Highly Conductive and Transparent PEDOT:PSS Films with a Fluorosurfactant for Stretchable and Flexible Transparent Electrodes

Highly conductive and transparent poly‐(3,4‐ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) films, incorporating a fluorosurfactant as an additive, have been prepared for stretchable and transparent electrodes. The fluorosurfactant‐treated PEDOT:PSS films show a 35% improvement in sheet resistance (R_s) compared to untreated films. In addition, the fluorosurfactant renders PEDOT:PSS solutions amenable for deposition on hydrophobic surfaces, including pre‐deposited, annealed films of PEDOT:PSS (enabling the deposition of thick, highly conductive, multilayer films) and stretchable poly(dimethylsiloxane) (PDMS) substrates (enabling stretchable electronics). Four‐layer PEDOT:PSS films have an R_s of 46 Ω per square with 82% transmittance (at 550 nm). These films, deposited on a pre‐strained PDMS substrate and buckled, are shown to be reversibly stretchable, with no change to R_s, during the course of over 5000 cycles of 0 to 10% strain. Using the multilayer PEDOT:PSS films as anodes, indium tin oxide (ITO)‐free organic photovoltaics are prepared and shown to have power conversion efficiencies comparable to that of devices with ITO as the anode. These results show that these highly conductive PEDOT:PSS films can not only be used as transparent electrodes in novel devices (where ITO cannot be used), such as stretchable OPVs, but also have the potential to replace ITO in conventional devices.     

Ultrasmooth,highly conductive and transparent PEDOT:PSS/silver nanowire composite electrode for flexible organic light-emitting devices

The next generation of optoelectronic devices requires transparent conductive electrodes to be flexible, inexpensive and compatible with large scale manufacturing processes. We report an ultrasmooth, highly conductive and transparent composite electrode on a flexible photopolymer substrate by employing a template stripping method. A random silver nanowire (AgNW) network buried in poly(3,4ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film constituted the composite electrode. Besides the effectively decreased surface roughness, its sheet resistance and transmittance are comparable to those of conventional PEDOT:PSS electrode. As a result, the efficiency of the OLEDs based on the composite electrode exhibited 25% enhancement compared to the OLEDs with conventional PEDOT:PSS electrode. Moreover, the performance of the flexible OLEDs remains stable after over one hundred bending cycles.     

Stretchable ITO-Free Organic Solar Cells with Intrinsic Anti-Reflection Substrate for High-Efficiency Outdoor and Indoor Energy Harvesting

Flexible photovoltaic devices are promising candidates for triggering the Internet of Things (IoT). However, the power conversion efficiencies (PCEs) of flexible organic photovoltaic (OPV) devices with high conductivity poly(3,4-ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS) electrodes on plastic are lagging behind the rigid devices due to the low transmittance of polyethylene terephthalate (PET)/PEDOT:PSS. Moreover, the poor stretchability of the commonly used plastic substrates largely hinders the practical application of wearable devices. Herein, a novel stretchable indium tin oxide (ITO)-free OPV device with a surface-texturing polydimethylsiloxane (PDMS) substrate for outdoor strong- and indoor dim-light energy harvesting is reported. The high diffuse transmittance and haze effect of the substrate enable stretchable ITO-free devices, yielding a high PCE of 15.3% under 1 sun illumination. More excitingly, the stretchable device based on textured PDMS/PEDOT:PSS maintains a comparable PCE of 20.5% (20.8% for the rigid device) under indoor light illumination. Notably, the stretchable device is much more insensitive to the light direction, maintaining 38.5% of the initial PCE at an extremely small incident angle of 10° (16.3% for glass/ITO-based counterpart). The texturing stretchable substrate provides a new direction for achieving high performance and enhanced light utilization for the stretchable light-harvesting device, suitable for indoor and outdoor applications.     

Achieving High Efficiency and Improved Stability in ITO‐Free Transparent Organic Light‐Emitting Diodes with Conductive Polymer Electrodes

Efficient transparent organic light‐emitting diodes (OLEDs) with improved stability based on conductive, transparent poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) electrodes are reported. Based on optical simulations, the device structures are carefully optimized by tuning the thickness of doped transport layers and electrodes. As a result, the performance of PEDOT:PSS‐based OLEDs reaches that of indium tin oxide (ITO)‐based reference devices. The efficiency and the long‐term stability of PEDOT:PSS‐based OLEDs are significantly improved. The structure engineering demonstrated in this study greatly enhances the overall performances of ITO‐free transparent OLEDs in terms of efficiency, lifetime, and transmittance. These results indicate that PEDOT:PSS‐based OLEDs have a promising future for practical applications in low‐cost and flexible device manufacturing.     

Effects of the ink concentration on multi-layer gravure-printed PEDOT:PSS

To date, highly conductive PEDOT:PSS is the most promising transparent electrode for printing-based flexible organic electronics. Spin-coating and slot-die coating have been commonly used for printing this material. Among the roll-to-roll printing processes, gravure is the most promising for manufacturing large area electronics offering the advantages of high speed and high printing definition. However, gravure printing highly conductive PEDOT encounters some technological limitations such as low thickness, layer inhomogeneity and high surface roughness resulting in a layer not suitable as electrode in electronic devices. In order to realize an electrode of highly conductive PEDOT by gravure printing, a multilayer approach with variable ink concentration was tried using IPA as process solvent. Variable solvent amount of overlapped printed layers was found to play an important role in the spreading of the PEDOT ink onto the pre-printed layers and in the smoothing of its existent peaks. In particular, adopting increasing ink dilution with increasing of the overlapped layers, multi-layer gravure-printed highly conductive PEDOT was successfully realized with characteristics suitable as transparent electrode for organic electronic devices (sheet resistance lower than 130 Ω/sq, conductivity higher than 450 S/cm and optical transmittance over 80%). This is the first time that such results were reached by gravure printing technique thanks to the easy proposed approach.     

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.     

Efficient ITO-free organic light-emitting diodes comprising PEDOT:PSS transparent electrodes optimized with 2-ethoxyethanol and post treatment

We demonstrate highly conductive poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) films introduced with a newly investigated solvent 2-ethoxyethanol. The films are optimized by simple solvent post treatment and show enhanced conductivities and reduced sheet resistances. Solvent post treatment for 2-ethoxyethanol added PEDOT:PSS films reduces insulating PSS and forms conductive PEDOT networks in conductive films, resulting in improved electrical properties. ITO-free white OLEDs are fabricated with post-treated PEDOT:PSS electrodes and show almost equal performance to ITO-based OLEDs. Our work demonstrate that the conductive PEDOT:PSS electrode optimized by 2-ethoxyethanol and post treatment promises its potential as alternative transparent electrode in flexible, low-cost, high-performance ITO-free OLEDs.     

Toward Stretchable Self‐Powered Sensors Based on the Thermoelectric Response of PEDOT:PSS/Polyurethane Blends

The development of new flexible and stretchable sensors addresses the demands of upcoming application fields like internet‐of‐things, soft robotics, and health/structure monitoring. However, finding a reliable and robust power source to operate these devices, particularly in off‐the‐grid, maintenance‐free applications, still poses a great challenge. The exploitation of ubiquitous temperature gradients, as the source of energy, can become a practical solution, since the recent discovery of the outstanding thermoelectric properties of a conductive polymer, poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS). Unfortunately the use of PEDOT:PSS is currently constrained by its brittleness and limited processability. Herein, PEDOT:PSS is blended with a commercial elastomeric polyurethane (Lycra), to obtain tough and processable self‐standing films. A remarkable strain‐at‐break of ≈700% is achieved for blends with 90 wt% Lycra, after ethylene glycol treatment, without affecting the Seebeck voltage. For the first time the viability of these novel blends as stretchable self‐powered sensors is demonstrated.     

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.     

Ice-Templated,Large-Area Silver Nanowire Pattern for Flexible Transparent Electrode

Flexible transparent electrodes are critically important for the emerging flexible and stretchable electronic and optoelectronic devices. To this end, transparent polymer films coated with silver nanowires (AgNWs) have been intensively studied in the past decade. However, it remains a grand challenge to achieve both high conductivity and transmittance in large-area films, mainly due to the poor alignment of AgNWs and their high junction resistance. Here, the successful attempt to realize large-area AgNW patterns on various substrates by a 2D ice-templating approach is reported. With a relatively low dosage of AgNWs (4 µg·cm⁻²), the resulted flexible electrode simultaneously achieves high optical transmittance (≈91%) and low sheet resistance (20 Ω·sq⁻¹). In addition, the electrode exhibits excellent durability during cyclic bending (≈10 000 times) and stretching (50% strain). The potential applications of the flexible transparent electrode in both touch screen and electronic skin sensor, which can monitor the sliding pressure and direction in real-time, are demonstrated. More importantly, it is believed that the study represents a facile and low-cost approach to assemble various nanomaterials into large-area functional patterns for advanced flexible devices.     

Neutral-pH PEDOT:PSS as over-coating layer for stable silver nanowire flexible transparent conductive films

The silver nanowire (AgNW) mesh film with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the over-coating layer is a promising flexible transparent conductive film technology. In this work, experimental studies show that the hygroscopic and acid properties of the common PEDOT:PSS lead to poor stabilities of the composite films, due to the conductivity degradation of PEDOT:PSS by the water absorption and the acid corrosion of AgNWs by PEDOT:PSS. By using the modified PEDOT:PSS of neutral pH as the over-coating layer, the long term shelf-life time, thermal and current stressing stabilities are all significantly improved without sacrifice of transparency, electrical conductivity and mechanical flexibility. Under both cases of thermal aging test at 210 °C for 20 min and 12 h continuous current stressing at a current density of 30 mA/cm², no obvious change of the conductivity is observed. The results clearly demonstrate that using the neutral-pH PEDOT:PSS as an over-coating layer can help to achieve flexible AgNW transparent conductive films with superior stability for flexible optoelectronic devices.     

Comparison of dimethyl sulfoxide treated highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) electrodes for use in indium tin oxide-free organic electronic photovoltaic devices

Indium tin oxide (ITO)-free organic photovoltaic (OPV) devices were fabricated using highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the transparent conductive electrode (TCE). The intrinsic conductivity of the PEDOT:PSS films was improved by two different dimethyl sulfoxide (DMSO) treatments – (i) DMSO was added directly to the PEDOT:PSS solution (PEDOT:PSS_ADD) and (ii) a pre-formed PEDOT:PSS film was immersed in DMSO (PEDOT:PSS_IMM). X-ray photoelectron spectroscopy (XPS) and conductive atomic force microscopy (CAFM) studies showed a large amount of PSS was removed from the PEDOT:PSS_IMM electrode surface. OPV devices based on a poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) bulk hetrojunction showed that the PEDOT:PSS_IMM electrode out-performed the PEDOT:PSS_ADD electrode, primarily due to an increase in short circuit current density from 6.62 mA cm⁻² to 7.15 mA cm⁻². The results highlight the importance of optimising the treatment of PEDOT:PSS electrodes and demonstrate their potential as an alternative TCE for rapid processing and low-cost OPV and other organic electronic devices.     

ITO-free organic solar cells using highly conductive phenol-treated PEDOT:PSS anodes

Phenol as one of the most polar solvent was used to enhance the conductivity of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films. The conductivity of PEDOT:PSS films improved to 1193 S/cm after treatment with phenol vapor and 1054 S/cm after treatment with phenol drop. The treated films also showed high transmittance in the visible region which is one of the crucial factors for optoelectronic devices such as organic solar cells and light emitting diodes. The mechanism of conductivity enhancement of treated thin PEDOT:PSS films was investigated by atomic force microscopy (AFM) and UV/Vis spectrophotometer. The AFM images showed that the ratio of PEDOT to PSS at top most of the surface was increased for treated film. Rearrangement of PEDOT segment throughout the film and hence conformational changes are the reasons for enhancement of conductivity. The modified PEDOT:PSS films were used as electrode for ITO-free organic solar cells (OSCs). These ITO-free OSCs showed almost equal operation to those for ITO electrodes.     

Highly conductive PEDOT:PSS films prepared through a treatment with geminal diols or amphiphilic fluoro compounds

Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films with high conductivity can have important application as the transparent electrode of optoelectronic devices. In this paper, we report the significant conductivity enhancement of PEDOT:PSS through a treatment with germinal diols which have two hydroxyl groups connected to one carbon atom or amphiphilic fluoro compounds which have hydrophobic fluorocarbon groups and hydrophilic hydroxyl or carboxylic groups. Several compounds, including hexafluoroacetone, cyclohexanehexone, formaldehyde, acetaldehyde, and perfluorobenzophenone, which could convert into geminal diols, were used to treat PEDOT:PSS films. The conductivity enhancements are generally consistent with the equilibrium constants for the conversion of these compounds into geminal diols. PEDOT:PSS films were also treated with several amphiphilic fluoro compounds. The conductivity was significantly enhanced when PEDOT:PSS films were treated with hexafluoroisopropanol, trifluoroacetic acid and heptafluorobutyric acid, while it hardly changed when they were treated with 2,2,2-trifluoroethanol. Conductivities of more than 1000 S cm⁻¹ were observed on the treated PEDOT:PSS films. The mechanism for the conductivity enhancement of PEDOT:PSS through the treatment with geminal diols or amphiphilic fluoro compounds is attributed to the phase segregation of PSSH from PEDOT:PSS and conformational change of the PEDOT chains as the results of the compounds-induced reduction in the Coulombic attraction between the positively charged PEDOT and negatively charged PSS chains.     

Room‐Temperature Nanosoldering of a Very Long Metal Nanowire Network by Conducting‐Polymer‐Assisted Joining for a Flexible Touch‐Panel Application

As an alternative to the brittle and expensive indium tin oxide (ITO) transparent conductor, a very simple, room‐temperature nanosoldering method of Ag nanowire percolation network is developed with conducting polymer to demonstrate highly flexible and even stretchable transparent conductors. The drying conducting polymer on Ag nanowire percolation network is used as a nanosoldering material inducing strong capillary‐force‐assisted stiction of the nanowires to other nanowires or to the substrate to enhance the electrical conductivity, mechanical stability, and adhesion to the substrate of the nanowire percolation network without the conventional high‐temperature annealing step. Highly bendable Ag nanowire/conducting polymer hybrid films with low sheet resistance and high transmittance are demonstrated on a plastic substrate. The fabricated flexible transparent electrode maintains its conductivity over 20 000 cyclic bends and 5 to 10% stretching. Finally, a large area (A4‐size) transparent conductor and a flexible touch panel on a non‐flat surface are fabricated to demonstrate the possibility of cost‐effective mass production as well as the applicability to the unconventional arbitrary soft surfaces. These results suggest that this is an important step toward producing intelligent and multifunctional soft electric devices as friendly human/electronics interface, and it may ultimately contribute to the applications in wearable computers.     

Textile‐Based Flexible Electroluminescent Devices

Flexible and transparent textile‐based conductors are developed by inkjet printing poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) onto polyethylene terephthalate (PET) mesh fabrics. The conductivity–transparency relationship is determined for textile‐based conductors with different thicknesses of the printed PEDOT:PSS film. The function of these textile‐based conductors is studied in the alternating current powder electroluminescent (ACPEL) devices and compared with indium tin oxide (ITO) glass in an ACPEL device of the same configuration. Textiles coated with conducting polymers are a potential alternative to coated polymer films for flexible, transparent conductors.     

Screen‐Printed Poly(3,4‐Ethylenedioxythiophene):Poly(Styrenesulfonate) Grids as ITO‐Free Anodes for Flexible Organic Light‐Emitting Diodes

Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) grids have been successfully constructed by roll‐to‐roll compatible screen‐printing techniques and have been used as indium tin oxide (ITO)‐free anodes for flexible organic light‐emitting diodes (OLEDs). The grid‐type transparent conductive electrodes (TCEs) can adopt thicker PEDOT: PSS grid lines to ensure the conductivity, while the mesh‐like grid structure can play an important role to maintain high optical transparency. By adjusting grid periods, grid thickness and treatment of organic additives, PEDOT: PSS TCEs with high optical transparency, low sheet resistance, and excellent mechanical flexibility have been achieved. Using the screen‐printed PEDOT: PSS grids as the anodes, ITO‐free OLEDs achieved peak current efficiency of 3.40 cd A^?1 at the current density of 10 mA cm^?2, which are 1.56 times better than the devices with ITO glass as the anodes. The improved efficiency is attributed to the light extraction effect and improved transparency by the grid structure. The superior optoelectronic performances of OLEDs based on flexible screen‐printed PEDOT: PSS grid anodes suggest their great prospects as ITO‐free anodes for flexible and wearable electronic applications.     

Flexible Electronics: Stretchable Electrodes and Their Future

Flexible electronics, as an emerging and exciting research field, have brought great interest to the issue of how to make flexible electronic materials that offer both durability and high performance at strained states. With the advent of on‐body wearable and implantable electronics, as well as increasing demands for human‐friendly intelligent soft robots, enormous effort is being expended on highly flexible functional materials, especially stretchable electrodes, by both the academic and industrial communities. Among different deformation modes, stretchability is the most demanding and challenging. This review focuses on the latest advances in stretchable transparent electrodes based on a new design strategy known as kirigami (the art of paper cutting) and investigates the recent progress on novel applications, including skin‐like electronics, implantable biodegradable devices, and bioinspired soft robotics. By comparing the optoelectrical and mechanical properties of different electrode materials, some of the most important outcomes with comments on their merits and demerits are raised. Key design considerations in terms of geometries, substrates, and adhesion are also discussed, offering insights into the universal strategies for engineering stretchable electrodes regardless of the material. It is suggested that highly stretchable and biocompatible electrodes will greatly boost the development of next‐generation intelligent life‐like electronics.     

Handheld and automated ultrasonic spray deposition of conductive PEDOT:PSS films and their application in AC EL devices

In this contribution we explore the spray deposition technique to achieve smooth films based on the conductive polymer PEDOT:PSS. Two different spray systems were used and compared namely: (a) handheld airbrush and (b) automated ultrasonic spray system. For each system a number of parameters were pre-adjusted during coating control experiments such as spray head distance, angle and cone for airbrush as well as flow rate, power and focus for ultrasonic nozzle. Water-based solutions of PEDOT:PSS having 20% of N-methylpyrrolidone (NMP) were sprayed on glass substrates at temperatures ranging from 75 to 150 °C. The resulting films were further chemically treated with ethylene glycol (EG) and evaluated with respect to their morphological, electrical and optical properties. Before EG-treatment the ultrasonic spraying resulted in smoother films with conductivity up to 2–3.9 times higher than their airbrushed counterparts. Deposition temperature proved to have minor effect on the morphological and electro-optical properties of PEDOT:PSS films. On the other hand, the film conductivity was enhanced, peaking at 610.1 S cm⁻¹ for ultrasonic spraying, when further chemically modified by EG. IR microspectroscopy mapping analysis, Raman spectroscopy and XRD data indicated a phase-separation between PEDOT and PSS chains and increasing crystallinity in the ultrasonically sprayed films. The application of such PEDOT:PSS films as transparent electrode in flexible AC EL devices is demonstrated.     

High-Throughput Screening of Self-Healable Polysulfobetaine Hydrogels and their Applications in Flexible Electronics

Hydrogels are promising materials in the applications of wound adhesives, wearable electronics, tissue engineering, implantable electronics, etc. The properties of a hydrogel rely strongly on its composition. However, the optimization of hydrogel properties has been a big challenge as increasing numbers of components are added to enhance and synergize its mechanical, biomedical, electrical, and self-healable properties. Here in this work, it is shown that high-throughput screening can efficiently and systematically explore the effects of multiple components (at least eight) on the properties of polysulfobetaine hydrogels, as well as provide a useful database for diverse applications. The optimized polysulfobetaine hydrogels that exhibit outstanding self-healing and mechanical properties, have been obtained by high-throughput screening. By compositing with poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), intrinsically self-healable and stretchable conductors are achieved. It is further demonstrated that a polysulfobetaine hydrogel-based electronic skin, which exhibits exceptionally fast self-healing capability of the whole device at ambient conditions. This work successfully extends high-throughput synthetic methodology to the field of hydrogel electronics, as well as demonstrates new directions of healable flexible electronic devices in terms of material development and device design.