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.     

Intrinsically Stretchable Organic Solar Cells beyond 10% Power Conversion Efficiency Enabled by Transfer Printing Method

Stretchable organic solar cells (OSCs) simultaneously possessing high-efficiency and robust mechanical properties are ideal power generators for the emerging wearable and portable electronics. Herein, after incorporating a low amount of trimethylsiloxy terminated polydimethylsiloxane (PDMS) additive, the intrinsic stretchability of PTB7-Th:IEICO-4F bulk heterojunction (BHJ) film is greatly improved from 5% to 20% strain without sacrificing the photovoltaic performance. The intimate multi-layers stacking of OSCs is also realized with the transfer printing method assisted by electrical adhesive “glue” D-Sorbitol. The resultant devices with 84% electrode transmittance exhibit a remarkable power conversion efficiency (PCE) of 10.1%, which is among the highest efficiency for intrinsically stretchable OSCs to date. The stretchable OSCs also demonstrate the ultra-flexibility, stretchability, and mechanical robustness, which keep the PCE almost unchanged at small bending radium of 2 mm for 300 times bending cycles and retain 86.7% PCE under tensile strain as large as 20% for the devices with 70% electrode transmittance. The results provide a universal method to fabricate highly efficient intrinsically stretchable OSCs.     

Conductive PEDOT:PSS on surface-functionalized chitosan biopolymers for stretchable skin-like electronics

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a promising alternative transparent electrode to replace conventional indium tix oxide (ITO) for flexible and stretchable electronics. For their applications in optoelectronic devices, realizing both high conductivity and transmittance for the films is of great necessity as a suitable high performance transparent electrode. Here, we demonstrate simultaneously enhanced electrical and optical properties of PEDOT:PSS films prepared on chitosan bio-substrates by using an organic surface modifier, 11-aminoundecanoic acid (11-AA). The sheet resistance of PEDOT:PSS films decreases from 1120.8 to 292.8 Ω/sq with an increase in a transmittance from 75.9 to 80.4% by 11-AA treatment on the chitosan films. The functional groups of 11-AA effectively enhance the adhesion property at the interface between the chitosan substrate and PEDOT:PSS by forming strong interfacial bondings and decrease insulating PSS from PEDOT:PSS films. The wearable heater devices and on-skin sensors based on the 11-AA-treated PEDOT:PSS on the chitosan bio-substrates are successfully fabricated, showing the excellent thermal and sensing performances. The 11-AA surface-modification approach for highly conductive PEDOT:PSS on chitosan bio-substrates presents a great potential for applications toward transparent, flexible and stretchable electronics.     

Semiconducting single-walled carbon nanotubes as interfacial modification layers for organic-Si solar cells

A semiconducting single-walled carbon nanotubes (s-SWCNTs) interlayer between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and n-Si was used for high performance organic-Si hybrid photovoltaic (PV) devices. The s-SWCNTs films with different thickness were utilized to investigate the PV effect on PEDOT:PSS/Si device performance. The surface potential of Si substrate with s-SWCNTs was dramatically reduced, which increased the compatibility between Si and PEDOT:PSS. In addition, s-SWCNTs with good semiconducting properties, guaranteed the charge transfer between Si and PEDOT:PSS. Therein, the electrical contact was dramatically improved with addition of s-SWCNTs interlayer, which led to increased fill factor. A power conversion efficiency (PCE) of 12.14% was achieved with an optimized thickness of s-SWCNTs layer. The s-SWCNTs interface layer was fabricated by a simple solution processed method, which was easily coupled with organic-Si solar cells to enhance the PCE.     

Plasmonic Au nanoparticles for enhanced broadband light absorption in inverted organic photovoltaic devices by plasma assisted physical vapour deposition

We use a low vacuum plasma assisted physical vapour deposition (PAPVD) method to deposit a Au nanoparticles (NPs) thin film onto the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer in inverted poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methylester (P3HT:PCBM) organic photovoltaic (OPV) devices. The Au NPs that incorporated into the PEDOT:PSS layer and reached to the active P3HT:PCBM layer can provide significant plasmonic broadband light absorption enhancement to the active layer. An approximately 50–90% improvement in short-circuit current density and in power convention efficiency has been achieved compared with those OPV devices without the plasmonic light absorption enhancement. This technique can be adopted and easily fit into most OPV device fabrication processes without changing other layers’ processing methods, morphologies, and properties.     

Directional dependence of electron blocking in PEDOT:PSS

The directional dependence of electron blocking by poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is investigated in organic photovoltaic devices. In a conventional OPV architecture we find that a doped interlayer forms between poly(3-hexylthiophene) (P3HT) and the PSS-rich top layer of spin-coated PEDOT:PSS films. In an inverted OPV architecture, we find no mixing between PEDOT:PSS and P3HT, which is due to the lower concentration of PSS in bulk PEDOT:PSS than is found in the PSS-rich top layer. Through electrical measurements of conventional and inverted photovoltaic devices we show that the interlayer is necessary for PEDOT:PSS to be electron blocking. This result implies that PEDOT:PSS is not intrinsically electron blocking and that its directional anisotropy must be considered when comparing the advantages and disadvantages of conventional and inverted architecture photovoltaic devices.     

All-solution processed organic solar cells with top illumination

All-solution processed organic solar cells with inverted device architecture were demonstrated. Devices contain opaque bottom electrodes and semitransparent top electrodes, resulting in top illuminated devices. Nanoparticles-based Ag ink was used for inkjet printing both top and bottom electrodes. Semi-transparent top electrode consists of high conductivity PEDOT:PSS and Ag current collecting grids. Printed electrodes were compared to evaporated Ag electrodes (both top and bottom) and to ITO electrode in terms of transmittance, roughness, sheet resistance and device performance. All-solution processed devices with top illumination have average PCE of 2.4%, using P3HT:PCBM as photoactive layer. Top-illuminated devices with inverted architecture and bottom-illuminated device with conventional architecture, containing the identical layers, but in the reverse sequence, were then compared. Performed studies have revealed an advantage of inverted cell architecture.     

High efficiency arrays of polymer solar cells fabricated by spray‐coating in air

We present bulk heterojunction organic solar cells fabricated by spray‐casting both the PEDOT:PSS hole‐transport layer (HTL) and active PBDTTT‐EFT:PC₇₁BM layers in air. Devices were fabricated in a (6 × 6) array across a large‐area substrate (25 cm²) with each pixel having an active area of 6.45 mm². We show that the film uniformity and operational homogeneity of the devices are excellent. The champion device with spray cast active layer on spin cast PEDOT:PSS had an power conversion efficiency (PCE) of 8.75%, and the best device with spray cast active layer and PEDOT:PSS had a PCE of 8.06%. The impacts of air and light exposure of the active layer on device performance are investigated and found to be detrimental. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhancement of organic solar cell efficiency by patterning the PEDOT:PSS hole transport layer using nanoimprint lithography

In order to improve the conversion efficiency of organic photovoltaic (OPV) cells, nano-patterned poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) (PEDOT:PSS) was used as a hole transfer layer (HTL). Using nanoimprint lithography, a process that is easily applied to large-area substrates, a spherical array of PEDOT:PSS droplets was formed. The effect of the PEDOT:PSS nanostructure was characterized by optical and electrical measurements. Because the hemispherical array of PEDOT:PSS scatters light efficiently, absorption of the incident light increases when the nanostructured layer is employed. The conversion efficiency of the nano-patterned OPV cells is 25% larger than that of non-patterned OPV cells, due to the increase in short-circuit current (J_sc).     

Isopropanol-treated PEDOT:PSS as electron transport layer in polymer solar cells

Isopropanol (IPA)-treated poly(3,4-ethylenedioxithiophene):poly(styrene sulfonate) (PEDOT:PSS) was applied as a new electron transport layer (ETL) in P3HT:PCBM bulk heterojunction polymer solar cell (BHJ-PSC) devices for the first time, revealing the electron transport property of IPA-treated PEDOT:PSS in sharp contrast to the well known hole transport property of the untreated PEDOT:PSS. Under the optimized condition for incorporating PEDOT:PSS ETL, the power conversion efficiency (PCE) of the ITO/untreated PEDOT:PSS (HTL)/P3HT:PCBM/IPA-treated PEDOT:PSS (ETL)/Al device (3.09%) is quite comparable to that of the reference ITO/untreated PEDOT:PSS (HTL)/P3HT:PCBM/Al device without any ETL (3.06%), and an annealing treatment of PEDOT:PSS ETL at 120 °C for 10 min led to a PCE of 3.25%, which even slightly surpasses that of the reference device, revealing the electron transport property of IPA-treated PEDOT:PSS. The electron transport property of IPA-treated PEDOT:PSS is interpreted by the lowering of the work function of PEDOT:PSS upon IPA treatment and incorporation as ETL as probed by scanning Kelvin probe microscopy (SKPM).     

Stretchable and Transparent Conductive PEDOT:PSS‐Based Electrodes for Organic Photovoltaics and Strain Sensors Applications

The development of transparent, conducting, and stretchable poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)‐based electrodes using a combination of a polyethylene oxide (PEO) polymer network and the surfactant Zonyl is reported. The latter improves the ductility of PEDOT:PSS and enables its deposition on hydrophobic surfaces such as polydimethylsiloxane (PDMS) elastomers, while the presence of a 3D matrix offers high electrical conductivity, elasticity, and mechanical recoverability. The resulting electrode exhibits attractive properties such as high electrical conductivity of up to 1230 S cm^?1 while maintaining high transparency of 95% at 550 nm. The potential of the electrode technology is demonstrated in indium‐tin‐oxide (ITO)‐free solar cells using the PBDB‐T‐2F:IT‐4F blend with a power conversion efficiency of 12.5%. The impact of repeated stretch‐and‐release cycles on the electrical resistance is also examined in the effort to evaluate the properties of the electrodes. The interpenetrated morphology of the PEDOT:PSS and polyethylene oxide network is found to exhibit beneficial synergetic effects resulting in excellent mechanical stretchability and high electrical conductivity. By carefully tuning the amount of additives, the ability to detect small changes in electrical resistance as a function of mechanical deformation is demonstrated, which enables the demonstration of stretchable and resilient on‐skin strain sensors capable of detecting small motions of the finger.     

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.     

Influence of aluminium electrode preparation on PCE values of polymeric solar cells based on P3HT and PCBM

The main goal of the paper was investigation of influence of aluminum electrode preparation via thermal evaporation (TE) and the magnetron sputtering (MS) on power conversion efficiency (PCE) of polymeric solar cells. The photovoltaic properties of such three kinds devices based on poly(3-hexylthiophene-2,5-diyl) (P3HT) as ITO/P3HT/Al, ITO/P3HT:PCBM (1:1, w/w)/Al and ITO/PEDOT:PSS/P3HT:PCBM (1:1, w/w)/Al were investigated. For the constructed devices impedance spectroscopy were analyzed. For devices lack of PEDOT:PSS layer or lack of PCBM, photovoltaic parameters were very low and similar to the parameters obtained for device with Al electrode prepared by magnetron sputtering. The devices comprising PEDOT:PSS with P3HT:PCBM showed the best photovoltaic parameters such as a V_OC of 0.60 V, J_SC of 4.61 mA/cm², FF of 0.21, and PCE of 5.7 × 10^?1%.     

An ammonia modified PEDOT: PSS for interfacial engineering in inverted planar perovskite solar cells

Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) is one of the most widely used hole transport layers (HTL) in inverted perovskite solar cells (PSCs) due to its simple solution-processed ability, high transparency, and conductivity. However, PEDOT:PSS-based devices suffer a lower open-circuit voltage (V_oc) than devices with the conventional structure. To address this issue, we fabricated ammonia-modified PEDOT:PSS films by simply doping PEDOT:PSS solution with different ratio of ammonia. The acidity of PEDOT:PSS can be neutralized by the doped ammonia, which inhibits the ion-exchange reaction between PSS-H and CH₃NH₃I, thus retarding the reduction of the work function for PEDOT:PSS to some extent. As a result, a superior power conversion efficiency (PCE) of 15.5% was obtained for the device based on the ammonia-doped PEDOT:PSS HTL than that of the pristine PEDOT:PSS-based device. We ascribe the PCE enhancement to the increased V_oc and fill factor (FF), which is attributed not only to the better energy-level alignment between the ammonia-modified PEDOT:PSS film and perovskite layer but also to the increased grain size and crystallinity of perovskite film.     

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.     

Improved efficiency of indium-tin-oxide-free organic light-emitting devices using PEDOT:PSS/graphene oxide composite anode

We have demonstrated an indium-tin-oxide free organic light-emitting device (OLED) with improved efficiency by doping poly (3,4-ethylene dioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) with graphene oxide (GO) as a composite anode. In comparison with a pure PEDOT:PSS anode, 55% enhancement in efficiency has been obtained for the OLEDs based on the PEDOT:PSS/GO composite anode at an optimal condition. The PEDOT:PSS/GO composite anode shows a lower hole-injection barrier, which contributes to the improved device efficiency. Moreover, both high transmittance and good surface morphology similar to that of the pure PEDOT:PSS film also contribute to the enhanced efficiency. It is obvious that composite anode will generally be applicable in organic optoelectronic devices which require smooth and transparent anode.     

Solution processed WO3 layer for the replacement of PEDOT:PSS layer in organic photovoltaic cells

Tungsten oxide layer is formed uniformly by a sol–gel technique on top of indium tin oxide as a neutral and photo-stable hole extraction layer (HEL). The solution processed tungsten oxide layer (sWO₃) is fully characterized by UV–Vis, XPS, UPS, XRD, AFM, and TEM. Optical transmission of ITO/sWO₃ substrates is nearly identical to ITOs. In addition, the sWO₃ layer induces nearly ohmic contact to P3HT as PEDOT:PSS layer does, which is determined by UPS measurement. In case that an optimized thickness (～10 nm) of the sWO₃ layer is incorporated in the organic photovoltaic devices (OPVs) with a structure of ITO/sWO₃/P3HT:PCBM/Al, the power conversion efficiency (PCE) is 3.4%, comparable to that of devices utilizing PEDOT:PSS as HEL. Furthermore, the stability of OPV utilizing sWO₃ is significantly enhanced due to the air- and photo-stability of the sWO₃ layer itself. PCEs are decreased to 40% and 0% of initial values, when PEDOT:PSS layers are exposed to air and light for 192 h, respectively. In contrast, PCEs are maintained to 90% and 87% of initial PCEs respectively, when sWO₃ layers are exposed to the same conditions. Conclusively, we find that solution processed tungsten oxide layers can be prepared easily, act as an efficient hole extraction layer, and afford a much higher stability than PEDOT:PSS layers.     

Simple and Low-Cost Vanadyl Oxalate as Hole Transporting Layer Enables Efficient Organic Solar Cells

Organic solar cells (OSCs) with the conventional configuration usually use polyethylenedioxythiophene:polystyrene sulfonate (PEDOT:PSS) as the hole-transporting layer (HTL); however, its acidity tends to affect the performance and long-term stability of the devices. Therefore, replacing PEDOT:PSS with other more stable HTLs is essential for realizing the practical applications of OSCs. To achieve this goal, a simple and low-cost vanadyl oxalate (VOC₂O₄) is identified as a HTL to facilitate high power conversion efficiencies (PCEs), good stability, and high thickness tolerance to be achieved in OSCs. The VOC₂O₄ thin film can be easily prepared by spin-coating from its aqueous solution onto ITO/glass substrate and thermally annealed at 100 °C to exhibit high transmittance, conductivity, and work function. It can be applied as a robust HTL with wide processing conditions, especially after being heated at 200 °C and treated with UV-ozone (UVO) to afford a very high PCE of 18.94% in OSCs. This value is among the highest PCEs obtained for binary OSCs. In addition, the derived OSCs exhibit high thickness tolerance and better stability than those based on PEDOT:PSS as HTL. These results reveal that VOC₂O₄ is an excellent HTL for OSCs, having great potential for large-area device 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.