Ultrathin Metal films for Transparent Electrodes of Flexible Optoelectronic Devices

The need for the development of transparent conductive electrodes (TCEs) supported on flexible polymer substrates has explosively increased in response to flexible polymer‐based photovoltaic and display technologies; these TCEs replace conventional indium tin oxide (ITO) that exhibits poor performance on heat‐sensitive polymers. An efficient, flexible TCE is required to exhibit high electrical conductance and high optical transmittance, as well as excellent mechanical flexibility and long‐term stability, simultaneously. Recent advances in technologies utilizing an ultrathin noble‐metal film in a dielectric/metal/dielectric structure, or its derivatives, have attracted attention as promising alternatives that can satisfy the requirements of flexible TCEs. This review will survey the background knowledge and recent updates of synthetic strategies and design rules toward highly efficient, flexible TCEs based on ultrathin metal films, with a special focus on the principal features and available methodologies involved in the fabrication of highly transparent, conductive, ultrathin noble‐metal films. This survey will also cover the practical applications of TCEs to flexible organic solar cells and light‐emitting diodes.     

Flexible Organic Photovoltaic Cells with In Situ Nonthermal Photoreduction of Spin‐Coated Graphene Oxide Electrodes

The first reduction methodology, compatible with flexible, temperature‐sensitive substrates, for the production of reduced spin‐coated graphene oxide (GO) electrodes is reported. It is based on the use of a laser beam for the in situ, non‐thermal, reduction of spin‐coated GO films on flexible substrates over a large area. The photoreduction process is one‐step, facile, and is rapidly carried out at room temperature in air without affecting the integrity of the graphene lattice or the flexibility of the underlying substrate. Conductive graphene films with a sheet resistance of as low as 700 Ω sq^?1 and transmittance of 44% can be obtained, much higher than can be achieved for flexible layers reduced by chemical means. As a proof of concept of our technique, laser‐reduced GO (LrGO) films are utilized as transparent electrodes in flexible, bulk heterojunction, organic photovoltaic (OPV) devices, replacing the traditional ITO. The devices displayed a power‐conversion efficiency of 1.1%, which is the highest reported so far for OPV device incorporating reduced GO as the transparent electrode. The in situ non‐thermal photoreduction of spin‐coated GO films creates a new way to produce flexible functional graphene electrodes for a variety of electronic applications in a process that carries substantial promise for industrial implementation.     

Electrohydrodynamic NanoDrip Printing of High Aspect Ratio Metal Grid Transparent Electrodes

The transparent conducting electrode is an essential component in many contemporary and future devices, ranging from displays to solar cells. Fabricating transparent electrodes requires a balancing act between sufficient electrical conductivity and high light transmittance, both affected by the involved materials, fabrication methodology, and design. While metal films possess the highest conductivity at room temperature, a decent optical transmittance can only be achieved with ultrathin films. Structuring the metal into optically invisible nanowires has been shown to be promising to complement or even substitute transparent conductive oxides as dominant transparent electrode material. Here the out‐of‐plane fabrication capability of the recently developed method of electrohydrodynamic NanoDrip printing to pattern gold and silver nanogrids with line widths from 80 to 500 nm is demonstrated. This fully additive process enables the printing of high aspect ratio nanowalls and by that significantly improves the electrical performance, while maintaining the optical transmittance at a high level. Metal grid transparent electrodes optimized for low sheet resistances (8 Ω sq^?1 at a relative transmittance of 94%) as well as optimized for high transmittance (97% at a sheet resistance of 20 Ω sq^?1) are reported, which can be tailored on demand for the use in various applications.     

Skin‐Like Oxide Thin‐Film Transistors for Transparent Displays

Flexible transparent display is a promising candidate to visually communicate with each other in the future Internet of Things era. The flexible oxide thin‐film transistors (TFTs) have attracted attention as a component for transparent display by its high performance and high transparency. The critical issue of flexible oxide TFTs for practical display applications, however, is the realization on transparent and flexible substrate without any damage and characteristic degradation. Here, the ultrathin, flexible, and transparent oxide TFTs for skin‐like displays are demonstrated on an ultrathin flexible substrate using an inorganic‐based laser liftoff process. In this way, skin‐like ultrathin oxide TFTs are conformally attached onto various fabrics and human skin surface without any structural damage. Ultrathin flexible transparent oxide TFTs show high optical transparency of 83% and mobility of 40 cm² V^?1 s^?1. The skin‐like oxide TFTs show reliable performance under the electrical/optical stress tests and mechanical bending tests due to advanced device materials and systematic mechanical designs. Moreover, skin‐like oxide logic inverter circuits composed of n‐channel metal oxide semiconductor TFTs on ultrathin, transparent polyethylene terephthalate film have been realized.     

High‐Performance Polypyrrole/Graphene/SnCl2 Modified Polyester Textile Electrodes and Yarn Electrodes for Wearable Energy Storage

Flexible supercapacitors have potential for wearable energy storage due to their high energy/power densities and long operating lifetimes. High electrochemical performance with robust mechanical properties is highly desired for flexible supercapacitor electrodes. Usually, the mechanical properties are improved by choosing high flexible textile substrates but at the much expense of electrochemical performance due to the nonideal contact between conductive materials and textile substrates. Herein, the authors present an efficient, scalable, and general strategy for the simultaneous fabrication of high‐performance textile electrodes and yarn electrodes. It is interesting to find that the conformal reduced graphene oxide (RGO) layer is uniformly and successively painted on the surface of SnCl₂ modified polyester fibers (M‐PEF) via a repeated “dyeing and drying” strategy. The large‐area textile electrodes and ultralong yarn electrodes are fabricated by using RGO/M‐PEF as substrate with subsequent deposition of polypyrrole. This work provides new opportunities for developing high flexible textile electrodes and yarn electrodes with further increased electrochemical performance and scalable production.     

Novel Film‐Casting Method for High‐Performance Flexible Polymer Electrodes

A new film‐casting method for polymer electrodes is reported, in which thickness‐controlled drop‐casting (TCDC), using polyaniline doped with camphorsulfonic acid (PANI:CSA) is used. By combining the advantages of conventional spin‐casting and drop‐casting methods, and by rigorously controlling the film formation parameters, flexible polymer electrodes with high conductivity and excellent transmittance can be produced. The PANI:CSA electrodes cast by the TCDC method exhibited constant thickness‐independent conductivities of ～600 S cm^?1 down to a film thickness of 0.2 μm, and a high optical transmittance of about 85% at 550 nm. Furthermore, the new casting method significantly reduced the sheet resistance (～90 Ω/square) of the PANI:CSA electrodes compared with the conventional spin‐cast films, enhancing the performance of the devices deposited on plastic substrates. The flexible polymer light‐emitting diode produced a brightness of 6000 cd m^?2, and the flexible polymer solar cell exhibited a power conversion efficiency of 2%, both of which were much higher than those of the devices fabricated by the conventional spin‐casting method.     

Optically Transparent,Ultrathin Pt Films as Versatile Metal Substrates for Molecular Optoelectronics

This contribution reports a simple, straightforward method (cool sputtering) of fabricating robust, homogeneous, conductive, and optically transparent ultrathin Pt films. Their morphological, structural, mechanical, electrical, and optical properties are reported. The morphology and structure of these Pt films are investigated by scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and X‐ray diffraction. The ultrathin Pt films, approximately 20 nm thick, are characterized by a homogenous, polycrystalline structure, with a tendency to adopt a (111) texture upon the thermal treatment. Moreover, thermal treatment (annealing or flaming) of the as‐prepared films also substantially improves their chemical and mechanical robustness. F films behave as bulk Pt in terms of electrical resistivity and suitability as working electrodes in cyclic voltammetry experiments. Overall, the unique combination of these excellent features: homogeneity, robustness, and conductivity, in addition to the high optical transparency in the 300–800 nm range of the electromagnetic spectrum, make ultrathin Pt films appropriate for a variety of applications in the field of molecular optoelectronics. The formation of functional molecular self‐assembled monolayers (SAMs) on these transparent, conductive films allows their optical monitoring using transmission optical spectroscopy, as well as the probing of their electrical properties. The potential of such Pt films as suitable metal substrates in opto‐ and nanoelectronics is proven by representative applications, including switching of prototypical photochromic and electrochromic species in SAMs and molecule–metal junctions.     

Highly Conductive and Environmentally Stable Organic Transparent Electrodes Laminated with Graphene

Improving the lifetime and the operational and thermal stability of organic thin‐film materials while maintaining high conductivity and mechanical flexibility is critical for flexible electronics applications. Here, it is reported that highly conductive and environmentally stable organic transparent electrodes (TEs) can be fabricated by mechanically laminating poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) films containing dimethylsulfoxide and Zonyl fluorosurfactant (PDZ films) with a monolayer graphene barrier. The proposed lamination process allows graphene to be coated onto the PDZ films uniformly and conformally with tight interfacial binding, free of wrinkles and air gaps. The laminated films exhibit an outstanding room‐temperature hole mobility of ≈85.1 cm² V^?1 s^?1 since the graphene can serve as an effective bypass for charge carriers. The significantly improved stability of the graphene‐laminated TEs against high mechanical/thermal stress, humidity, and ultraviolet irradiation is particularly promising. Furthermore, the incorporation of the graphene barrier increases the expected lifetime of the TEs by more than two orders of magnitude.     

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.     

Highly Flexible Transparent Electrodes Containing Ultrathin Silver for Efficient Polymer Solar Cells

Transparent electrodes (TEs) having electrooptical trade‐offs better than state‐of‐the‐art indium tin oxide (ITO) are continuously sought as they are essential to enable flexible electronic and optoelectronic devices. In this work, a TiO₂‐Ag‐ITO (TAI)‐based TE is introduced and its use is demonstrated in an inverted polymer solar cell (I‐PSCs). Thanks to the favorable nucleation and wetting conditions provided by the TiO₂, the ultrathin silver film percolates and becomes continuous with high smoothness at very low thicknesses (3–4 nm), much lower than those required when it is directly deposited on a plastic or glass substrate. Compared to conventional ITO‐TE, the proposed TAI‐TE exhibits exceptionally lower electrical sheet resistance (6.2 Ω sq^?1), higher optical transmittance, a figure‐of‐merit two times larger, and mechanical flexibility, the latter confirmed by the fact that the resistance increases only 6.6% after 10³ tensile bending cycles. The I‐PSCs incorporating the TAI‐TE show record power conversion efficiency (8.34%), maintained at 96% even after 400 bending cycles.     

Reduced Graphene Oxide Micromesh Electrodes for Large Area,Flexible, Organic Photovoltaic Devices

A laser‐based patterning technique—compatible with flexible, temperature‐sensitive substrates—for the production of large area reduced graphene oxide micromesh (rGOMM) electrodes is presented. The mesh patterning can be accurately controlled in order to significantly enhance the electrode transparency, with a subsequent slight increase in the sheet resistance, and therefore improve the tradeoff between transparency and conductivity of reduced graphene oxide (rGO) layers. In particular, rGO films with an initial transparency of ≈20% are patterned, resulting in rGOMMs films with a ≈59% transmittance and a sheet resistance of ≈565 Ω sq^?1, that is significantly lower than the resistance of ≈780 Ω sq^?1, exhibited by the pristine rGO films at the same transparency. As a proof‐of‐concept application, rGOMMs are used as the transparent electrodes in flexible organic photovoltaic (OPV) devices, achieving power conversion efficiency of 3.05%, the highest ever reported for flexible OPV devices incorporating solution‐processed graphene‐based electrodes. The controllable and highly reproducible laser‐induced patterning of rGO hold enormous promise for both rigid and flexible large‐scale organic electronic devices, eliminating the lag between graphene‐based and indium–tin oxide electrodes, while providing conductivity and transparency tunability for next generation flexible electronics.     

Trilayer Nanomesh Films with Tunable Wettability as Highly Transparent,Flexible, and Recyclable Electrodes

Metallic mesh materials are promising candidates to replace traditional transparent conductive oxides such as indium tin oxide (ITO) that is restricted by the limited indium resource and its brittle nature. The challenge of metal based transparent conductive networks is to achieve high transmittance, low sheet resistance, and small perforation size simultaneously, all of which significantly relate to device performances in optoelectronics. In this work, trilayer dielectric/metal/dielectric (D/M/D) nanomesh electrodes are reported with precisely controlled perforation size, wire width, and uniform hole distribution employing the nanosphere lithography technique. TiO₂/Au/TiO₂ nanomesh films with small hole diameter (≤700 nm) and low thickness (≤50 nm) are shown to yield high transmittance (>90%), low sheet resistance (≤70 Ω sq^?1), as well as outstanding flexural endurance and feasibility for large area patterning. Further, by tuning the surface wettability, these films are applied as easily recyclable flexible electrodes for electrochromic devices. The simple and cost‐effective fabrication of diverse D/M/D nanomesh transparent conductive films with tunable optoelectronic properties paves a way for the design and realization of specialized transparent electrodes in optoelectronics.     

Uniformly Interconnected Silver‐Nanowire Networks for Transparent Film Heaters

The fabrication and design principles for using silver‐nanowire (AgNW) networks as transparent electrodes for flexible film heaters are described. For best practice, AgNWs are synthesized with a small diameter and network structures of the AgNW films are optimized, demonstrating a favorably low surface resistivity in transparent layouts with a high figure‐of‐merit value. To explore their potential in transparent electrodes, a transparent film heater is constructed based on uniformly interconnected AgNW networks, which yields an effective and rapid heating of the film at low input voltages. In addition, the AgNW‐based film heater is capable of accommodating a large amount of compressive or tensile strains in a completely reversible fashion, thereby yielding an excellent mechanical flexibility. The AgNW networks demonstrated here possess attractive features for both conventional and emerging applications of transparent flexible electrodes.     

3D Micromolding of Arrayed Waveguide Gratings on Upconversion Luminescent Layers for Flexible Transparent Displays without Mirrors,Electrodes, and Electric Circuits

A new technique for the fabrication of arrayed waveguide gratings on upconversion luminescent layers for flexible transparent displays is reported. Ho³⁺‐ and Yb³⁺‐codoped NaYF₄ nanoparticles are synthesized by hydrothermal techniques. Transparent films consisting of two transparent polymers on the NaYF₄ nanoparticle films exhibit mechanical flexibility and high transparence in visible region. Patterned NaYF₄ nanoparticle films are fabricated by calcination‐free micromolding in capillaries. Arrayed waveguide gratings consisting of the two transparent polymers are formed on the patterned NaYF₄ nanoparticle films by micromolding in capillaries. Green and red luminescence is observed from the upconversion luminescent layers of the NaYF₄ nanoparticle films in the arrayed waveguide gratings under excitation at 980 nm laser light. Arrayed waveguide gratings on the upconversion luminescent layers are fabricated with Er³⁺‐doped NaYF₄ nanoparticles which can convert two photons at 850 and 1500 nm into single photon at 550 nm. These results demonstrate that flexible transparent displays can be fabricated by constructing arrayed waveguide gratings on upconversion luminescent layers, which can operate in nonprojection mode without mirrors, transparent electrodes, and electric circuits.     

ITO‐Free and Flexible Organic Photovoltaic Device Based on High Transparent and Conductive Polyaniline/Carbon Nanotube Thin Films

The synthesis and characterization of thin films of polyaniline/carbon nanotubes nanocomposites is reported, as well as their utilization as transparent electrodes in ITO‐free organic photovoltaic devices. These films are generated by interfacial synthesis, which provides them with the unique ability to be deposited onto any substrate as transparent films, thus enabling the production of flexible solar cells using substrates like PET. Very high carbon nanotube loadings can be achieved using these films without significantly affecting their transparency (≈80–90% transmittance at 550 nm). Sheet resistances as low as 300 Ω/□ are obtained using secondary polyaniline doping in the presence of carbon nanotubes. These films present excellent mechanical stability, exhibiting no lack in performance after 100 bend cycles. Flexible and completely ITO‐free organic photovoltaic devices are built using these films as transparent electrodes, and high efficiencies (up to 2.27%) are achieved.     

Transparent Ultrathin Oxygen‐Doped Silver Electrodes for Flexible Organic Solar Cells

An effective method for depositing highly transparent and conductive ultrathin silver (Ag) electrodes using minimal oxidation is reported. The minimal oxidation of Ag layers significantly improves the intrinsic optical and structural properties of Ag without any degradation of its electrical conductivity. Oxygen‐doped Ag (AgO_x) layers of thicknesses as low as 6 nm exhibit completely 2D and continuous morphologies on ZnO films, smaller optical reflections and absorbances, and smaller sheet resistances compared with those of discontinuous and granular‐type Ag layers of the same thickness. A ZnO/AgO_x/ZnO (ZAOZ) electrode using an AgO_x (O/Ag = 3.4 at%) layer deposited on polyethylene terephthalate substrates at room temperature shows an average transmittance of 91%, with a maximum transmittance of 95%, over spectral range 400?1000 nm and a sheet resistance of 20 Ω sq^?1. The average transmittance value is increased by about 18% on replacing a conventional ZnO/Ag/ZnO (ZAZ) electrode with the ZAOZ electrode. The ZAOZ electrode is a promising bottom transparent conducting electrode for highly flexible inverted organic solar cells (IOSCs), and it achieves a power conversion efficiency (PCE) of 6.34%, whereas an IOSC using the ZAZ electrode exhibits a much lower PCE of 5.65%.     

“Regioselective Deposition” Method to Pattern Silver Electrodes Facilely and Efficiently with High Resolution: Towards All‐Solution‐Processed,High‐Performance,Bottom‐Contacted,Flexible, Polymer‐Based Electronics

“Regioselectivity deposition” method is developed to pattern silver electrodes facilely and efficiently by solution‐process with high resolution (down to 2 μm) on different substrates in A4 paper size. With the help of this method, large‐area, flexible, high‐performance polymer field‐effect transistors based on the silver electrodes and polyimide insulator are fabricated with bottom‐contact configuration by all‐solution processes. The polymer devices exhibit high performance with average field‐effect mobility over 1.0 cm² V^?1 s^?1 (the highest mobility up to 1.5 cm² V^?1 s^?1) and excellent environmental stability and flexibility, indicating the cost effectiveness of this method for practical applications in organic electronics.     

Epidermal Supercapacitor with High Performance

Recent development in epidermal and bionic electronics systems has promoted the increasing demand for supercapcacitors with micrometer‐thickness and good compatibility. Here, a highly flexible free‐standing epidermal supercapacitor (SC‐E) with merely 1 μm thickness and high performance is developed. Single‐walled carbon nanotube/poly(3,4‐ethylenedioxythiophene) hybrid films with unique inner‐connected reticulation are adopted as electrodes for ultrathin structure and high electric conductivity. Then, based on two substrates with different surface energies, a stepwise lift‐off method is presented to peel off the ultrathin integrated supercapacitor from the substrates nondestructively. As a result of the high conductive hybrid electrodes and the thin electrolyte layer, the as‐designed supercapacitors (based on the total mass of two electrodes) achieve a good capacitance of 56 F g^?1 and a superhigh power density of 332 kW kg^?1, which manifest superior performance in contrast to the other devices fabricated by traditional electrodes. Meanwhile, the ultrashort response time of 11.5 ms enables the epidermal supercapacitor (SC‐E) work for high‐power units. More importantly, the free‐standing structure and outstanding flexibility (10⁵ times bending) endow the SC‐E with excellent compatibility to be integrated and work in the next generation of smart and epidermal systems.     

A Transparent, High Barrier, and High Heat Substrate for Organic Electronics

The use of plastic film substrates for organic electronic devices promises to enable new applications, such as flexible displays and conformal lighting, and a new low-cost paradigm through high-volume roll-to-roll fabrication. Unfortunately, presently available substrates cannot yet deliver this promise because of the challenge in achieving the required combination of optical transparency, impermeability to water and oxygen, mechanical flexibility, high-temperature capability, and chemical resistance. Here, we describe the development and performance of a plastic substrate comprising a high heat polycarbonate film combined with a unique transparent coating package that is aimed at meeting this challenge.     

Wearable Force Touch Sensor Array Using a Flexible and Transparent Electrode

Transparent electrodes have been widely used for various electronics and optoelectronics, including flexible ones. Many nanomaterial‐based electrodes, in particular 1D and 2D nanomaterials, have been proposed as next‐generation transparent and flexible electrodes. However, their transparency, conductivity, large‐area uniformity, and sometimes cost are not yet sufficient to replace indium tin oxide (ITO). Furthermore, the conventional ITO is quite rigid and susceptible to mechanical fractures under deformations (e.g., bending, folding). In this study, the authors report new advances in the design, fabrication, and integration of wearable and transparent force touch (touch and pressure) sensors by exploiting the previous efforts in stretchable electronics as well as novel ideas in the transparent and flexible electrode. The optical and mechanical experiment, along with simulation results, exhibit the excellent transparency, conductivity, uniformity, and flexibility of the proposed epoxy‐copper‐ITO (ECI) multilayer electrode. By using this multi‐layered ECI electrode, the authors present a wearable and transparent force touch sensor array, which is multiplexed by Si nanomembrane p‐i‐n junction‐type (PIN) diodes and integrated on the skin‐mounted quantum dot light‐emitting diodes. This novel integrated system is successfully applied as a wearable human–machine interface (HMI) to control a drone wirelessly. These advances in novel material structures and system‐level integration strategies create new opportunities in wearable smart displays.