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.     

Optically Transparent and Mechanically Robust Ionic Hydrogel Electrodes for Bright Electroluminescent Devices Achieving High Stretchability Over 1400%

To realize wearable displays and interactive soft robots, significant research efforts are focused on developing highly deformable alternating-current electroluminescent (ACEL) devices. Although soft emission layers are well developed, designing stretchable, conductive, and transparent soft electrodes remains challenging. In this study, ionic hydrogels are prepared comprising a double network (DN) of poly(N-hydroxyethylacrylamide-co-acrylamide)/crosslinked chitosan swollen in aqueous lithium bis(trifluoromethanesulfonyl) imide. Owing to the finely tuned DN structure of the polymeric crosslinker and transparent electrolyte, the developed ionic hydrogels exhibit remarkable stretchability (1400%), excellent optical transmittance (>99%), and high conductivity (1.95 × 10⁻² Sm⁻¹). Based on the high performance of the ionic hydrogels, ACEL devices are fabricated with an emission layer containing phosphor microparticles and demonstrate stable, high luminance under extreme deformation, and ultra-high elongation. The excellent transparency of the ionic hydrogel further enables the fabrication of novel soft ACEL devices with tandem structures by stacking several emission and electrode layers, in which each emission layer is independently controlled with a switch circuit.     

Transparent conductive PVP/AgNWs films for flexible organic light emitting diodes by spraying method

In this study, a simple spraying method is used to prepare the transparent conductive films (TCFs) based on Ag nanowires (AgNWs). Polyvinylpyrrolidone (PVP) is introduced to modify the interface of substrate. The transmittance and bending performance are improved by optimizing the number of spraying times and the solution concentration and controlling the annealing time. The spraying times of 20, the concentration of 2 mg/mL and the annealing time of 10 min are chosen to fabricate the PVP/AgNWs films. The transmittance of PVP/AgNWs films is 53.4%—67.9% at 380—780 nm, and the sheet resistance is 30 Ω/□ which is equivalent to that of commercial indium tin oxide (ITO). During cyclic bending tests to 500 cycles with bending radius of 5 mm, the changes of resistivity are negligible. The performance of PVP/AgNW transparent electrodes has little change after being exposed to the normal environment for 1 000 h. The adhesion to polymeric substrate and the ability to endure bending stress in AgNWs network films are both significantly improved by introducing PVP. Spraying method makes AgNWs form a stratified structure on large-area polymer substrates, and the vacuum annealing method is used to weld the AgNWs together at junctions and substrates, which can improve the electrical conductivity. The experimental results indicate that PVP/AgNW transparent electrodes can be used as transparent conductive electrodes in flexible organic light emitting diodes (OLEDs).     

Large-Area Flexible Organic Solar Cells with a Robust Silver Nanowire-Polymer Composite as Transparent Top Electrode

Upscaling of efficient flexible organic solar cells (OSCs) is still a challenging task, where flexible transparent electrode is a key limiting factor. Silver nanowires (AgNWs) are widely used as flexible transparent electrodes to fabricate efficient small-area flexible OSCs, but the high surface roughness of AgNWs electrodes causes large leakage current and performance deterioration in large-area OSCs. In this study, it is reported that a strategy of switching the bottom AgNWs electrode and the top Ag film electrode to avoid the detrimental effect of the high surface roughness of AgNWs electrodes. Mechanical robustness of the AgNWs has been enhanced by introducing a cross-linked poly(sodium 4-styrenesulfonate) layer. The AgNWs-polymer transparent film is fabricated by water transfer printing as the top electrode. 21 cm² flexible organic modules containing 10 sub-cells are fabricated and delivered power conversion efficiencies of 12.3% with the design of switched electrodes.     

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.     

Aligned Silver Nanowires Enabled Highly Stretchable and Transparent Electrodes with Unusual Conductive Property

Transparent conductors for the next generation of soft electronic devices need to be highly stretchable, conductive, and transparent, while an inevitable challenge lies in enhancing them simultaneously. Cost‐effective silver nanowires (AgNWs) are widely used but the conventional random network yields a high junction resistance as well as degraded conductivity in the stretched state. Here, a novel, facile, and versatile agitation‐assisted assembly approach is reported to control the orientation direction and density of AgNWs and to layer‐by‐layer deposit the AgNWs monolayer or multilayers onto the prestrained soft substrate. This electrode demonstrates an unprecedented low sheet resistance of 2.8 Ω sq^?1 as well as high transparency of 85% and high stretchability of 40%. It is interesting to note that contrary to most other reports, such a device shows higher conductivity in the stretched state compared to the released state.     

Highly conductive PEDOT:PSS film by doping p-toluenesulfonic acid and post-treatment with dimethyl sulfoxide for ITO-free polymer dispersed liquid crystal device

In this paper, the highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film realized by applying the doping technique and the post-treatment process is demonstrated. The conductivity of the spin coated PEDOT:PSS film enhanced greatly from 0.7 S/cm to 736 S/cm after 1.25% of p-toluenesulfonic acid solution (50 wt%) was doped into the PEDOT:PSS aqueous dispersion. The post-treatment using dimethyl sulfoxide further improved the conductivity to 1549 S/cm. The highly conductive PEDOT:PSS film was used as transparent electrode to fabricate ITO-free polymer dispersed liquid crystal (PDLC) cell. The experimental results showed that the electro-optical properties of the PDLC cell fabricated by the highly conductive PEDOT:PSS film were comparable to those of the PDLC cell constructed by ITO. This study reveals that the highly conductive PEDOT:PSS film is a prospective material for manufacturing ITO-free liquid crystal devices.     

Breathable and Flexible Polymer Membranes with Mechanoresponsive Electric Resistance

Flexible low‐resistance membranes play an important role in soft electronics as sensors for robotics, body movement monitoring, nanogenerators to collect kinetic energy from body movements, and flexible batteries. Despite great efforts, low‐resistance, mechanically stable large‐dimensional membranes that tolerate very high deformability without sacrificing resistance produce low joule heating and allow passage of gases for human comfort are still being sought. Here, one of the solutions is provided by sandwiching a network of silver nanowires (AgNWs) between two highly porous electrospun thermoplastic polyurethane (TPU) membranes. The membranes are mechanically robust (both for bending and stretching) with a strong interface and large strain before breakage (more than 700%). The sheet resistance is as low as <0.1 (±0.01) Ω sq^?1, and changed to only 1.6 (±0.43) Ω sq^?1 upon stretching to 100% strain. The combination of polymer elasticity and the AgNW network structure provides a reversible change in resistance beyond 100% strain. A detailed thermographic analysis is employed to in situ image and characterize the AgNW network morphology during various stretched conditions. It is believed that this flexible, sandwich‐like, electrically conductive membrane is a good candidate for smart wearable devices and soft robots.     

Highly Stable Ag–Au Core–Shell Nanowire Network for ITO-Free Flexible Organic Electrochromic Device

Solid and flexible electrochromic (EC) devices require a delicate design of every component to meet the stringent requirements for transparency, flexibility, and deformation stability. However, the electrode technology in flexible EC devices stagnates, wherein brittle indium tin oxide (ITO) is the primary material. Meanwhile, the inflexibility of metal oxide usually used in an active layer and the leakage issue of liquid electrolyte further negatively affect EC device performance and lifetime. Herein, a novel and fully ITO-free flexible organic EC device is developed by using Ag–Au core–shell nanowire (Ag–Au NW) networks, EC polymer and LiBF₄/propylene carbonate/poly(methyl methacrylate) as electrodes, active layer, and solid electrolyte, respectively. The Ag–Au NW electrode integrated with a conjugated EC polymer together display excellent stability in harsh environments due to the tight encapsulation by the Au shell, and high area capacitance of 3.0 mF cm⁻² and specific capacitance of 23.2 F g⁻¹ at current density of 0.5 mA cm⁻². The device shows high EC performance with reversible transmittance modulation in the visible region (40.2% at 550 nm) and near-infrared region ( − 68.2% at 1600 nm). Moreover, the device presents excellent flexibility ( > 1000 bending cycles at the bending radius of 5 mm) and fast switching time (5.9 s).     

Multifunctional Flexible Biointerfaces for Simultaneous Colocalized Optophysiology and Electrophysiology

Recent developments in optophysiology techniques such as optogenetics have revolutionized the ability to actuate cell activity. Further combining optophysiology and electrophysiology will integrate the advantages from both optical and electrical modalities and yield enabling technologies that allow simultaneous monitoring of cellular activity in response to modulation, which are crucial for biomedical applications. However, multifunctional devices that can deliver optical stimuli to regions beneath the electrodes and perform simultaneous sensing remain largely unexplored. Existing transparent microelectrode technologies depend on external bulk optical instruments for optical interventions. Here, innovative monolithic integrated multifunctional microsystems are demonstrated by applying transparent nanogrid electrodes onto microscale light sources to permit simultaneous electrophysiology and optical modulation at the same anatomical site. The nanogrid electrodes have transmittances > 70% with a low normalized impedance of 5.9 Ω cm². Additional features of the devices include superior mechanical flexibility, minimized light‐induced electrical artifacts, and excellent biocompatibility. Ex vivo experiments demonstrate that the multifunctional devices can record abnormal heart rhythm in transgenic mouse hearts and simultaneously restore the sinus rhythm via optogenetic pacing. This work provides a versatile approach for constructing multifunctional colocalized biointerfaces containing crosstalk‐free optical and electrical modalities with expanded opportunities in both fundamental and applied biomedical research.     

Percolating Network of Ultrathin Gold Nanowires and Silver Nanowires toward “Invisible” Wearable Sensors for Detecting Emotional Expression and Apexcardiogram

2 nm thin gold nanowires (AuNWs) have extremely high aspect ratio (≈10 000) and are nanoscale soft building blocks; this is different from conventional silver nanowires (AgNWs), which are more rigid. Here, highly sensitive, stretchable, patchable, and transparent strain sensors are fabricated based on the hybrid films of soft/hard networks. They are mechanically stretchable, optically transparent, and electrically conductive and are fabricated using a simple and cost‐effective solution process. The combination of soft and more rigid nanowires enables their use as high‐performance strain sensors with the maximum gauge factor (GF) of ≈236 at low strain (<5%), the highest stretchability of up to 70% strain, and the optical transparency is from 58.7% to 66.7% depending on the amount of the AuNW component. The sensors can detect strain as low as 0.05% and are energy efficient to operate at a voltage as low as 0.1 V. These attributes are difficult to achieve with a single component of either AuNWs or AgNWs. The outstanding sensing performance indicates their potential applications as “invisible” wearable sensors for biometric information collection, as demonstrated in applications for detecting facial expressions, respiration, and apexcardiogram.     

A simple and effective method via PH1000 modified Ag-Nanowires electrode enable efficient flexible nonfullerene organic solar cells

Flexible transparent electrodes (FTEs) play an important role in determining the performance of flexible organic solar cells (OSCs), Ag-nanowires (AgNWs) with the unique merits of high conductivity, excellent flexibility, and good thermal stability has been taken into more consideration in fabricating highly efficient FTEs. However, the pristine AgNWs film usually suffers a huge surface roughness and incompatibility with the organic absorption layer, thus always leads to a poor power conversion efficiency (PCE). Herein, we demonstrated a simple and effective way through employing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PH1000) to modify the surface of AgNWs to prepare high-quality FTEs. Based on the PH1000 (100 nm)/AgNWs FTEs, the optimized flexible OSC with PM6:Y6 as active layer exhibits a highest PCE of 12.71%, with an open-circuit voltage (V_oc) of 0.814 V, a short-circuit current (J_sc) of 22.61 mA/cm², and a fill factor (FF) of 0.691, respectively. Which is much higher than the PCE (7.20%) of pristine AgNWs FTEs based device. The enhanced device performance was attributed to the improved morphologies both of the FTEs and the active layers, more effective charge transport and collection efficiency, as well as the decreased charge recombination properties. This work provides an efficient way to fabricate high-quality FTEs and realize efficient flexible OSCs.     

Ultrafast Switchable Passive Radiative Cooling Smart Windows with Synergistic Optical Modulation

Switchable passive radiative cooling (PRC) smart windows can modulate sunlight transmission and spontaneously emit heat to outer space through atmospheric transparent window, presenting great potential in building energy conservation. However, realizing stable and on-demand control of the cooling efficiency for PRC materials is still challenging. Herein, an electro-controlled polymer-dispersed liquid crystal (PDLC) smart window showing PRC property is designed and prepared by adding mid-infrared emitting reactive monomers into the conventional PDLC matrix. It is found that not only the electro-optical properties but also the PRC efficiency of PRC PDLC film are tunable by regulating the content of the mid-infrared emitting components, film thickness, and micromorphology. This advanced PRC PDLC material achieves a near/sub-ambient temperature when the solar irradiance is below 400 W m⁻² and can dynamically manage daytime cooling efficiency. Importantly, its PRC efficiency is capable of being tuned in an on-demand and ultrafast millisecond-scale way, whose controllable transparency enables multistage heat regulation. This study is hoped to provide new inspiration in the preparation of advanced optical devices and energy-efficient equipment.     

Hybrid Silver Nanowire and Graphene‐Based Solution‐Processed Transparent Electrode for Organic Optoelectronics

The research on transparent conductive electrodes is in rapid ascent in order to respond to the requests of novel optoelectronic devices. The synergic coupling of silver nanowires (AgNWs) and high‐quality solution‐processable exfoliated graphene (EG) enables an efficient transparent conductor with low‐surface roughness of 4.6 nm, low sheet resistance of 13.7 Ω sq^?1 at high transmittance, and superior mechanical and chemical stabilities. The developed AgNWs–EG films are versatile for a wide variety of optoelectronics. As an example, when used as a bottom electrode in organic solar cell and polymer light‐emitting diode, the devices exhibit a power conversion efficiency of 6.6% and an external quantum efficiency of 4.4%, respectively, comparable to their commercial indium tin oxide counterparts.     

Thermally Stable Transparent Resistive Random Access Memory based on All‐Oxide Heterostructures

An all‐oxide transparent resistive random access memory (T‐RRAM) device based on hafnium oxide (HfO_x) storage layer and indium‐tin oxide (ITO) electrodes is fabricated in this work. The memory device demonstrates not only good optical transmittance but also a forming‐free bipolar resistive switching behavior with room‐temperature R_OFF/R_ON ratio of 45, excellent endurance of ≈5 × 10⁷ cycles and long retention time over 10⁶ s. More importantly, the HfO_x based RRAM carries great ability of anti‐thermal shock over a wide temperature range of 10 K to 490 K, and the high R_OFF/R_ON ratio of ≈40 can be well maintained under extreme working conditions. The field‐induced electrochemical formation and rupture of the robust metal‐rich conductive filaments in the mixed‐structure hafnium oxide film are found to be responsible for the excellent resistance switching of the T‐RRAM devices. The present all‐oxide devices are of great potential for future thermally stable transparent electronic applications.     

Reversible Switching Phenomenon in Diarylethene Molecular Devices with Reduced Graphene Oxide Electrodes on Flexible Substrates

Photoswitching molecular electronic devices with reduced graphene oxide (rGO) top electrodes on flexible substrates are fabricated and characterized. It has been reported previously that diarylethene molecular devices with poly‐(3,4‐ethylenedioxythiophene) stabilized with poly‐(4‐styrenesulfonic acid)/Au top electrodes can hold two stable electrical conductance states when the devices are exposed to UV or visible light during device fabrication. However, those devices fail to show the reversible switching phenomenon in response to illumination after device fabrication. By employing conducting and transparent rGO top electrodes, it is demonstrated that the diarylethene molecular devices show a reversible switching phenomenon, i.e., the fabricated devices change their conductance state in response to the alternating illumination with UV and visible light. Furthermore, the molecular devices with rGO top electrodes also exhibit good longtime stability and reliable electrical characteristics when subjected to various mechanical stresses (bending radius down to 5 mm and bending cycle over 10⁴).     

Monolithic Dual‐Material 3D Printing of Ionic Skins with Long‐Term Performance Stability

Artificial “ionic skin” is of great interest for mimicking the functionality of human skin, such as subtle pressure sensing. However, the development of ionic skin is hindered by the strict requirements of device integration and the need for devices with satisfactory performance. Here, a dual‐material printing strategy for ionic skin fabrication to eliminate signal drift and performance degradation during long‐term use is proposed, while endowing the ionic skins with high sensitivity by 3D printing of ionic hydrogel electrodes with microstructures. The ionic skins are fabricated by alternative digital light processing 3D printing of two photocurable precursors: hydrogel and water‐dilutable polyurethane acrylate (WPUA), in which the ionically conductive hydrogel layers serve as soft, transparent electrodes and the electrically insulated WPUA as flexible, transparent dielectric layers. This novel dual‐material printing strategy enables strong chemical bonding between the hydrogel and the WPUA, endowing the device with designed characteristics. The resulting device has high sensitivity, minimal hysteresis, a response time in the millisecond range, and excellent repetition durability for pressure sensing. The results demonstrate the potential of the dual‐material 3D printing strategy as a pathway to realize highly stable and high‐performance ionic skin fabrication to monitor human physiological signals and human–machine interactions.     

All-solution-processed foldable transparent electrodes of Ag nanowire mesh and metal matrix films for flexible electronics

In this study, we developed foldable transparent electrodes composed of Ag nanowire (AgNW) networks welded by Ag nanoparticles (AgNPs) reduced from commercial Ag ink. All the processes used were solution-based. Using the Meyer rod method, uniform AgNW networks were roll-to-roll coated on large-area polymer substrates, and the spin-coated AgNPs firmly welded the AgNWs together at junctions and to substrates. The hybrid films consisting of AgNWs and the Ag film matrix exhibited higher electrical conductivity (5.0–7.3 × 10⁵ S/m) than and equivalent transparency (90–95%) to the AgNW networks. Furthermore, the hybrid films showed significantly better bending stability than AgNW networks. During cyclic bending tests to 10,000 cycles at 5 mm bending radius and even when almost folded with r_b of 1 mm, the resistivity changes were negligible because AgNWs were tightly held and adhered to the substrate by Ag films covering wires, thereby hindering fracturing of AgNWs under tension. Because the films were fabricated at a low temperature, there was no oxidation on the surfaces of the films. Hence, flexible organic light-emitting diodes (f-OLEDs) were successfully fabricated on polyethylene terephthalates (PET) coated with the hybrid films. The f-OLED in the bent state was comparable to that in the flat state, validating the potential applications of these transparent hybrid films as electrodes in various flexible electronics.     

Flexible transparent conductive film based on silver nanowires and reduced graphene oxide

Silver nanowires (AgNWs) with diameter of 90—150 nm and length of 20—50 μm were successfully synthesized by a polyol process. Graphene oxide (GO) was prepared by Hummers method, and was reduced with strong hydrazine hy-drate at room temperature. The flexible transparent conductive films (TCFs) were fabricated using the mixed cellulose eater (MCE) as matrix and AgNWs and reduced graphene oxide (rGO) as conductive fillers by the improved vacuum fil-tration process. Then, the optical, electrical and mechanical properties of the AgNWs-rGO films were investigated. The results show that for the AgNWs-rGO film produced with the deposition densities of AgNWs and rGO as 110 mg·m-2 and 55 mg·m-2, the optical transmission at 550 nm is 88.4% with Rs around 891 Ω·sq-1, whereas the optical transmission for the AgNWs-rGO film with deposition densities of AgNWs and rGO of 385 mg·m-2 and 55 mg·m-2 is 79.0% at 550 nm with Rs around 9.6 Ω·sq-1. There is little overt increase in Rs of the AgNWS-rGO film after tape tests for 200 times. The bending test results indicate that the change in Rs of AgNWs-MCE film is less than 2% even after 200 cycles of compressive or tensile bending. The excellent mechanical properties of the AgNWs-rGO film can be attributed to the burying of AgNWs and rGO at the surface of MCE     

Cephalopod-Inspired Stretchable Self-Morphing Skin Via Embedded Printing and Twisted Spiral Artificial Muscles

Cutaneous muscles drive the texture-modulation behavior of cephalopods by protruding several millimeters out of the skin. Inspired by cephalopods, a self-morphing, stretchable smart skin containing embedded-printed electrodes and actuated by Twisted Spiral Artificial Muscles (TSAMs) is proposed. Electrothermally actuated TSAMs are manufactured from inexpensive polymer fibers to mimic the papillae muscles of cephalopods. These spirals can produce strains of nearly 2000% using a voltage of only 0.02 V mm⁻¹. Stretchable and low-resistance liquid metal electrodes are embedded-printed inside the self-morphing skin to facilitate the electrothermal actuation of TSAMs. Theoretical and numerical models are proposed to describe the embedded printing of low-viscosity Newtonian liquid metals as conductive electrodes in a soft elastomeric substrate. Experimental mechanical tests are performed to demonstrate the robustness and electrical stability of the electrodes. Two smart skin prototypes are fabricated to highlight the capabilities of the proposed self-morphing system, including a texture-modulating wearable soft glove and a waterproof skin that emulates the texture-modulation behavior of octopi underwater. The proposed self-morphing stretchable smart skin can find use in a wide range of applications, such as refreshable Braille displays, haptic feedback devices, turbulence tripping, and antifouling devices for underwater vehicles.