Highly Efficient (>10%) Flexible Organic Solar Cells on PEDOT‐Free and ITO‐Free Transparent Electrodes

A novel approach to fabricate flexible organic solar cells is proposed without indium tin oxide (ITO) and poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) using junction‐free metal nanonetworks (NNs) as transparent electrodes. The metal NNs are monolithically etched using nanoscale shadow masks, and they exhibit excellent optoelectronic performance. Furthermore, the optoelectrical properties of the NNs can be controlled by both the initial metal layer thickness and NN density. Hence, with an extremely thin silver layer, the appropriate density control of the networks can lead to high transmittance and low sheet resistance. Such NNs can be utilized for thin‐film devices without planarization by conductive materials such as PEDOT:PSS. A highly efficient flexible organic solar cell with a power conversion efficiency (PCE) of 10.6% and high device yield (93.8%) is fabricated on PEDOT‐free and ITO‐free transparent electrodes. Furthermore, the flexible solar cell retains 94.3% of the initial PCE even after 3000 bending stress tests (strain: 3.13%).     

“Quasi‐freestanding” Graphene‐on‐Single Walled Carbon Nanotube Electrode for Applications in Organic Light‐emitting Diode

An air‐stable transparent conductive film with “quasi‐freestanding” graphene supported on horizontal single walled carbon nanotubes (SWCNTs) arrays is fabricated. The sheet resistance of graphene films stacked via layer‐by‐layer transfer (LBL) on quartz, and modified by 1‐Pyrenebutyric acid N‐hydroxysuccinimide ester (PBASE), is reduced from 273 Ω/sq to about 76 Ω/sq. The electrical properties are stable to heat treatment (up to 200 ºC) and ambient exposure. Organic light‐emitting diodes (OLEDs) constructed of this carbon anode (T ≈ 89.13% at 550 nm) exhibit ≈88% power efficiency of OLEDs fabricated on an ITO anode (low turn on voltage ≈3.1 eV, high luminance up to ≈29 490 cd/m², current efficiency ≈14.7 cd/A). Most importantly, the entire graphene‐on‐SWCNT hybrid electrodes can be transferred onto plastic (PET) forming a highly‐flexible OLED device, which continues to function without degradation in performance at bending angles >60°.     

Reverse‐Offset Printed Ultrathin Ag Mesh for Robust Conformal Transparent Electrodes for High‐Performance Organic Photovoltaics

Mechanically durable transparent electrodes are needed in flexible optoelectronic devices to realize their long‐term stable functioning, for applications in various fields such as energy, healthcare, and soft robotics. Several promising transparent electrodes based on nanomaterials have been previously reported to replace the conventional and fragile indium‐tin oxide (ITO); however, obtaining feasible printed transparent electrodes for ultraflexible devices with a multistack structure is still a great challenge. Here, a printed ultrathin (uniform thickness of 100 nm) Ag mesh transparent electrode is demonstrated, simultaneously achieving high conductance, high transparency, and good mechanical properties. It shows a 17 Ω sq^?1 sheet resistance (R_sh) with 93.2% transmittance, which surpasses the performance of sputtered ITO electrodes and other ultrathin Ag mesh transparent electrodes. The conductance is stable after 500 cycles of 100% stretch/release deformation, with an insignificant increase (10.6%) in R_sh by adopting a buckling structure. Furthermore, organic photovoltaics (OPVs) using our Ag mesh transparent electrodes achieve a power conversion efficiency of 8.3%, which is comparable to the performance of ITO‐based OPVs.     

High‐Performance Flexible Transparent Electrode with an Embedded Metal Mesh Fabricated by Cost‐Effective Solution Process

A new structure of flexible transparent electrodes is reported, featuring a metal mesh fully embedded and mechanically anchored in a flexible substrate, and a cost‐effective solution‐based fabrication strategy for this new transparent electrode. The embedded nature of the metal‐mesh electrodes provides a series of advantages, including surface smoothness that is crucial for device fabrication, mechanical stability under high bending stress, strong adhesion to the substrate with excellent flexibility, and favorable resistance against moisture, oxygen, and chemicals. The novel fabrication process replaces vacuum‐based metal deposition with an electrodeposition process and is potentially suitable for high‐throughput, large‐volume, and low‐cost production. In particular, this strategy enables fabrication of a high‐aspect‐ratio (thickness to linewidth) metal mesh, substantially improving conductivity without considerably sacrificing transparency. Various prototype flexible transparent electrodes are demonstrated with transmittance higher than 90% and sheet resistance below 1 ohm sq^?1, as well as extremely high figures of merit up to 1.5 × 10⁴, which are among the highest reported values in recent studies. Finally using our embedded metal‐mesh electrode, a flexible transparent thin‐film heater is demonstrated with a low power density requirement, rapid response time, and a low operating voltage.     

A Biodegradable and Stretchable Protein‐Based Sensor as Artificial Electronic Skin for Human Motion Detection

Due to the natural biodegradability and biocompatibility, silk fibroin (SF) is one of the ideal platforms for on‐skin and implantable electronic devices. However, the development of SF‐based electronics is still at a preliminary stage due to the SF film intrinsic brittleness as well as the solubility in water, which prevent the fabrication of SF‐based electronics through traditional techniques. In this article, a flexible and stretchable silver nanofibers (Ag NFs)/SF based electrode is synthesized through water‐free procedures, which demonstrates outstanding performance, i.e., low sheet resistance (10.5 Ω sq^?1), high transmittance (>90%), excellent stability even after bending cycles >2200 times, and good extensibility (>60% stretching). In addition, on the basis of such advanced (Ag NFs)/SF electrode, a flexible and tactile sensor is further fabricated, which can simultaneously detect pressure and strain signals with a large monitoring window (35 Pa–700 kPa). Besides, this sensor is air‐permeable and inflammation‐free, so that it can be directly laminated onto human skins for long‐term health monitoring. Considering the biodegradable and skin‐comfortable features, this sensor may become promising to find potential applications in on‐skin or implantable health‐monitoring devices.     

Lithium Titanate Cuboid Arrays Grown on Carbon Fiber Cloth for High‐Rate Flexible Lithium‐Ion Batteries

High‐rate performance flexible lithium‐ion batteries are desirable for the realization of wearable electronics. The flexibility of the electrode in the battery is a key requirement for this technology. In the present work, spinel lithium titanate (Li₄Ti₅O₁₂, LTO) cuboid arrays are grown on flexible carbon fiber cloth (CFC) to fabricate a binder‐free composite electrode (LTO@CFC) for flexible lithium‐ion batteries. Experimental results show that the LTO@CFC electrode exhibits a remarkably high‐rate performance with a capacity of 105.8 mAh g^?1 at 50C and an excellent electrochemical stability against cycling (only 2.2% capacity loss after 1000 cycles at 10C). A flexible full cell fabricated with the LTO@CFC as the anode and LiNi_0.5Mn_1.5O₄ coated on Al foil as the cathode displays a reversible capacity of 109.1 mAh g^?1 at 10C, an excellent stability against cycling and a great mechanical stability against bending. The observed high‐rate performance of the LTO@CFC electrode is due to its unique corn‐like architecture with LTO cuboid arrays (corn kernels) grown on CFC (corn cob). This work presents a new approach to preparing LTO‐based composite electrodes with an architecture favorable for ion and electron transport for flexible energy storage devices.     

Pressure Welding of Silver Nanowires Networks at Room Temperature as Transparent Electrodes for Efficient Organic Light‐Emitting Diodes

In this work, polymethylmethacrylate (PMMA) as a superior mediate for the pressure welding of silver nanowires (Ag NWs) networks as transparent electrodes without any thermal treatment is demonstrated. After a pressing of 200 kg cm^?2, not only the sheet resistance but also the surface roughness of the PMMA‐mediated Ag NWs networks decreases from 2.6 kΩ sq^?1 to 34.3 Ω sq^?1 and from 76.1 to 12.6 nm, respectively. On the other hand, high transparency of an average transmittance in the visible wavelengths of 93.5% together with a low haze value of 2.58% can be achieved. In terms of optoelectronic applications, the promising potential of the PMMA‐mediated pressure‐welded Ag NWs networks used as a transparent electrode in a green organic light‐emitting diode (OLED) device is also demonstrated. In comparison with the OLED based on commercial tin‐doped indium oxide electrode, the increments of power efficiency and external quantum efficiency (EQE) from 80.1 to 85.9 lm w^?1 and 19.2% to 19.9% are demonstrated. In addition, the PMMA‐mediated pressure welding succeeds in transferring Ag NWs networks to flexible polyethylene naphthalate and polyimide substrates with the sheet resistance of 42 and 91 Ω sq^?1 after 10 000 times of bending, respectively.     

Ultraflexible Transparent Bio‐Based Polymer Conductive Films Based on Ag Nanowires

The unstable mechanical properties of flexible transparent conductive films (TCFs) make it difficult for them to meet the requirements for displays or wearable devices. Here, the relationship between the mechanism behind the bending behavior and the electrical properties, which is important for improving the mechanical stability of flexible TCFs, is explored. Flexible TCFs are reported based on silver nanowires (AgNWs) and bio‐based poly(ethylene‐co‐1,4‐cyclohexanedimethylene 2,5‐furandicarboxylate)s (PECFs), with a low sheet resistance (23.8 Ω sq^?1 at 84.6% transmittance) and superior mechanical properties. The electrical properties of the AgNW/PECFs composite film show almost no change after bending for 2000 times.     

Roll‐to‐Roll Production of Graphene Hybrid Electrodes for High‐Efficiency,Flexible Organic Photoelectronics

Despite nearly two decades of research, the absence of ideal, flexible, and transparent electrodes has been the biggest bottleneck for realizing flexible and printable electronics via roll‐to‐roll (R2R) method. A fabrication of poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate):graphene:ethyl cellulose (PEDOT:PSS:G:EC) hybrid electrodes by R2R process, which allows for the elimination of strong acid treatment. The high‐performance flexible printable electrode includes a transmittance (T) of 78% at 550 nm and a sheet resistance of 13 Ω sq⁻¹ with excellent mechanical stability. These features arise from the PSS interacting strongly with the ethyoxyl groups from EC promoting a favorable phase separation between PEDOT and PSS chains, and the highly uniform and conductive G:EC enable rearrangement of the PEDOT chains with more expanded conformation surrounded by G:EC via the π–π interaction between G:EC and PEDOT. The hybrid electrodes are fully functional as universal electrodes for outstanding flexible electronic applications. Organic solar cells based on the hybrid electrode exhibit a high power conversion efficiency of 9.4% with good universality for active layer. Moreover, the organic light‐emitting diodes and photodetector devices hold the same level to or outperform those based on indium tin oxide flexible transparent electrodes.     

Hybrid Copper‐Nanowire–Reduced‐Graphene‐Oxide Coatings: A “Green Solution” Toward Highly Transparent,Highly Conductive,and Flexible Electrodes for (Opto)Electronics

This study reports a novel green chemistry approach to assemble copper‐nanowires/reduced‐graphene‐oxide hybrid coatings onto inorganic and organic supports. Such films are robust and combine sheet resistances (<30 Ω sq^?1) and transparencies in the visible region (transmittance > 70%) that are rivalling those of indium–tin oxide. These electrodes are suitable for flexible electronic applications as they show a sheet resistance change of <4% after 10 000 bending cycles at a bending radius of 1.0 cm, when supported on polyethylene terephthalate foils. Significantly, the wet‐chemistry method involves the preparation of dispersions in environmentally friendly solvents and avoids the use of harmful reagents. Such inks are processed at room temperature on a wide variety of surfaces by spray coating. As a proof‐of‐concept, this study demonstrates the successful use of such coatings as electrodes in high‐performance electrochromic devices. The robustness of the electrodes is demonstrated by performing several tens of thousands of cycles of device operation. These unique conducting coatings hold potential for being exploited as transparent electrodes in numerous optoelectronic applications such as solar cells, light‐emitting diodes, and displays.     

Wearable Large‐Scale Perovskite Solar‐Power Source via Nanocellular Scaffold

Dramatic advances in perovskite solar cells (PSCs) and the blossoming of wearable electronics have triggered tremendous demands for flexible solar‐power sources. However, the fracturing of functional crystalline films and transmittance wastage from flexible substrates are critical challenges to approaching the high‐performance PSCs with flexural endurance. In this work, a nanocellular scaffold is introduced to architect a mechanics buffer layer and optics resonant cavity. The nanocellular scaffold releases mechanical stresses during flexural experiences and significantly improves the crystalline quality of the perovskite films. The nanocellular optics resonant cavity optimizes light harvesting and charge transportation of devices. More importantly, these flexible PSCs, which demonstrate excellent performance and mechanical stability, are practically fabricated in modules as a wearable solar‐power source. A power conversion efficiency of 12.32% for a flexible large‐scale device (polyethylene terephthalate substrate, indium tin oxide‐free, 1.01 cm²) is achieved. This ingenious flexible structure will enable a new approach for development of wearable electronics.     

Silver‐Quantum‐Dot‐Modified MoO3 and MnO2 Paper‐Like Freestanding Films for Flexible Solid‐State Asymmetric Supercapacitors

Free‐standing paper‐like thin‐film electrodes have great potential to boost next‐generation power sources with highly flexible, ultrathin, and lightweight requirements. In this work, silver‐quantum‐dot‐ (2–5 nm) modified transition metal oxide (including MoO₃ and MnO₂) paper‐like electrodes are developed for energy storage applications. Benefitting from the ohmic contact at the interfaces between silver quantum dots and MoO₃ nanobelts (or MnO₂ nanowires) and the binder‐free nature and 0D/1D/2D nanostructured 3D network of the fabricated electrodes, substantial improvements on the electrical conductivity, efficient ionic diffusion, and areal capacitances of the hybrid nanostructure electrodes are observed. With this proposed strategy, the constructed asymmetric supercapacitors, with Ag quantum dots/MoO₃ “paper” as anode, Ag quantum dots/MnO₂ “paper” as cathode, and neutral Na₂SO₄/polyvinyl alcohol hydrogel as electrolyte, exhibit significantly enhanced energy and power densities in comparison with those of the supercapacitors without modification of Ag quantum dots on electrodes; present excellent cycling stability at different current densities and good flexibility under various bending states; offer possibilities as high‐performance power sources with low cost, high safety, and environmental friendly properties.     

Spontaneously Embedded Scattering Structures in a Flexible Substrate for Light Extraction

A flexible hazy substrate (FHS) with embedded air bubbles to increase light extraction efficiency of organic light‐emitting diodes (OLEDs) is reported. In order to embed the air bubbles in the flexible substrate, micropatterned substrates are fabricated by plasma treatment, and then coated with a planarization layer. During the planarization layer coating, air bubbles are trapped between the substrate and the planarization layer. The haze of the FHS can be controlled from 1.7% to 68.4% by changing the size of micropatterns by adjusting the plasma treatment time. The FHS shows average haze of 68.4%, average total transmittance of 90.3%, and extremely flat surface with average roughness (R _a) of 1.2 nm. Rigorous coupled‐wave analysis and finite‐difference time‐domain simulations are conducted to demonstrate that the air bubbles in the substrate can effectively extract photons that are trapped in the substrate. The FHS increases the power efficiency of OLEDs by 22% and further increases by 91% combined with an external extraction layer. Moreover, the FHS has excellent mechanical flexibility. No defect has been observed after 10 000 bending cycles at bending radius of 4 mm.     

Fully Integrated Design of a Stretchable Solid‐State Lithium‐Ion Full Battery

A solid‐state lithium‐ion battery, in which all components (current collector, anode and cathode, electrolyte, and packaging) are stretchable, is introduced, giving rise to a battery design with mechanical properties that are compliant with flexible electronic devices and elastic wearable systems. By depositing Ag microflakes as a conductive layer on a stretchable carbon–polymer composite, a current collector with a low sheet resistance of ≈2.7 Ω □^?1 at 100% strain is obtained. Stretchable electrodes are fabricated by integrating active materials with the elastic current collector. A polyacrylamide–“water‐in‐salt” electrolyte is developed, offering high ionic conductivity of 10^?3 to 10^?2 S cm^?1 at room temperature and outstanding stretchability up to ≈300% of its original length. Finally, all these components are assembled into a solid‐state lithium‐ion full cell in thin‐film configuration. Thanks to the deformable individual components, the full cell functions when stretched, bent, or even twisted. For example, after stretching the battery to 50%, a reversible capacity of 28 mAh g^?1 and an average energy density of 20 Wh kg^?1 can still be obtained after 50 cycles at 120 mA g^?1, confirming the functionality of the battery under extreme mechanical stress.     

Flexible Wire‐Shaped Supercapacitors in Parallel Double Helix Configuration with Stable Electrochemical Properties under Static/Dynamic Bending

Wire‐shaped flexible supercapacitors (SCs) have aroused much attention due to their small size, light weight, high flexibility, and deformability. However, the previously reported wire‐shaped SCs usually involve complex assembly processes, encounter potential structural instabilities, and the influence of dynamic bending on the electrochemical stability of wire‐shaped SCs is also not clear. Here, a parallel double helix wire‐shaped supercapacitor (PDWS) protocol has been developed with two symmetric titanium@MnO₂ fiber electrodes winded on a flexible nylon fiber by a simple and reliable process. The PDWSs show an operate voltage of 0.8 V, a high capacitance of 15.6 mF cm^–2 and an energy density of 1.4 µWh cm^–2. Due to rational structure design, the PDWSs demonstrate excellent mechanical and electrochemical stability under both static and dynamic deformations. Over 3500 bending cycles, 88.0% of the initial capacitance can still be retained. In terms of dynamic bending, it is found that the cyclic voltammetry curves show periodically fluctuations simultaneously with the bending frequency and the intensity of fluctuation increases with higher bending frequency, while the dynamic capacitance is almost not affected. With extraordinary mechanical flexibility and excellent electrochemical stability, the high performance PDWS is considered to be a promising power source for wearable electronics.     

Bamboo‐Like Nitrogen‐Doped Carbon Nanotube Forests as Durable Metal‐Free Catalysts for Self‐Powered Flexible Li–CO2 Batteries

The Li–CO₂ battery is a promising energy storage device for wearable electronics due to its long discharge plateau, high energy density, and environmental friendliness. However, its utilization is largely hindered by poor cyclability and mechanical rigidity due to the lack of a flexible and durable catalyst electrode. Herein, flexible fiber‐shaped Li–CO₂ batteries with ultralong cycle‐life, high rate capability, and large specific capacity are fabricated, employing bamboo‐like N‐doped carbon nanotube fiber (B‐NCNT) as flexible, durable metal‐free catalysts for both CO₂ reduction and evolution reactions. Benefiting from high N‐doping with abundant pyridinic groups, rich defects, and active sites of the periodic bamboo‐like nodes, the fabricated Li–CO₂ battery shows outstanding electrochemical performance with high full‐discharge capacity of 23 328 mAh g^?1, high rate capability with a low potential gap up to 1.96 V at a current density of 1000 mA g^?1, stability over 360 cycles, and good flexibility. Meanwhile, the bifunctional B‐NCNT is used as the counter electrode for a fiber‐shaped dye‐sensitized solar cell to fabricate a self‐powered fiber‐shaped Li–CO₂ battery with overall photochemical–electric energy conversion efficiency of up to 4.6%. Along with a stable voltage output, this design demonstrates great adaptability and application potentiality in wearable electronics with a breath monitor as an example.     

Highly Deformable and See‐Through Polymer Light‐Emitting Diodes with All‐Conducting‐Polymer Electrodes

Despite the high expectation of deformable and see‐through displays for future ubiquitous society, current light‐emitting diodes (LEDs) fail to meet the desired mechanical and optical properties, mainly because of the fragile transparent conducting oxides and opaque metal electrodes. Here, by introducing a highly conductive nanofibrillated conducting polymer (CP) as both deformable transparent anode and cathode, ultraflexible and see‐through polymer LEDs (PLEDs) are demonstrated. The CP‐based PLEDs exhibit outstanding dual‐side light‐outcoupling performance with a high optical transmittance of 75% at a wavelength of 550 nm and with an excellent mechanical durability of 9% bending strain. Moreover, the CP‐based PLEDs fabricated on 4 µm thick plastic foils with all‐solution processing have extremely deformable and foldable light‐emitting functionality. This approach is expected to open a new avenue for developing wearable and attachable transparent displays.     

Highly Reliable Ag Nanowire Flexible Transparent Electrode with Mechanically Welded Junctions

Deformation behavior of the Ag nanowire flexible transparent electrode under bending strain is studied and results in a novel approach for highly reliable Ag nanowire network with mechanically welded junctions. Bending fatigue tests up to 500 000 cycles are used to evaluate the in situ resistance change while imposing fixed, uniform bending strain. In the initial stages of bending cycles, the thermally annealed Ag nanowire networks show a reduction in fractional resistance followed by a transient and steady‐state increase at later stages of cycling. SEM analysis reveals that the initial reduction in resistance is caused by mechanical welding as a result of applied bending strain, and the increase in resistance at later stages of cycling is determined to be due to the failure at the thermally locked‐in junctions. Based on the observations from this study, a new methodology for highly reliable Ag nanowire network is proposed: formation of Ag nanowire networks with no prior thermal annealing but localized junction formation through simple application of mechanical bending strain. The non‐annealed, mechanically welded Ag nanowire network shows significantly enhanced cyclic reliability with essentially 0% increase in resistance due to effective formation of localized wire‐to‐wire contact.     

Fatigue‐Free,Electrically Reliable Copper Electrode with Nanohole Array

Design and fabrication of reliable electrodes is one of the most important challenges in flexible devices, which undergo repeated deformation. In conventional approaches, mechanical and electrical properties of continuous metal films degrade gradually because of the fatigue damage. The designed incorporation of nanoholes into Cu electrodes can enhance the reliability. In this study, the electrode shows extremely low electrical resistance change during bending fatigue because the nanoholes suppress crack initiation by preventing protrusion formation and damage propagation by crack tip blunting. This concept provides a key guideline for developing fatigue‐free flexible electrodes.     

An Optically Flat Conductive Outcoupler Using Core/Shell Ag/ZnO Nanochurros

Transparent conductive electrodes (TCEs) featuring a smooth surface are indispensable for preserving pristine electrical characteristics in optoelectronic and transparent electronic devices. For high‐efficiency organic light emitting diodes (OLEDs), a high outcoupling efficiency, which is crucial, is only achieved by incorporating a wavelength‐scale undulating surface into a TCE layer, but this inevitably degrades device performance. Here, an optically flat, high‐conductivity TCE composed of core/shell Ag/ZnO nanochurros (NCs) is reported embedded within a resin film on a polyethylene terephthalate substrate, simultaneously serving as an efficient outcoupler and a flexible substrate. The ZnO NCs are epitaxially grown on the {100} planes of a pentagonal Ag core and the length of ZnO shells is precisely controlled by the exposure time of Xe lamp. Unlike Ag nanowires films, the Ag/ZnO NCs films markedly boost the optical tunneling of light. Green‐emitting OLEDs (2.78 × 3.5 mm²) fabricated with the Ag/ZnO TCE exhibit an 86% higher power efficiency at 1000 cd m^?2 than ones with an Sn‐doped indium oxide TCE. A full‐vectorial electromagnetic simulation suggests the suppression of plasmonic absorption losses within their Ag cores. These results provide a feasibility of multifunctional TCEs with synthetically controlled core/shell nanomaterials toward the development of high‐efficiency LED and solar cell devices.