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.     

Printable Transparent Conductive Films for Flexible Electronics

Printed electronics are an important enabling technology for the development of low‐cost, large‐area, and flexible optoelectronic devices. Transparent conductive films (TCFs) made from solution‐processable transparent conductive materials, such as metal nanoparticles/nanowires, carbon nanotubes, graphene, and conductive polymers, can simultaneously exhibit high mechanical flexibility, low cost, and better photoelectric properties compared to the commonly used sputtered indium‐tin‐oxide‐based TCFs, and are thus receiving great attention. This Review summarizes recent advances of large‐area flexible TCFs enabled by several roll‐to‐roll‐compatible printed techniques including inkjet printing, screen printing, offset printing, and gravure printing using the emerging transparent conductive materials. The preparation of TCFs including ink formulation, substrate treatment, patterning, and postprocessing, and their potential applications in solar cells, organic light‐emitting diodes, and touch panels are discussed in detail. The rational combination of a variety of printed techniques with emerging transparent conductive materials is believed to extend the opportunities for the development of printed electronics within the realm of flexible electronics and beyond.     

An Overview of the Development of Flexible Sensors

Flexible sensors that efficiently detect various stimuli relevant to specific environmental or biological species have been extensively studied due to their great potential for the Internet of Things and wearable electronics applications. The application of flexible and stretchable electronics to device‐engineering technologies has enabled the fabrication of slender, lightweight, stretchable, and foldable sensors. Here, recent studies on flexible sensors for biological analytes, ions, light, and pH are outlined. In addition, contemporary studies on device structure, materials, and fabrication methods for flexible sensors are discussed, and a market overview is provided. The conclusion presents challenges and perspectives in this field.     

Ultrastretchable and Wireless Bioelectronics Based on All‐Hydrogel Microfluidics

Hydrogel bioelectronics that can interface biological tissues and flexible electronics is at the core of the growing field of healthcare monitoring, smart drug systems, and wearable and implantable devices. Here, a simple strategy is demonstrated to prototype all‐hydrogel bioelectronics with embedded arbitrary conductive networks using tough hydrogels and liquid metal. Due to their excellent stretchability, the resultant all‐hydrogel bioelectronics exhibits stable electrochemical properties at large tensile stretch and various modes of deformation. The potential of fabricated all‐hydrogel bioelectronics is demonstrated as wearable strain sensors, cardiac patches, and near‐field communication (NFC) devices for monitoring various physiological conditions wirelessly. The presented simple platform paves the way of implantable hydrogel electronics for Internet‐of‐Things and tissue–machine interfacing applications.     

Cover Picture: Fabrication of Elastomeric Wires by Selective Electroless Metallization of Poly(dimethylsiloxane) (Adv. Mater. 1/2008)

Tricia Carmichael and co‐workers employ a simple, low‐cost method for the fabrication of patterned metal films on elastomeric poly(dimethylsiloxane) (PDMS) substrates, as described on p. 59. The metal/PDMS composites are electrically conductive and mechanically flexible, making them suitable for use in the fabrication of lightweight, flexible devices such as wearable electronics, biocompatible sensors, and artificial nerves, skins, and muscles. Copper wires on PDMS remain conductive when subjected to linear strains of up to 52 %. The utility of these wires is demonstrated by using them as laminated top contacts in an organic light‐emitting device.     

Laser‐Induced Molybdenum Carbide–Graphene Composites for 3D Foldable Paper Electronics

Versatile and low‐cost manufacturing processes/materials are essential for the development of paper electronics. Here, a direct‐write laser patterning process is developed to make conductive molybdenum carbide–graphene (MCG) composites directly on paper substrates. The hierarchically porous MCG structures are converted from fibrous paper soaked with the gelatin‐mediated inks containing molybdenum ions. The resulting Mo₃C₂ and graphene composites are mechanically stable and electrochemically active for various potential applications, such as electrochemical ion detectors and gas sensors, energy harvesters, and supercapacitors. Experimentally, the electrical conductivity of the composite is resilient to mechanical deformation with less than 5% degradation after 750 cycles of 180° repeated folding tests. As such, the direct laser conversion of MCGs on papers can be applicable for paper‐based electronics, including the 3D origami folding structures.     

基于微结构的柔性压力传感器设计、制备及性能

随着科技的快速发展,电子皮肤和柔性可穿戴设备由于在人体运动、健康监测、智能机器人等领域具有重要应用而引起了人们广泛的关注。传统的基于贵金属或金属氧化物半导体的压力传感器成本高、柔韧性差,而新型的基于微结构的柔性压力传感器具有灵敏度高、应变范围宽、低成本、低功耗、响应速度快等优势,在电子皮肤和柔性可穿戴设备等方面发挥重要作用,成为当前柔性电子材料与器件主要研究热点之一。本文系统总结了近年来颇受关注的基于金字塔形、微球形、微柱形、仿生结构、褶皱等不同柔性基底微结构和多孔导电聚合物材料的柔性压力传感器在材料选择、结构设计、制备方法、传感性能等方面取得的重要进展,并对柔性压力传感器的未来发展进行了展望。      

纳米银导电油墨及其在柔性印刷电子中的应用

目的 探究纳米银导电油墨及其在柔性印刷电子中的应用。方法 通过总结国内外文献,从纳米银颗粒及其导电油墨的制备、印刷工艺、烧结工艺以及在柔性印刷电子技术中的应用几方面总结近年来的研究进展。结果 在油墨制备及使用中,简化制备工艺、降低生产成本、实现绿色环保、低温烧结,同时提高油墨的基材适应性是未来纳米银导电油墨的改进重点。直写技术具有精度高、速度快等优势,正逐渐替代丝网印刷技术成为主流。烧结工艺的研究重点在于实现低温烧结,其中化学烧结工艺简单,但提高导电性是研究重点。其他烧结方式则设备昂贵,环境要求高。结论 作为功能性电子材料,纳米银导电油墨因出色的电性能和印刷适性,正在被广泛应用于柔性印刷电子中。近年来通过对纳米银及其导电油墨的深入研究及技术改进,在纳米银颗粒的制备、低温烧结技术、节能环保加工工艺等方面获得了一定的进展。与此同时,将其作为功能材料应用于制备柔性传感器中,RFID标签天线、柔性电极、超级电容器、太阳能电池等正受到广泛研究与应用。     

一种抗冻、可拉伸有机水凝胶的制备及 在柔性应变传感器中的应用

针对导电水凝胶柔性应变传感器在低温环境容易被冻结而发生失效的问题,通过溶剂置换策略制备了一种抗冻、可拉伸的聚多巴胺还原氧化石墨烯/海藻酸钠/聚丙烯酰胺（PDA-rGO/SA/PAM）有机水凝胶。实验结果表明：制得的有机水凝胶具有优异的抗冻性能、良好的机械性能以及灵敏的传感性能。此外,组装的有机水凝胶柔性应变传感器可以检测多种人体运动形式,例如手指弯曲、手腕弯曲、面部微表情等,对未来可穿戴柔性电子产品的发展起到了一定的推动作用。     

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.     

Large‐Scale Direct‐Writing of Aligned Nanofibers for Flexible Electronics

Nanofibers/nanowires usually exhibit exceptionally low flexural rigidities and remarkable tolerance against mechanical bending, showing superior advantages in flexible electronics applications. Electrospinning is regarded as a powerful process for this 1D nanostructure; however, it can only be able to produce chaotic fibers that are incompatible with the well‐patterned microstructures in flexible electronics. Electro‐hydrodynamic (EHD) direct‐writing technology enables large‐scale deposition of highly aligned nanofibers in an additive, noncontact, real‐time adjustment, and individual control manner on rigid or flexible, planar or curved substrates, making it rather attractive in the fabrication of flexible electronics. In this Review, the ground‐breaking research progress in the field of EHD direct‐writing technology is summarized, including a brief chronology of EHD direct‐writing techniques, basic principles and alignment strategies, and applications in flexible electronics. Finally, future prospects are suggested to advance flexible electronics based on orderly arranged EHD direct‐written fibers. This technology overcomes the limitations of the resolution of fabrication and viscosity of ink of conventional inkjet printing, and represents major advances in manufacturing of flexible electronics.     

Effects of inter-tube distance and alignment on tunnelling resistance and strain sensitivity of nanotube/polymer composite films

A model for carbon nanotube (CNT)/polymer composite conductivity is developed, considering the effect of inter-tube tunnelling through the polymer. The statistical effects of inter-tube distance and alignment on the tunnelling are investigated through numerical modelling, to highlight their role in the conductance and piezoresistance of the composite film. The impact of critical parameters, including the concentration, alignment and aspect ratio of the CNTs and the tunnelling barrier height of the polymer is statistically evaluated using a large number of randomly generated CNT/polymer composite films. A numerical model is presented for the tunnelling resistance as a function of CNT concentration and polymer properties, which provides good agreement with the reported conductance in the literature. In particular, for a low concentration of CNTs close to the percolation threshold, we demonstrate how tunnelling dominates the conductance properties and leads to significant increase in the piezoresistance of the composite. This is important for gaining insight into the optimum concentration and alignment of the CNTs in the composite film for applications such as strain sensors, anisotropic conductive films, transparent electrodes and flexible electronics.     

Review of recent achievements in self-healing conductive materials and their applications

Self-healing materials have attracted increasing attention because of their wide range of applications. It can be expected to offer obvious advantages in conductive materials with self-healing properties, which are regarded as promising candidates for the fabrication of self-healing electronics, energy storage devices, sensors, anticorrosive coating and conductive adhesives. In this review, we focused on recent efforts to develop self-healing conductive composites including their preparation methods, properties and applications. The self-healing conductive materials were presented based on different conductive mediums, such as metal, carbon, conductive polymer, ionic liquids. In addition, their novel applications of the self-healing conductive materials in conductive coatings, energy storage devices and sensors are highlighted. Finally, the future challenges of conductive materials with self-healing properties are proposed.     

Grain‐Boundary‐Induced Drastic Sensing Performance Enhancement of Polycrystalline‐Microwire Printed Gas Sensors

The development of materials with high efficiency and stable signal output in a bent state is important for flexible electronics. Grain boundaries provide lasting inspiration and a promising avenue for designing advanced functionalities using nanomaterials. Combining bulk defects in polycrystalline materials is shown to result in rich new electronic structures, catalytic activities, and mechanical properties for many applications. However, direct evidence that grain boundaries can create new physicochemical properties in flexible electronics is lacking. Here, a combination of bulk electrosensitive measurements, density functional theory calculations, and atomic force microscopy technology with quantitative nanomechanical mapping is used to show that grain boundaries in polycrystalline wires are more active and mechanically stable than single‐crystalline wires for real‐time detection of chemical analytes. The existence of a grain boundary improves the electronic and mechanical properties, which activate and stabilize materials, and allow new opportunities to design highly sensitive, flexible chemical sensors.     

Fabric Organic Electrochemical Transistors for Biosensors

Flexible fabric biosensors can find promising applications in wearable electronics. However, high‐performance fabric biosensors have been rarely reported due to many special requirements in device fabrication. Here, the preparation of organic electrochemical transistors (OECTs) on Nylon fibers is reported. By introducing metal/conductive polymer multilayer electrodes on the fibers, the OECTs show very stable performance during bending tests. The devices with functionalized gates are successfully used as various biosensors with high sensitivity and selectivity. The fiber‐based OECTs are woven together with cotton yarns successfully by using a conventional weaving machine, resulting in flexible and stretchable fabric biosensors with high performance. The fabric sensors show much more stable signals in the analysis of moving aqueous solutions than planar devices due to a capillary effect in fabrics. The fabric devices are integrated in a diaper and remotely operated by using a mobile phone, offering a unique platform for convenient wearable healthcare monitoring.     

Carbon nanotubes for electronics manufacturing and packaging:from growth to integration

Carbon nanotubes (CNTs) possess excellent electrical, thermal and mechanical properties. They are light in weight yet stronger than most of the other materials. They can be made both highly conductive and semi-conductive. They can be made from nano-sized small catalyst particles and extend to tens of millimeters long. Since CNTs emerged as a hot topic in the early 1990s, numerous research efforts have been spent on the study of the various properties of this new material. CNTs have been proposed as alternative materials of potential excellence in a lot of applications such as electronics, chemical sensors, mechanical sensors/actuators and composite materials, etc. This paper reviews the use of CNTs particularly in electronics manufacturing and packaging
field. The progresses of three most important applications, including CNT-based thermal interface materials, CNT-based interconnections and CNT-based cooling devices are reviewed. The growth and post-growth processing of CNTs for specific applications are introduced and the tailoring of CNTs properties, i.e., electrical resistivity, thermal  conductivity and strength, etc., is discussed with regard to specific application requirement. As the semiconductor industry is still driven by the need of getting smaller and faster, CNTs and the related composite systems as emerging new materials are likely to provide the solution to the future challenges as we make more and more complex electronics devices and systems.     

Nanomaterial‐Enabled Stretchable Conductors: Strategies,Materials and Devices

Stretchable electronics are attracting intensive attention due to their promising applications in many areas where electronic devices undergo large deformation and/or form intimate contact with curvilinear surfaces. On the other hand, a plethora of nanomaterials with outstanding properties have emerged over the past decades. The understanding of nanoscale phenomena, materials, and devices has progressed to a point where substantial strides in nanomaterial‐enabled applications become realistic. This review summarizes recent advances in one such application, nanomaterial‐enabled stretchable conductors (one of the most important components for stretchable electronics) and related stretchable devices (e.g., capacitive sensors, supercapacitors and electroactive polymer actuators), over the past five years. Focusing on bottom‐up synthesized carbon nanomaterials (e.g., carbon nanotubes and graphene) and metal nanomaterials (e.g., metal nanowires and nanoparticles), this review provides fundamental insights into the strategies for developing nanomaterial‐enabled highly conductive and stretchable conductors. Finally, some of the challenges and important directions in the area of nanomaterial‐enabled stretchable conductors and devices are discussed.     

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.     

Highly Sensitive,Flexible MEMS Based Pressure Sensor with Photoresist Insulation Layer

Pressure sensing is a crucial function for flexible and wearable electronics, such as artificial skin and health monitoring. Recent progress in material and device structure of pressure sensors has brought breakthroughs in flexibility, self‐healing, and sensitivity. However, the fabrication process of many pressure sensors is too complicated and difficult to integrate with traditional silicon‐based Micro‐Electro‐Mechanical System(MEMS). Here, this study demonstrates a scalable and integratable contact resistance‐based pressure sensor based on a carbon nanotube conductive network and a photoresist insulation layer. The pressure sensors have high sensitivity (95.5 kPa⁻¹), low sensing threshold (16 Pa), fast response speed (<16 ms), and zero power consumption when without loading pressure. The sensitivity, sensing threshold, and dynamic range are all tunable by conveniently modifying the hole diameter and thickness of insulation layer.     

A Nature‐Inspired,Flexible Substrate Strategy for Future Wearable Electronics

Flexibility plays a vital role in wearable electronics. Repeated bending often leads to the dramatic decrease of conductivity because of the numerous microcracks formed in the metal coating layer, which is undesirable for flexible conductors. Herein, conductive textile‐based tactile sensors and metal‐coated polyurethane sponge‐based bending sensors with superior flexibility for monitoring human touch and arm motions are proposed, respectively. Tannic acid, a traditional mordant, is introduced to attach to various flexible substrates, providing a perfect platform for catalyst absorbing and subsequent electroless deposition (ELD). By understanding the nucleation, growth, and structure of electroless metal deposits, the surface morphology of metal nanoparticles can be controlled in nanoscale with simple variation of the plating time. When the electroless plating time is 20 min, the normalized resistance (R/R₀) of as‐made conductive fibers is only 1.6, which is much lower than a 60 min ELD sample at the same conditions (R/R₀ ≈ 5). This is because a large number of unfilled gaps between nanoparticles prevent metal films from cracking under bending. Importantly, the Kelvin problem is relevant to deposited conductive coatings because metallic cells have a honeycomb‐like structure, which is a rationale to explain the relationships of conductivity and flexibility.