25th Anniversary Article: The Evolution of Electronic Skin (E‐Skin): A Brief History,Design Considerations,and Recent Progress

Human skin is a remarkable organ. It consists of an integrated, stretchable network of sensors that relay information about tactile and thermal stimuli to the brain, allowing us to maneuver within our environment safely and effectively. Interest in large‐area networks of electronic devices inspired by human skin is motivated by the promise of creating autonomous intelligent robots and biomimetic prosthetics, among other applications. The development of electronic networks comprised of flexible, stretchable, and robust devices that are compatible with large‐area implementation and integrated with multiple functionalities is a testament to the progress in developing an electronic skin (e‐skin) akin to human skin. E‐skins are already capable of providing augmented performance over their organic counterpart, both in superior spatial resolution and thermal sensitivity. They could be further improved through the incorporation of additional functionalities (e.g., chemical and biological sensing) and desired properties (e.g., biodegradability and self‐powering). Continued rapid progress in this area is promising for the development of a fully integrated e‐skin in the near future.     

Flexible strain sensors fabricated using carbon-based nanomaterials: A review

Flexible strain sensors have experienced growing demand due to their several potential applications, such as personalized health monitoring, human motion detection, structural health monitoring, smart garments, and robots. Recently, several academic results have been reported concerning flexible and stretchable strain sensors. These reports indicate that the materials and design methods have an important influence on the performance of strain sensors. Carbon-based nanomaterials including carbon-based nanofibers, carbon nanotubes, graphene, and carbon black nanoparticles play a key role in the fabrication of flexible strain sensors with excellent properties. In terms of design, carbon-based nanomaterials are generally combined with polymers to maintain the flexibility and stability of a strain sensor. Various combined methods were successfully developed using different assembly structures of carbon-based nanomaterials in polymers, such as uniform mixing and ordered structures, including films, fibers, nanofiber membranes, yarns, foams, and fabrics. The working mechanisms of the flexible strain sensors, including changing the conductive network between overlapped nanomaterials, tunneling effect, and crack propagation, are also different compared with that of traditional semiconductor and metal sensors. The effects of the carbon-based nanomaterial structures in polymers on the strain sensing performance have been comprehensively studied and analyzed. The potential applications of flexible strain sensors and current challenges have been summarized and evaluated. This review provides some suggestions for further development of flexible and stretchable strain sensors with outstanding performance.     

Highly Stretchable Superhydrophobic Composite Coating Based on Self‐Adaptive Deformation of Hierarchical Structures

With the rapid development of stretchable electronics, functional textiles, and flexible sensors, water‐proof protection materials are required to be built on various highly flexible substrates. However, maintaining the antiwetting of superhydrophobic surface under stretching is still a big challenge since the hierarchical structures at hybridized micro‐nanoscales are easily damaged following large deformation of the substrates. This study reports a highly stretchable and mechanically stable superhydrophobic surface prepared by a facile spray coating of carbon black/polybutadiene elastomeric composite on a rubber substrate followed by thermal curing. The resulting composite coating can maintain its superhydrophobic property (water contact angle ≈170° and sliding angle <4°) at an extremely large stretching strain of up to 1000% and can withstand 1000 stretching–releasing cycles without losing its superhydrophobic property. Furthermore, the experimental observation and modeling analysis reveal that the stable superhydrophobic properties of the composite coating are attributed to the unique self‐adaptive deformation ability of 3D hierarchical roughness of the composite coating, which delays the Cassie–Wenzel transition of surface wetting. In addition, it is first observed that the damaged coating can automatically recover its superhydrophobicity via a simple stretching treatment without incorporating additional hydrophobic materials.     

An Elastic Autonomous Self‐Healing Capacitive Sensor Based on a Dynamic Dual Crosslinked Chemical System

Adopting self‐healing, robust, and stretchable materials is a promising method to enable next‐generation wearable electronic devices, touch screens, and soft robotics. Both elasticity and self‐healing are important qualities for substrate materials as they comprise the majority of device components. However, most autonomous self‐healing materials reported to date have poor elastic properties, i.e., they possess only modest mechanical strength and recoverability. Here, a substrate material designed is reported based on a combination of dynamic metal‐coordinated bonds (β‐diketone–europium interaction) and hydrogen bonds together in a multiphase separated network. Importantly, this material is able to undergo self‐healing and exhibits excellent elasticity. The polymer network forms a microphase‐separated structure and exhibits a high stress at break (≈1.8 MPa) and high fracture strain (≈900%). Additionally, it is observed that the substrate can achieve up to 98% self‐healing efficiency after 48 h at 25 °C, without the need of any external stimuli. A stretchable and self‐healable dielectric layer is fabricated with a dual‐dynamic bonding polymer system and self‐healable conductive layers are created using polymer as a matrix for a silver composite. These materials are employed to prepare capacitive sensors to demonstrate a stretchable and self‐healable touch pad.     

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。     

Bioinspired Dual-Mode Stretchable Strain Sensor Based on Magnetic Nanocomposites for Strain/Magnetic Discrimination

Recently, flexible stretchable sensors have been gaining attention for their excellent adaptability for electronic skin applications. However, the preparation of stretchable strain sensors that achieve dual-mode sensing while still retaining ultra-low detection limit of strain, high sensitivity, and low cost is a pressing task. Herein, a high-performance dual-mode stretchable strain sensor (DMSSS) based on biomimetic scorpion foot slit microstructures and multi-walled carbon nanotubes (MWCNTs)/graphene (GR)/silicone rubber (SR)/Fe₃O₄ nanocomposites is proposed, which can accurately sense strain and magnetic stimuli. The DMSSS exhibits a large strain detection range (≈160%), sensitivity up to 100.56 (130–160%), an ultra-low detection limit of strain (0.16% strain), and superior durability (9000 cycles of stretch/release). The sensor can accurately recognize sign language movement, as well as realize object proximity information perception and whole process information monitoring. Furthermore, human joint movements and micro-expressions can be monitored in real-time. Therefore, the DMSSS of this work opens up promising prospects for applications in sign language pose recognition, non-contact sensing, human-computer interaction, and electronic skin.     

A Solution‐Processable,Omnidirectionally Stretchable,and High‐Pressure‐Sensitive Piezoresistive Device

The development of omnidirectionally stretchable pressure sensors with high performance without stretching‐induced interference has been hampered by many challenges. Herein, an omnidirectionally stretchable piezoresistive pressure‐sensing device is demonstrated by combining an omniaxially stretchable substrate with a 3D micropattern array and solution‐printing of electrode and piezoresistive materials. A unique substrate structural design and materials mean that devices that are highly sensitive are rendered, with a stable out‐of‐plane pressure response to both static (sensitivity of 0.5 kPa^?1 and limit of detection of 28 Pa) and dynamic pressures and the minimized in‐plane stretching responsiveness (a small strain gauge factor of 0.17), achieved through efficient strain absorption of the electrode and sensing materials. The device can detect human‐body tremors, as well as measure the relative elastic properties of human skin. The omnidirectionally stretchable pressure sensor with a high pressure sensitivity and minimal stretch‐responsiveness yields great potential to skin‐attachable wearable electronics, human–machine interfaces, and soft robotics applications.     

Ultrasensitive Strain Sensor Based on Separation of Overlapped Carbon Nanotubes

Although there have been remarkable improvements in stretchable strain sensors, the development of strain sensors with scalable fabrication techniques and which both high sensitivity and stretchability simultaneously is still challenging. In this work, a stretchable strain sensor based on overlapped carbon nanotube (CNT) bundles coupled with a silicone elastomer is presented. The strain sensor with overlapped CNTs is prepared by synthesizing line‐patterned vertically aligned CNT bundles and rolling and transferring them to the silicone elastomer. With the sliding and disconnection of the overlapped CNTs, the strain sensor performs excellently with a broad sensing range (≥145% strain), ultrahigh sensitivity (gauge factor of 42 300 at a strain of 125–145%), high repeatability, and durability. The performance of the sensor is also tunable by controlling the overlapped area of CNT bundles. Detailed mechanisms of the sensor and its applications in human motion detection are also further investigated. With the novel structure and mechanism, the sensor can detect a wide range of strains with high sensitivity, demonstrating the potential for numerous applications including wearable healthcare devices.     

Conductive Silk‐Based Composites Using Biobased Carbon Materials

There is great interest in developing conductive biomaterials for the manufacturing of sensors or flexible electronics with applications in healthcare, tracking human motion, or in situ strain measurements. These biomaterials aim to overcome the mismatch in mechanical properties at the interface between typical rigid semiconductor sensors and soft, often uneven biological surfaces or tissues for in vivo and ex vivo applications. Here, the use of biobased carbons to fabricate conductive, highly stretchable, flexible, and biocompatible silk‐based composite biomaterials is demonstrated. Biobased carbons are synthesized via hydrothermal processing, an aqueous thermochemical method that converts biomass into a carbonaceous material that can be applied upon activation as conductive filler in composite biomaterials. Experimental synthesis and full‐atomistic molecular dynamics modeling are combined to synthesize and characterize these conductive composite biomaterials, made entirely from renewable sources and with promising applications in fields like biomedicine, energy, and electronics.     

Ultraminiature and Flexible Sensor Based on Interior Corner Flow for Direct Pressure Sensing in Biofluids

Conventional pressure sensing devices are well developed for either indirect evaluation or internal measuring of fluid pressure over millimeter scale. Whereas, specialized pressure sensors that can directly work in various liquid environments at micrometer scale remain challenging and rarely explored, but are of great importance in many biomedical applications. Here, pressure sensor technology that utilizes capillary action to self‐assemble the pressure‐sensitive element is introduced. Sophisticated control of capillary flow, tunable sensitivity to liquid pressure in various mediums, and multiple transduction modes are realized in a polymer device, which is also flexible (thickness of 8 µm), ultraminiature (effective volume of 18 × 100 × 580 µm³), and transparent, enabling the sensor to work in some extreme situations, such as in narrow inner spaces (e.g., a microchannel of 220 µm in width and 100 µm in height), or on the surface of small objects (e.g., a 380 µm diameter needle). Potential applications of this sensor include disposables for in vivo and short‐term measurements.     

Stretchable Electronic Sensors of Nanocomposite Network Films for Ultrasensitive Chemical Vapor Sensing

A stretchable, transparent, and body‐attachable chemical sensor is assembled from the stretchable nanocomposite network film for ultrasensitive chemical vapor sensing. The stretchable nanocomposite network film is fabricated by in situ preparation of polyaniline/MoS₂ (PANI/MoS₂) nanocomposite in MoS₂ suspension and simultaneously nanocomposite deposition onto prestrain elastomeric polydimethylsiloxane substrate. The assembled stretchable electronic sensor demonstrates ultrasensitive sensing performance as low as 50 ppb, robust sensing stability, and reliable stretchability for high‐performance chemical vapor sensing. The ultrasensitive sensing performance of the stretchable electronic sensors could be ascribed to the synergistic sensing advantages of MoS₂ and PANI, higher specific surface area, the reliable sensing channels of interconnected network, and the effectively exposed sensing materials. It is expected to hold great promise for assembling various flexible stretchable chemical vapor sensors with ultrasensitive sensing performance, superior sensing stability, reliable stretchability, and robust portability to be potentially integrated into wearable electronics for real‐time monitoring of environment safety and human healthcare.     

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.     

A Polypyrrole Elastomer Based on Confined Polymerization in a Host Polymer Network for Highly Stretchable Temperature and Strain Sensors

For the purpose of stretchable electronics, broad interests have been paid to elastic conductors by which high tensile strain over 100% can be readily achieved. Here, a scalable‐processing, dyeing‐like strategy for highly stretchable polypyrrole elastomer (1450% in strain) is conceived without particular topological design. This approach effectively improves the mechanical properties of the classic insoluble polypyrrole by confined polymerization within an elastic polymer network. In terms of the easy processing, it is technically possible to prepare stretchable electronics with arbitrary shape and size for wearable electronics with low cost. The mechanism of interpenetrated networks coexisting with microphase separation is comprehensively illustrated at molecular scale. The as‐fabricated polypyrrole elastomers are utilized as temperature or strain sensors for automatic fishing and region‐distinct dual signal sensing. Further integration of multiple sensors offers immediate alarm for old people falling at home, which thereby proves its promising potential in practical applications.     

An Ultra‐Shapeable,Smart Sensing Platform Based on a Multimodal Ferrofluid‐Infused Surface

The development of wearable, all‐in‐one sensors that can simultaneously monitor several hazard conditions in a real‐time fashion imposes the emergent requirement for a smart and stretchable hazard avoidance sensing platform that is stretchable and skin‐like. Multifunctional sensors with these features are problematic and challenging to accomplish. In this context, a multimodal ferrofluid‐based triboelectric nanogenerator (FO‐TENG), featuring sensing capabilities to a variety of hazard stimulus such as a strong magnetic field, noise level, and falling or drowning is reported. The FO‐TENG consists of a deformable elastomer tube filled with a ferrofluid, as a triboelectric layer, surrounded by a patterned copper wire, as an electrode, endowing the FO‐TENG with excellent waterproof ability, conformability, and stretchability (up to 300%). In addition, The FO‐TENG is highly flexible and sustains structural integrity and detection capability under repetitive deformations, including bending and twisting. This FO‐TENG represents a smart multifaceted sensing platform that has a unique capacity in diverse applications including hazard preventive wearables, and remote healthcare monitoring.     

Advances in Rational Design and Materials of High‐Performance Stretchable Electromechanical Sensors

Stretchable and wearable sensor technology has attracted significant interests and created high technological impact on portable healthcare and smart human–machine interfaces. Wearable electromechanical systems are an important part of this technology that has recently witnessed tremendous progress toward high‐performance devices for commercialization. Over the past few years, great attention has been paid to simultaneously enhance the sensitivity and stretchability of the electromechanical sensors toward high sensitivity, ultra‐stretchability, low power consumption or self‐power functionalities, miniaturisation as well as simplicity in design and fabrication. This work presents state‐of‐the‐art advanced materials and rational designs of electromechanical sensors for wearable applications. Advances in various sensing concepts and structural designs for intrinsic stretchable conductive materials as well as advanced rational platforms are discussed. In addition, the practical applications and challenges in the development of stretchable electromechanical sensors are briefly mentioned and highlighted.     

A Self‐Powered and Flexible Organometallic Halide Perovskite Photodetector with Very High Detectivity

Flexible and self‐powered photodetectors (PDs) are highly desirable for applications in image sensing, smart building, and optical communications. In this paper, a self‐powered and flexible PD based on the methylammonium lead iodide (CH₃NH₃PBI₃) perovskite is demonstrated. Such a self‐powered PD can operate even with irregular motion such as human finger tapping, which enables it to work without a bulky external power source. In addition, with high‐quality CH₃NH₃PBI₃ perovskite thin film fabricated with solvent engineering, the PD exhibits an impressive detectivity of 1.22 × 10¹³ Jones. In the self‐powered voltage detection mode, it achieves a large responsivity of up to 79.4 V mW^?1 cm^?2 and a voltage response of up to ≈90%. Moreover, as the PD is made of flexible and transparent polymer films, it can operate under bending and functions at 360 ° of illumination. As a result, the self‐powered, flexible, 360 ° omnidirectional perovskite PD, featuring high detectivity and responsivity along with real‐world sensing capability, suggests a new direction for next‐generation optical communications, sensing, and imaging applications.     

Biofriendly,Stretchable, and Reusable Hydrogel Electronics as Wearable Force Sensors

The ever‐growing overlap between stretchable electronic devices and wearable healthcare applications is igniting the discovery of novel biocompatible and skin‐like materials for human‐friendly stretchable electronics fabrication. Amongst all potential candidates, hydrogels with excellent biocompatibility and mechanical features close to human tissues are constituting a promising troop for realizing healthcare‐oriented electronic functionalities. In this work, based on biocompatible and stretchable hydrogels, a simple paradigm to prototype stretchable electronics with an embedded three‐dimensional (3D) helical conductive layout is proposed. Thanks to the 3D helical structure, the hydrogel electronics present satisfactory mechanical and electrical robustness under stretch. In addition, reusability of stretchable electronics is realized with the proposed scenario benefiting from the swelling property of hydrogel. Although losing water would induce structure shrinkage of the hydrogel network and further undermine the function of hydrogel in various applications, the worn‐out hydrogel electronics can be reused by simply casting it in water. Through such a rehydration procedure, the dehydrated hydrogel can absorb water from the surrounding and then the hydrogel electronics can achieve resilience in mechanical stretchability and electronic functionality. Also, the ability to reflect pressure and strain changes has revealed the hydrogel electronics to be promising for advanced wearable sensing applications.     

Laser‐Induced Freestanding Graphene Papers: A New Route of Scalable Fabrication with Tunable Morphologies and Properties for Multifunctional Devices and Structures

The recently emergent laser‐induced graphene (LIG) technology has endowed the fabrication of smart devices with one‐step processing and scalable/designable features. Graphene paper (GP), an important architecture of 2D layered carbon, however, is never produced through LIG. Herein, a novel strategy is reported for production of freestanding GP through LIG technology. It is first determined that the unique spatial configuration of polyimide (PI) paper is critical for the preparation of GP without the appearance of intense shape distortion. Benefiting from the mechanism, the as‐produced laser‐induced graphene paper (LIGP) is foldable, trimmable, and integratable to customized shapes and structures with the largest dimension of 40 × 35 cm². Based on the processing–structure–property relationship study, one is capable of controlling and tuning various physical and chemical properties of LIGPs, rendering them unique for assembling flexible electronics and smart structures, e.g., human/robotic motion detectors, liquid sensors, water–oil separators, antibacterial media, and flame retardant/deicing/self‐sensing composites. With the key findings, the escalation of LIGP for commercialization, roll‐to‐roll manufacturing, and multidisciplinary applications are highly expected.     

Mechanically Flexible Conductors for Stretchable and Wearable E‐Skin and E‐Textile Devices

Considerable progress in materials development and device integration for mechanically bendable and stretchable optoelectronics will broaden the application of “Internet‐of‐Things” concepts to a myriad of new applications. When addressing the needs associated with the human body, such as the detection of mechanical functions, monitoring of health parameters, and integration with human tissues, optoelectronic devices, interconnects/circuits enabling their functions, and the core passive components from which the whole system is built must sustain different degrees of mechanical stresses. Herein, the basic characteristics and performance of several of these devices are reported, particularly focusing on the conducting element constituting them. Among these devices, strain sensors of different types, energy storage elements, and power/energy storage and generators are included. Specifically, the advances during the past 3 years are reported, wherein mechanically flexible conducting elements are fabricated from (0D, 1D, and 2D) conducting nanomaterials from metals (e.g., Au nanoparticles, Ag flakes, Cu nanowires), carbon nanotubes/nanofibers, 2D conductors (e.g., graphene, MoS₂), metal oxides (e.g., Zn nanorods), and conducting polymers (e.g., poly(3,4‐ethylenedioxythiophene):poly(4‐styrene sulfonate), polyaniline) in combination with passive fibrotic and elastomeric materials enabling, after integration, the so‐called electronic skins and electronic textiles.     

Nanomaterial-Enabled Flexible and Stretchable Sensing Systems: Processing,Integration, and Applications

Nanomaterial-enabled flexible and stretchable electronics have seen tremendous progress in recent years, evolving from single sensors to integrated sensing systems. Compared with nanomaterial-enabled sensors with a single function, integration of multiple sensors is conducive to comprehensive monitoring of personal health and environment, intelligent human–machine interfaces, and realistic imitation of human skin in robotics and prosthetics. Integration of sensors with other functional components promotes real-world applications of the sensing systems. Here, an overview of the design and integration strategies and manufacturing techniques for such sensing systems is given. Then, representative nanomaterial-enabled flexible and stretchable sensing systems are presented. Following that, representative applications in personal health, fitness tracking, electronic skins, artificial nervous systems, and human–machine interactions are provided. To conclude, perspectives on the challenges and opportunities in this burgeoning field are considered.