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.     

Intense-pulsed-light irradiation of Ag nanowire-based transparent electrodes for use in flexible organic light emitting diodes

Silver nanowire (AgNW) based transparent electrodes are inherently coarse and therefore typically are only ever weakly bonded to a substrate. A remarkable improvement in the characteristics of a AgNW network film has, however, been achieved through a simple and short process of irradiating it with intense pulsed light (IPL). This not only avoids any severe deterioration in the optical characteristics of the AgNW film, but also significantly improves its electrical conductivity, adhesion to a polymeric substrate, and ability to endure bending stress. Most important of all, however, is the finding that the surface roughness of AgNW networks can also be improved by radiation. In a series of measurements made of organic light emitting diodes fabricated using these treated electrodes, it was revealed that the leakage current can be notably reduced by IPL treatment.     

Highly flexible organic light-emitting diodes based on ZnS/Ag/WO3 multilayer transparent electrodes

We report our study on highly flexible organic light-emitting diodes based on ZnS/Ag/WO₃ (ZAW) multilayer transparent electrodes in which high conductivity and ductility of Ag layers allow for efficient sheet conduction and flexibility while ZnS and WO₃ layers provide a means for enhancement in optical transmission and/or carrier-injection. Devices with ZAW anodes fabricated on planarized plastic substrates not only exhibit a performance and operational stability comparable to or better than those of ITO-based devices but also show a mechanical flexibility that is far superior to that of ITO-based devices. Experimental results show that a consistent performance can be obtained in ZAW-based devices upon repeated bending down to a radius of curvature of 5 mm, below which the flexibility of the devices is limited ultimately by the delamination occurring at cathode/organic interfaces rather than by the ZAW electrodes themselves.     

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.     

Combined alternative electrodes for semi-transparent and ITO-free small molecule organic solar cells

We investigate various electrode combinations of bottom and top contacts for organic photovoltaic (OPV) cells. Silver (Ag), indium tin oxide (ITO), poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and silver nanowires (AgNW) are used as bottom electrodes. As top electrodes, thin silver layers (t-Ag) and free-standing carbon nanotube (f-CNT) sheets are employed. The manufactured zinc phthalocyanine (ZnPc): fullerene C₆₀ small molecule bulk heterojunction OPV cells with different kinds of bottom electrodes show efficiencies of 1.9∼2.2% and 1.1∼1.5%, when comprised of t-Ag and f-CNT top contacts, respectively. We demonstrate alternative electrodes beyond ITO, silver, and aluminum, which can be readily used for organic photovoltaics technology.     

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.     

Inkjet-printed Ag grid combined with Ag nanowires to form a transparent hybrid electrode for organic electronics

Networks of silver nanowires (AgNW) have been shown to facilitate high transparency, high conductivity, and good mechanical stability. However,the loose characteristic and local insulation problems due to gaps between the nanowires limit their application as electrodes. This study investigates an inkjet-printed Ag grid combined with AgNW to form a transparent hybrid electrode. The printed Ag grid on AgNW film connects the gaps between the Ag nanowires to increase the overall electric conductivity. The printed Ag-grid/AgNW hybrid electrodes have low resistivity (22.5 Ω/□) while maintaining a high transmittance (87.5%). These values are similar to standard indium tin oxide (ITO) on glass which has resistivity of 20Ω/□ and transmittance of 89% at 550 nm. In addition, these hybrid electrodes are also very flexible when fabricated on a photopolymer substrate. A spin-coating process combined with a peel-off process enable the fabrication of flexible ultra-smooth Ag-grid/AgNW electrodes. We tested the transparent and flexible electrode as the anode of a flexible organic light emitting diode (F-OLED). The light emitting layer of the F-OLED is 35 nm thick tris-(8-hydroxyquinoline) aluminum doped with 0.5% 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-(1)-benzopyropyrano(6,7-8-I,j)quinolizin-11-one. The maximum brightness and current efficiency of the F-OLED are 10000 cd/m² and 12 cd/A, respectively, even when bent around a radius of 2 mm. The good performance of the device with Ag-grid/AgNW hybrid electrodes show that enhanced conductive inkjet-printed Ag nanoparticles combined with Ag nanowires can produce high quality electrodes for flexible organic optoelectronic 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.     

Indium tin oxide-free semi-transparent inverted polymer solar cells using conducting polymer as both bottom and top electrodes

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is investigated as a transparent cathode to replace indium tin oxide (ITO) in inverted polymer solar cells. Increasing the thickness of the PEDOT:PSS electrode leads to a reduction in transparency and sheet resistance which lowers the photocurrent but increases the fill factor of the solar cells. The offset of photocurrent and fill factor as the thickness is increased leads to a saturation of the power conversion efficiency to 3%. These electrodes were applied to flexible substrates showing similar device performance to glass based devices. Cyclic bending test of these flexible polymer electrodes show improved conversion efficiency retention (92%) when compared to flexible ITO based electrodes (50%) after 300 bend cycles. In addition to using PEDOT:PSS as a cathode replacement for ITO in inverted solar cells, its use as a semi-transparent anode replacement to Ag is also examined. Semi-transparent inverted solar cells fabricated with ITO as the cathode and PEDOT:PSS as the top anode electrode were demonstrated showing efficiencies of 2.51% while replacement of both ITO and Ag with PEDOT:PSS as both the cathode and anode show efficiencies of 0.47%.     

Flexible organic solar cells using an oxide/metal/oxide trilayer as transparent electrode

Organic solar cells (OSCs) have attracted much attention as a clean and renewable energy convention system, owning to the low-cost and easy-processing nature of organic semiconductors. While indium tin oxide (ITO) is commonly used in OSCs as the transparent conductive electrode, the rising cost of indium, the high temperature process and the poor flexibility of ITO, make it incompatible with large-scale roll-to-roll manufacture of OSCs. In this paper, the MoO₃/thin metal/MoO₃ trilayer structure was used to replace the ITO electrode in OSCs. The optical and electrical properties of the trilayer were shown to depend on the material and thickness of the intermediate metal layer. The maximum power conversion efficiency of up to 2.5% under simulated 1 sun AM 1.5 solar illumination was achieved for OSCs based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM), compared to a maximum efficiency of 3.1% for the ITO-based devices. Moreover, due to the flexible nature of the trilayer structure, the OSCs with the trilayer electrode exhibited good mechanical flexibility. The efficiency of the flexible device was only reduced by ∼6% from its original performance after 500 bending cycles with a bending radius of 1.3 cm. Therefore, the performance of the ITO-free devices on rigid/flexible substrates suggests that this oxide/metal/oxide trilayer electrode is a promising ITO replacement in OSCs.     

Improved efficiency of indium-tin-oxide-free flexible organic light-emitting devices

An indium-tin-oxide (ITO)-free flexible organic light-emitting device (OLED) with improved efficiency has been demonstrated by employing a template stripping process to create an ultrasmooth PEDOT: PSS anode on a photopolymer substrate. The device performance has been improved owing to lowered surface roughness of the PEDOT: PSS anode. A 38% enhancement in efficiency has been obtained. The ITO-free OLEDs on the polymer substrate have shown flexibility, and the device is free of cracks and dark spots under small bending radius. Moreover, the elimination of the H₂SO₄ residues on the surface of the H₂SO₄-treated PEDOT: PSS by the template stripping has demonstrated its beneficial effect on the device stability.     

Photolithographic patterning of PEDOT:PSS with a silver interlayer and its application in organic light emitting diodes

A patterning scheme for poly(3,4-ethylenedioxythio-phene):poly(styrenesulfonate) (PEDOT:PSS) is reported. With a silver interlayer, the conductive PEDOT:PSS film can be patterned down to micrometer scales by traditional photolithography, and this patterning scheme can be applied on large-area flexible substrates. Through systematical investigations, the patterning processes have no obvious influence on both the bulk and surface properties of PEDOT:PSS films. Efficient organic light emitting diodes (OLEDs) are realized based on this patterned PEDOT:PSS anode, and they show comparable performance to those devices with an indium tin oxide (ITO) anode. High-resolution OLED pixel arrays are also demonstrated. Our interlayer approach here has an advantage of patterning PEDOT:PSS with high resolution and large scale, and it is also compatible with traditional photolithographic processes which substantially save the capital cost. Results indicate that the photographically patterned conductive PEDOT:PSS film becomes a promising candidate for eletrical eletrode material in organic electronic applications.     

Transparent and flexible amorphous InZnAlO films grown by roll-to-roll sputtering for acidic buffer-free flexible organic solar cells

We report on transparent and flexible amorphous In–Zn–Al–O (a-IZAO) films prepared by roll-to-roll (RTR) sputtering for use as anodes in acidic buffer free flexible organic solar cells (FOSCs). The presence of Zn and Al structural stabilizers in the In₂O₃ matrix produced a completely amorphous structure with the high optical transmittance of 89.25% and the low resistivity of 2.123 × 10⁻³ Ω-cm, as well as the high work function of 5.14 eV, making the a-IZAO films suitable for use as flexible anodes for FOSCs. In addition, the a-IZAO films showed no change in resistance (ΔR) during outer and inner bending fatigue tests due to their good mechanical flexibility. Relative to the power conversion efficiency (1.944%) of a PEDOT:PSS-based FOSCs, a FOSC fabricated by using an a-IZAO anode and without the use of acidic PEDOT:PSS buffer showed greater power conversion efficiency (2.509%), owing to the absence of interfacial reactions between the acidic PEDOT:PSS and the a-IZAO anode.     

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.     

Electrical characterization of organic solar cell contact degradation resulting from ambient exposure

The electrical and photocurrent characteristics resulting from low light ambient degradation of organic bulk heterojunction solar cells are reported. The degradation is associated with the contacts and the active layer shows no evidence of any change in properties. Ambient exposure induces an exponential current–voltage characteristic in the contact region. An empirical model for the cell current–voltage characteristics shows how the cell properties may be corrected to recover the characteristics of the active layer. Modeling compares the effects of ohmic and exponential contact resistance on the solar cell response of a typical cell.     

Simultaneous enhancement of the efficiency and stability of organic solar cells using PEDOT:PSS grafted with a PEGME buffer layer

We report a simple processing method to simultaneously improve the efficiency and stability of organic solar cells (OSCs). Poly(4-styrene sulfonate)-doped poly(3,4-ethylenedioxy-thiophene (PEDOT:PSS), widely used as hole transport layer (HTL) in OSCs, tends to accelerate the degradation of devices because of its hygroscopic and acidic properties. In this regard, we have modified PEDOT:PSS to reduce its hygroscopic and acidic properties through a condensation reaction between PEDOT:PSS and poly(ethylene glycol) methyl ether (PEGME) in order to improve the efficiency and stability of OSCs. As a result, the power conversion efficiency (PCE) increased by 21%, from 2.57% up to 3.11%. A better energy level alignment by the reduced work function of the modified PEDOT:PSS with a highest occupied molecular orbital (HOMO) level of poly(3-hexylthiophene-2,5-diyl) (P3HT) is considered the origin of the improved the efficiency. The half-life of OSCs with PEDOT:PSS modified with PEGME buffer layer also increased up to 3.5 times compared to that of devices with pristine PEDOT:PSS buffer layer.     

Ultra-thin flexible screen printed rechargeable polymer battery for wearable electronic applications

This research has demonstrated how an ultra-thin rechargeable battery technology has been fabricated using screen printing technology. The screen printing process enabled the sequential deposition of current collector, electrode and separator/electrolyte materials onto a polyethylene terephthalate (PET) substrate in order to form both flexible and rechargeable electrodes for a battery application. The anode and cathode fabricated were based on the conducting poly (3,4-ethylenedioxythiophen): poly (styrene sulfonate) (PEDOT: PSS) and polyethyleneimine (PEI) which were combined to form the electrodes. The difference in the oxidation level between the two electrodes produced an open circuit voltage of 0.60 V and displayed a practical specific capacity of 5.5 mAh g⁻¹. The battery developed had an active surface area of 400 mm² and a device thickness of 440 μm. The chemistry developed during this study displayed long-term cycling potential and proves the stability of the cells for continued usage. This technology has direct uses in future personal wearable electronic devices.     

Orthogonally weaved silver nanowire networks for very efficient organic optoelectronic devices

We demonstrate a simple but effective method to control the orientation of silver nanowires (AgNWs). Shear-flow-induced AgNW preferable orientation is realized by judiciously controlling the process parameters in the bar-coating method. This controllability of the NW direction enables the formation of AgNW cross-linking networks for transparent conductive electrode (TCE) applications. We experimentally demonstrate that the orthogonally weaved AgNW networks possess predominant advantages of lower percolation limit, higher transmission, and lower sheet resistance compared with the randomly orientated AgNW counterparts. The phenomenon is also confirmed with theoretical calculation by the Monte Carlo method. These high-quality AgNW TCEs exhibit a high transmittance of ∼94% with a sheet resistance of ∼20 Ω/sq, which meet the requirements of modern optoelectronic devices. Very efficient organic light-emitting diodes (OLEDs) and organic solar cells (OSCs) prepared by these AgNW TCEs are demonstrated. The OLED exhibits exceptionally high luminance efficiency, power efficacy, and external quantum efficiency of 92 cd/A, 111 lm/W, and 26.8%, respectively. The OSCs also deliver a high power conversion efficiency of up to 7.5%.     

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.