Cover Picture: Microsolidics: Fabrication of Three‐Dimensional Metallic Microstructures in Poly(dimethylsiloxane) (Adv. Mater. 5/2007)

Flexible metallic wires embedded in poly(dimethylsiloxane) are produced with microscale dimensions by injecting heated, liquid solder into microfluidic channels and cooling, as reported by George Whitesides and co‐workers on p. 727. This approach is used to fabricate complex, metallic microstructures that are twisted (as shown), rolled, or woven into fabrics. The structures can be rigid or flexible, depending on the type of solder used, and breaks in the metal can be “healed” by reheating the device. This method of fabrication may find applications in flexible electronic circuits, 3D metallic microstructures, and hybrid electronic–microfluidic devices.     

Formation of Single Micro‐ and Nanowires with Extreme Aspect Ratios in Microfluidic Channels

Shown here is the site‐specific formation of single extraordinarily long metal–organic micro‐ and nanowires using a microfluidic device made of poly(dimethylsiloxane) (PDMS). This approach exploits two concepts, i) the diffusion of organic precursor molecules through PDMS and ii) the use of microfluidic channels as a growth template. To initiate wire formation, metal and organic precursor solutions are filled into different supply channels that are separated by PDMS. As the precursor diffuses through PDMS, and thereby infiltrates the adjacent channel, the growth of micro‐ and nanowires starts at the side walls of this adjacent channel. The formation yields single wires with sizes ranging from several hundreds of micrometers to millimeters at diameters of 0.5–2 µm. The principles of this formation pathway are demonstrated with the reaction of tetrathiafulvalene (TTF) and gold(III) ions that yields Au‐TTF wires. The influence of various reaction parameters including the choice of solvents and the chip fabrication protocol on the reaction are evaluated. Based on these findings, a further microfluidic device design with orthogonally arranged channels is developed, and the formation of single wires in a channel‐defined pattern is demonstrated. Moreover, the possibility of pulsed precursor supply allows for advanced control over the growth of the wires.     

Highly Stable and Stretchable Conductive Films through Thermal‐Radiation‐Assisted Metal Encapsulation

Stretchable conductors are the basic units of advanced flexible electronic devices, such as skin‐like sensors, stretchable batteries and soft actuators. Current fabrication strategies are mainly focused on the stretchability of the conductor with less emphasis on the huge mismatch of the conductive material and polymeric substrate, which results in stability issues during long‐term use. Thermal‐radiation‐assisted metal encapsulation is reported to construct an interlocking layer between polydimethylsiloxane (PDMS) and gold by employing a semipolymerized PDMS substrate to encapsulate the gold clusters/atoms during thermal deposition. The stability of the stretchable conductor is significantly enhanced based on the interlocking effect of metal and polymer, with high interfacial adhesion (>2 MPa) and cyclic stability (>10 000 cycles). Also, the conductor exhibits superior properties such as high stretchability (>130%) and large active surface area (>5:1 effective surface area/geometrical area). It is noted that this method can be easily used to fabricate such a stretchable conductor in a wafer‐scale format through a one‐step process. As a proof of concept, both long‐term implantation in an animal model to monitor intramuscular electric signals and on human skin for detection of biosignals are demonstrated. This design approach brings about a new perspective on the exploration of stretchable conductors for biomedical applications.     

Advanced Carbon for Flexible and Wearable Electronics

Flexible and wearable electronics are attracting wide attention due to their potential applications in wearable human health monitoring and care systems. Carbon materials have combined superiorities such as good electrical conductivity, intrinsic and structural flexibility, light weight, high chemical and thermal stability, ease of chemical functionalization, as well as potential mass production, enabling them to be promising candidate materials for flexible and wearable electronics. Consequently, great efforts are devoted to the controlled fabrication of carbon materials with rationally designed structures for applications in next‐generation electronics. Herein, the latest advances in the rational design and controlled fabrication of carbon materials toward applications in flexible and wearable electronics are reviewed. Various carbon materials (carbon nanotubes, graphene, natural‐biomaterial‐derived carbon, etc.) with controlled micro/nanostructures and designed macroscopic morphologies for high‐performance flexible electronics are introduced. The fabrication strategies, working mechanism, performance, and applications of carbon‐based flexible devices are reviewed and discussed, including strain/pressure sensors, temperature/humidity sensors, electrochemical sensors, flexible conductive electrodes/wires, and flexible power devices. Furthermore, the integration of multiple devices toward multifunctional wearable systems is briefly reviewed. Finally, the existing challenges and future opportunities in this field are summarized.     

Self‐Assembly of Enzyme‐Like Nanofibrous G‐Molecular Hydrogel for Printed Flexible Electrochemical Sensors

Conducting hydrogels provide great potential for creating designer shape‐morphing architectures for biomedical applications owing to their unique solid–liquid interface and ease of processability. Here, a novel nanofibrous hydrogel with significant enzyme‐like activity that can be used as “ink” to print flexible electrochemical devices is developed. The nanofibrous hydrogel is self‐assembled from guanosine (G) and KB(OH)₄ with simultaneous incorporation of hemin into the G‐quartet scaffold, giving rise to significant enzyme‐like activity. The rapid switching between the sol and gel states responsive to shear stress enables free‐form fabrication of different patterns. Furthermore, the replication of the G‐quartet wires into a conductive matrix by in situ catalytic deposition of polyaniline on nanofibers is demonstrated, which can be directly printed into a flexible electrochemical electrode. By loading glucose oxidase into this novel hydrogel, a flexible glucose biosensor is developed. This study sheds new light on developing artificial enzymes with new functionalities and on fabrication of flexible bioelectronics.     

Desktop‐Stereolithography 3D‐Printing of a Poly(dimethylsiloxane)‐Based Material with Sylgard‐184 Properties

The advantageous physiochemical properties of poly(dimethylsiloxane) (PDMS) have made it an extremely useful material for prototyping in various technological, scientific, and clinical areas. However, PDMS molding is a manual procedure and requires tedious assembly steps, especially for 3D designs, thereby limiting its access and usability. On the other hand, automated digital manufacturing processes such as stereolithography (SL) enable true 3D design and fabrication. Here the formulation, characterization, and SL application of a 3D‐printable PDMS resin (3DP‐PDMS) based on commercially available PDMS‐methacrylate macromers, a high‐efficiency photoinitiator and a high‐absorbance photosensitizer, is reported. Using a desktop SL‐printer, optically transparent submillimeter structures and microfluidic channels are demonstrated. An optimized blend of PDMS‐methacrylate macromers is also used to SL‐print structures with mechanical properties similar to conventional thermally cured PDMS (Sylgard‐184). Furthermore, it is shown that SL‐printed 3DP‐PDMS substrates can be rendered suitable for mammalian cell culture. The 3DP‐PDMS resin enables assembly‐free, automated, digital manufacturing of PDMS, which should facilitate the prototyping of devices for microfluidics, organ‐on‐chip platforms, soft robotics, flexible electronics, and sensors, among others.     

Writing and Functionalisation of Suspended DNA Nanowires on Superhydrophobic Pillar Arrays

Nanowire arrays and networks with precisely controlled patterns are very interesting for innovative device concepts in mesoscopic physics. In particular, DNA templates have proven to be versatile for the fabrication of complex structures that obtained functionality via combinations with other materials, for example by functionalisation with molecules or nanoparticles, or by coating with metals. Here, the controlled motion of the a three‐phase contact line (TCL) of DNA‐loaded drops on superhydrophobic substrates is used to fabricate suspended nanowire arrays. In particular, the deposition of DNA wires is imaged in situ, and different patterns are obtained on hexagonal pillar arrays by controlling the TCL velocity and direction. Robust conductive wires and networks are achieved by coating the wires with a thin layer of gold, and as proof of concept conductivity measurements are performed on single suspended wires. The plastic material of the superhydrophobic pillars ensures electrical isolation from the substrate. The more general versatility of these suspended nanowire networks as functional templates is outlined by fabricating hybrid organic–metal–semiconductor nanowires by growing ZnO nanocrystals onto the metal‐coated nanowires.     

Highly elastic conductive polymeric MEMS

Polymeric structures with integrated, functional microelectrical mechanical systems (MEMS) elements are increasingly important in various applications such as biomedical systems or wearable smart devices. These applications require highly flexible and elastic polymers with good conductivity, which can be embedded into a matrix that undergoes large deformations. Conductive polydimethylsiloxane (PDMS) is a suitable candidate but is still challenging to fabricate. Conductivity is achieved by filling a nonconductive PDMS matrix with conductive particles. In this work, we present an approach that uses new mixing techniques to fabricate conductive PDMS with different fillers such as carbon black, silver particles, and multiwalled carbon nanotubes. Additionally, the electrical properties of all three composites are examined under continuous mechanical stress. Furthermore, we present a novel, low-cost, simple three-step molding process that transfers a micro patterned silicon master into a polystyrene (PS) polytetrafluoroethylene (PTFE) replica with improved release features. This PS/PTFE mold is used for subsequent structuring of conductive PDMS with high accuracy. The non sticking characteristics enable the fabrication of delicate structures using a very soft PDMS, which is usually hard to release from conventional molds. Moreover, the process can also be applied to polyurethanes and various other material combinations.     

Highly elastic conductive polymeric MEMS

Abstract

Polymeric structures with integrated, functional microelectrical mechanical systems (MEMS) elements are increasingly important in various applications such as biomedical systems or wearable smart devices. These applications require highly flexible and elastic polymers with good conductivity, which can be embedded into a matrix that undergoes large deformations. Conductive polydimethylsiloxane (PDMS) is a suitable candidate but is still challenging to fabricate. Conductivity is achieved by filling a nonconductive PDMS matrix with conductive particles. In this work, we present an approach that uses new mixing techniques to fabricate conductive PDMS with different fillers such as carbon black, silver particles, and multiwalled carbon nanotubes. Additionally, the electrical properties of all three composites are examined under continuous mechanical stress. Furthermore, we present a novel, low-cost, simple three-step molding process that transfers a micro patterned silicon master into a polystyrene (PS) polytetrafluoroethylene (PTFE) replica with improved release features. This PS/PTFE mold is used for subsequent structuring of conductive PDMS with high accuracy. The non sticking characteristics enable the fabrication of delicate structures using a very soft PDMS, which is usually hard to release from conventional molds. Moreover, the process can also be applied to polyurethanes and various other material combinations.     

Cover Picture: Direct Growth of Flexible Carbon Nanotube Electrodes (Adv. Mater. 3/2008)

Entangled networks of multiwalled carbon nanotubes (CNTs) integrated into a highly conducting carbon layer can be grown on a range of substrates including glassy carbon and metal foils. On p. 566, Gordon Wallace and co‐workers report the fabrication of a continuous flexible CNT electrode with high surface area and conductivity. The electrode demonstrates a stable battery capacity of 572 mAh g^–1. This discovery provides a direct route for the generation of large‐scale flexible CNT electrode materials.     

Polymer‐Assisted Metal Deposition (PAMD) for Flexible and Wearable Electronics: Principle,Materials, Printing,and Devices

The rapid development of flexible and wearable electronics favors low‐cost, solution‐processing, and high‐throughput techniques for fabricating metal contacts, interconnects, and electrodes on flexible substrates of different natures. Conventional top‐down printing strategies with metal‐nanoparticle‐formulated inks based on the thermal sintering mechanism often suffer from overheating, rough film surface, low adhesion, and poor metal quality, which are not desirable for most flexible electronic applications. In recent years, a bottom‐up strategy termed as polymer‐assisted metal deposition (PAMD) shows great promise in addressing the abovementioned challenges. Here, a detailed review of the development of PAMD in the past decade is provided, covering the fundamental chemical mechanism, the preparation of various soft and conductive metallic materials, the compatibility to different printing technologies, and the applications for a wide variety of flexible and wearable electronic devices. Finally, the attributes of PAMD in comparison with conventional nanoparticle strategies are summarized and future technological and application potentials are elaborated.     

Splashing-Assisted Femtosecond Laser-Activated Metal Deposition for Mold- and Mask-Free Fabrication of Robust Microstructured Electrodes for Flexible Pressure Sensors (Small 24/2023)

Flexible pressure sensors play an indispensable role in flexible electronics. Microstructures on flexible electrodes have been proven to be effective in improving the sensitivity of pressure sensors. However, it remains a challenge to develop such microstructured flexible electrodes in a convenient way. Inspired by splashed particles from laser processing, herein, a method for customizing microstructured flexible electrodes by femtosecond laser-activated metal deposition is proposed. It takes advantage of the catalyzing particles scattered during femtosecond laser ablation and is particularly suitable for moldless, maskless, and low-cost fabrication of microstructured metal layers on polydimethylsiloxane (PDMS). Robust bonding at the PDMS/Cu interface is evidenced by the scotch tape test and the duration test over 10 000 bending cycles. Benefiting from the firm interface, the developed flexible capacitive pressure sensor with microstructured electrodes presents several conspicuous features, including a sensitivity (0.22 kPa⁻¹) 73 times higher than the one using flat Cu electrodes, ultralow detection limit (<1 Pa), rapid response/recovery time (4.2/5.3 ms), and excellent stability. Moreover, the proposed method, inheriting the merits of laser direct writing, is capable of fabricating a pressure sensor array in a maskless manner for spatial pressure mapping.     

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%).     

Transparente leitfähige Elektroden

Transparent conductive oxides and alternative transparent electrodes for organic photovoltaics and OLEDs Organic, photoactive devices, such as OLEDs or organic solar cells, currently use indium tin oxide (ITO) as transparent electrode. Whereas ITO is industry‐proven for many years and shows very good electrical and optical properties, its application for lowcost and flexible devices might not be optimal. For such applications innovative technologies such as networkbased metal nanowire or carbon nanotube electrodes, graphene, conductive polymers, metal thin‐films and alternative transparent conductive oxides emerge. Although some of these technologies are rather experimental and far from application, some of them have the potential to replace ITO in selected applications.     

Replication of a thin polydimethylsiloxane stamp and its application to dual-nanoimprint lithography for 3D hybrid nano/micropatterns

This paper presents the fabrication of a thin and flexible polydimethylsiloxane (PDMS) stamp with a thickness of a few tens of um and its application to nanoimprint lithography (NIL). The PDMS material generally has a low elastic modulus and high adhesive characteristics. Therefore, after being treated, the thin PDMS stamp is easily deformed and torn, adhering to itself and other materials. This paper introduces the use of a metal ring around the flange of a thin PDMS stamp to assist with the handling of this material. A PDMS stamp with a motheye pattern in nanometer scale was inserted between a substrate and a microstamp with concave patterns in micrometer scale. Subsequently, three-dimensional (3D) hybrid nano/micropatterns were fabricated by pressing these two stamps and curing the resist. The fabricated hybrid patterns were measured and verified in both the microscale and nanoscale. The process, termed "dual NIL," can be applied to the fabrication of optical components or bio-sensors that require repetitive nanopatterns on micropatterns.     

Dual-axis thermal convective inclinometer based on CNT/PDMS composite

This paper presents the design, fabrication, and characterization of a novel inclination-angle sensor (inclinometer) using heating and sensing elements based on conductive polydimethylsiloxane (PDMS) composited with carbon nanotubes (CNTs). The inclinometer consists of a PDMS cube-shaped chamber, a CNTs/PDMS composite-based heater, and four CNTs/PDMS composite-based temperature sensors. The working mechanism of this sensor is based on thermal convective sensing theory on the basis of the detection of thermal disturbance caused by inclination-induced convection in a sealed chamber. In order to prepare the conductive CNTs/PDMS composite, toluene was applied as a solvent to facilitate CNT dispersion in PDMS matrix and then was removed by evaporation. The resistive heating and thermal sensing properties of CNT/PDMS composite-based elements were tested and analyzed first. Then, the responses to inclination-angle were monitored and reported. Experimental results demonstrate that the inclinometer can measure dual-axis angular position in the range of 360° with high stability and repeatability.     

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.     

拉伸应变下镍包碳纤维填充导电橡胶取向及电阻响应

导电橡胶因其超高的弹性和良好的导电性而在柔性电子材料领域受到广泛关注。受载时导电填料重新排列会产生相应的电阻变化。本研究选取镍包碳纤维（Nickel coated carbon fiber,CF-Ni）填充于基胶聚二甲基硅氧烷（Polydimethylsiloxane,PDMS）中制备导电橡胶。基于MATLAB平台,观察了导电橡胶中CF-Ni纤维的静态分布,并构建了纤维取向率的计算方法;随后施加动态应变载荷,选用3D打印的样品,在拉伸应变下,对其进行了纤维在胶体中取向变化的同步观察。结果表明:CF-Ni纤维沿拉伸应变方向发生偏转,最大偏转角度可达20°; CF-Ni纤维的取向分布及拉伸应变下纤维的偏转会对导电橡胶的电学性能产生影响,在60%的应变量下,CF-Ni/PDMS表面电阻最大变化为600%。导电橡胶电阻对拉伸应变载荷的响应为CF-Ni/PDMS用于制备柔性传感器奠定了基础。      

Patterned Paper as a Low-Cost, Flexible Substrate for Rapid Prototyping of PDMS Microdevices via "Liquid Molding"

This report describes the use of patterned paper as a low-cost, flexible substrate for rapidly prototyping PDMS microdevices via "liquid molding". The entire fabrication process consists simply of three steps: (1) fabrication of patterned paper in NC membrane by direct wax printing (or modified wax printing that we call "transfer wax printing"); (2) formation of liquid mold on wax-patterned NC membrane; (3) PDMS molding and curing on wax-patterned NC membrane anchored with liquid micropatterns. All these procedures can be finished within only 1.5 h without the use of a photomask, photoresist, UV lamp, etc. Through the use of wax-patterned NC membrane coupled with a liquid mold as a template, different PDMS microdevices such as microwells and microchannels have been fabricated to demonstrate the usefulness of the method for PDMS microfabrication. The height of microwells and microchannels can also be tailored flexibly by adjusting the liquid filling volume. This method for prototyping PDMS microdevices has some favorable merits including simple operation procedures, fast concept-to-device time, and low cost, indicating its potential for simple PDMS microdevice fabrication and applications.     

Liquid Metal Droplet and Graphene Co‐Fillers for Electrically Conductive Flexible Composites

Colloidal liquid metal alloys of gallium, with melting points below room temperature, are potential candidates for creating electrically conductive and flexible composites. However, inclusion of liquid metal micro‐ and nanodroplets into soft polymeric matrices requires a harsh auxiliary mechanical pressing to rupture the droplets to establish continuous pathways for high electrical conductivity. However, such a destructive strategy reduces the integrity of the composites. Here, this problem is solved by incorporating small loading of nonfunctionalized graphene flakes into the composites. The flakes introduce cavities that are filled with liquid metal after only relatively mild press‐rolling (<0.1 MPa) to form electrically conductive continuous pathways within the polymeric matrix, while maintaining the integrity and flexibility of the composites. The composites are characterized to show that even very low graphene loadings (≈0.6 wt%) can achieve high electrical conductivity. The electrical conductance remains nearly constant, with changes less than 0.5%, even under a relatively high applied pressure of >30 kPa. The composites are used for forming flexible electrically‐conductive tracks in electronic circuits with a self‐healing property. The demonstrated application of co‐fillers, together with liquid metal droplets, can be used for establishing electrically‐conductive printable‐composite tracks for future large‐area flexible electronics.