidyloxypropyl)trimethoxysilane (GOPS) on the electrical properties of PEDOT:PSS films

Poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) has been reported as a successful functional material in a broad variety of applications. One of the most important advantages of PEDOT:PSS is its water‐solubility, which enables simple and environmental friendly manufacturing processes. Unfortunately, this also implies that pristine PEDOT:PSS films are unsuitable for applications in aqueous environments. To reach stability in polar solvents, (3‐glycidyloxypropyl)trimethoxysilane (GOPS) is typically used to cross‐link PEDOT:PSS. Although this strategy is widely used, its mechanism and effect on PEDOT:PSS performance have not been articulated yet. Here, we present a broad study that provides a better understanding of the effect of GOPS on the electrical and electronic properties of PEDOT:PSS. We show that the GOPS reacts with the sulfonic acid group of the excess PSS, causing a change in the PEDOT:PSS film morphology, while the oxidation level of PEDOT remains unaffected. This is at the origin of the observed conductivity changes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 814–820     

Tuning of PEDOT:PSS Properties Through Covalent Surface Modification

Conductive polymer (poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS) is an attractive platform for the design of flexible electronic, optoelectronic, and (bio)sensor devices. Practical application of PEDOT:PSS often requires an incorporation of specific molecules or moieties for tailoring of its physical–chemical properties. In this article, a method for covalent modification of PEDOT:PSS using arenediazonium tosylates was proposed. The procedure includes two steps: chemisorption of diazo‐cations on the PEDOT:PSS surface followed by thermal decomposition of the diazonium salt and the covalent bond formation. Structural and surface properties of the samples were evaluated by XPS, SEM‐EDX, AFM, goniometry, and a range of electric and optical measurements. The developed modification procedure enables tuning of the PEDOT:PSS surface properties such as conductivity and optical absorption. The possibility to introduce various organic functional groups (from hydrophilic to hydrophobic) and to create new groups for further functionalization makes the developed procedure multipurpose. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 378–387     

Water uptake in the hydrophilic poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) solid-contact of all-solid-state polymeric ion-selective electrodes

Solid-contact (SC) ion-selective electrodes (ISEs) utilizing thin films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and plasticized poly(vinylchloride) (PVC) have been produced using a spin casting procedure. This study was carried out with a view of characterizing this popular and well known SC ISE using a series of complementary surface analysis techniques. This work revealed that PEDOT:PSS prevents the separation of an undesirable water layer at the buried interface of this SC ISE due to the high miscibility of water in the hydrophilic PEDOT:PSS layer. The lack of a clearly defined and molecularly sharp buried interface prohibits the formation of a distinct water layer presumably by eliminating sites that promote the accumulation of water. This outcome is important to the chemical sensor community since it provides further insights into the compatibility of sensor components in SC ISEs.     

Enhanced electrical properties of PEDOT:PSS via synergistic effect

As a representing conducting polymer, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has been widely employed in organic electronics. However, the electrical conductivity for pristine PEDOT:PSS is only between 0.1 and 0.5 S/cm. In order to enhance the conductivity, the silver nanowires (Ag NWs) were synthesized to dope PEDOT:PSS. It was found the electrical conductivity of PEDOT:PSS was improved to about 200 S/cm with Ag NWs. When double-wall carbon nanotube (DWCNT) was employed together with Ag NWs, the electrical conductivity was further improved to over 2800 S/cm. We proposed the synergistic working model between Ag NWs and CNTs for such enhancement. In this work, UV-vis-NIR spectra and SEM images were also employed to investigate the mechanism of electrical conductivity enhancement.     

Improving Efficiency of Organic Photovoltaic Cells Using PEDOT:PSS and MWCNT Nanocomposites as a Hole Conducting Layer

In this study, polymeric nanocomposites of poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) and functionalized multi-walled carbon nanotubes (MWCNTs) were spin coated on a pre-patterned ITO glass and used as a hole conducting layer in organic photovoltaic cells. The multi-layered ITO/MWCNT-PEDOT:PSS/CuPc/C60/Al devices were fabricated to investigate the current density-voltage characteristics and power conversion efficiency. The power conversion efficiency obtained from the device with a concentration of 1.0 wt% MWCNT in the PEDOT:PSS layer was increased twice as those adopted from device without MWCNT doping in the PEDOT:PSS layer and current density-voltage characteristics was also improved well with incorporation of MWCNTs.     

Why does the electrical conductivity in PEDOT:PSS decrease with PSS content? A study combining thermoelectric measurements with impedance spectroscopy

We have investigated the electrical transport properties of poly(3,4‐ethylenedioxythiophen)/poly(4‐styrene‐sulfonate) (PEDOT:PSS) with PEDOT‐to‐PSS ratios from 1:1 to 1:30. By combining impedance spectroscopy with thermoelectric measurements, we are able to independently determine the variation of electrical conductivity and charge carrier density with PSS content. We find the charge carrier density to be independent of the PSS content. Using a generalized effective media theory, we show that the electrical conductivity in PEDOT:PSS can be understood as percolation between sites of highly conducting PEDOT:PSS complexes with a conductivity of 2.3 (Ωcm)^?1 in a matrix of excess PSS with a low conductivity of 10^?3 (Ω cm)^?1. In addition to the transport properties, the thermoelectric power factors and Seebeck coefficients have been determined. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Enzymatic‐catalyzed polymerization of water‐soluble electrically conductive polymer PEDOT:PSS

Water‐soluble electrically conductive polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) was synthesized by the enzymatic‐catalyzed method using 3,4‐ethylenedioxythiophene (EDOT) as monomer, poly(styrenesulfonate) (PSS) as water‐soluble polyelectrolyte, horseradish peroxidase enzyme as catalyst, and hydrogen peroxide (H₂O₂) as oxidant. Fourier transform infrared spectra and UV–vis absorption spectra confirm the successful enzymatic‐catalyzed polymerization of PEDOT. Dynamic light scattering data confirm the formation of a stable PEDOT:PSS aqueous dispersion. The thermo gravimetric data show that the obtained PEDOT is stable over a fairly high range of temperatures. The atomic force microscopy height images show that the PEDOT:PSS aqueous dispersion can form excellent homogeneous and smooth films on various substrates by conventional solution processing techniques, which renders this PEDOT:PSS aqueous dispersion a very promising candidate for various application in electronic devices. This enzymatic polymerization is a new approach for the synthesis of optical and electrical active PEDOT polymer, which benefits simple setting, high yields, and environmental friendly route. Copyright © 2014 John Wiley & Sons, Ltd.     

Characterization of poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS) adsorption on cellulosic materials

The interaction between poly(3,4-ethylene dioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS) and cellulosic fibers was characterized in order to obtain further understanding of the conductivity properties of the modified cellulosic fiber material. Microcrystalline cellulose (MCC) was used as a model surface to study the adsorption behavior at various pH and salt concentrations, while samples of low-conductivity paper, normally used for the production of electrical insulation papers, were dipped into PEDOT:PSS dispersion and air-dried for X-ray photoelectron spectroscopy (XPS) studies. The results showed a strong interaction between the MCC and PEDOT:PSS, which implied a broad molecular distribution of the conducting polymer. With increasing pH, less amount of the conducting polymer was adsorbed whereas the amount adsorbed passed through a maximum value with varying salt concentration. Zeta potential measurement and polyelectrolyte titration were used to determine the surface charge of both suspended MCC particles and dispersed PEDOT:PSS at various pH levels and salt concentrations. Dip-coated paper samples exhibited two peaks in the S(2p) XPS spectra at 168–169 and 164–165 eV which correspond to the sulfur signals of sulfonate (in PSS) and in thiophene (in PEDOT), respectively. It was found that the PEDOT:PSS with a ratio of 1:2.5 was adsorbed more in the base paper than that with a ratio of 1:6. The PEDOT:PSS ratio on the surface of the cellulosic material was higher than that in the bulk liquid for all samples. The results indicated that PEDOT was preferentially adsorbed rather than PSS. The degree of washing of the conducting polymer did not significantly affect the PEDOT enhancement on the surface.     

Preparation of electrically conducting cellulose fibres utilizing polyelectrolyte multilayers of poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) and poly(allyl amine)

The primary goal with this work is to create electrically conductive cellulose fibres, this has been done to explore possible new applications for fibre based material. This research uses various methods to create polyelectrolyte multilayers (PEMs) on bleached softwood fibres and on SiO₂ model surfaces, by sequentially treating these materials with poly(3,4-ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS) and poly(allyl amine) (PAH). Paper sheets were then produced from the PEM-modified pulp and evaluated in terms of tensile strength, adsorbed amount of polymer, and electrical conductivity. To evaluate the influence of fibre charge on the measured paper properties, pulps of two different initial fibre charge densities were prepared via carboxymethylation. Because of the bluish colour of PEDOT:PSS, the build-up of PEM could be easily followed, since the fibres grew increasingly darker blue throughout the modification sequence. The conductivity of the fibre network increased by 2−3 orders of magnitude when the pulp of a higher fibre charge density was used. This suggests that it is more important to create a fibrous network with a high fibre-fibre joint strength and a large total joined area in the sheet rather than to maximize the adsorbed amount of PEDOT:PSS. A difference in conductivity could also be noted depending on the polyelectrolyte adsorbed in the outer layer, PAH lowered the conductivity compared to PEDOT:PSS. Evaluating the mechanical properties revealed that the use of PEDOT:PSS reduces the tensile strength of the paper. When five double layers had been adsorbed onto the carboxymethylated sample in which PEDOT:PSS formed the outer layer, calculations indicated a 25% decrease in tensile strength compared to that of reference material without PEMs. ESEM studies indicate that PEM treatment produces a significantly changed and somewhat smoother fibre surface.