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.     

Stretchable Transistor-Structured Artificial Synapses for Neuromorphic Electronics

Stretchable synaptic transistors, a core technology in neuromorphic electronics, have functions and structures similar to biological synapses and can concurrently transmit signals and learn. Stretchable synaptic transistors are usually soft and stretchy and can accommodate various mechanical deformations, which presents significant prospects in soft machines, electronic skin, human–brain interfaces, and wearable electronics. Considerable efforts have been devoted to developing stretchable synaptic transistors to implement electronic device neuromorphic functions, and remarkable advances have been achieved. Here, this review introduces the basic concept of artificial synaptic transistors and summarizes the recent progress in device structures, functional-layer materials, and fabrication processes. Classical stretchable synaptic transistors, including electric double-layer synaptic transistors, electrochemical synaptic transistors, and optoelectronic synaptic transistors, as well as the applications of stretchable synaptic transistors in light-sensory systems, tactile-sensory systems, and multisensory artificial-nerves systems, are discussed. Finally, the current challenges and potential directions of stretchable synaptic transistors are analyzed. This review presents a detailed introduction to the recent progress in stretchable synaptic transistors from basic concept to applications, providing a reference for the development of stretchable synaptic transistors in the future.     

Rubbery Electronics Fully Made of Stretchable Elastomeric Electronic Materials

Stretchable electronics outperform existing rigid and bulky electronics and benefit a wide range of species, including humans, machines, and robots, whose activities are associated with large mechanical deformation and strain. Due to the nonstretchable nature of most electronic materials, in particular semiconductors, stretchable electronics are mostly realized through the strategies of architectural engineering to accommodate mechanical stretching rather than imposing strain into the materials directly. On the other hand, recent development of stretchable electronics by creating them entirely from stretchable elastomeric electronic materials, i.e., rubbery electronics, suggests a feasible a venue. Rubbery electronics have gained increasing interest due to the unique advantages that they and their associated manufacturing technologies have offered. This work reviews the recent progress in developing rubbery electronics, including the crucial stretchable elastomeric materials of rubbery conductors, rubbery semiconductors, and rubbery dielectrics. Thereafter, various rubbery electronics such as rubbery transistors, integrated electronics, rubbery optoelectronic devices, and rubbery sensors are discussed.     

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.     

Stretchable Organic Semiconductor Devices

Stretchable electronics are essential for the development of intensely packed collapsible and portable electronics, wearable electronics, epidermal and bioimplanted electronics, 3D surface compliable devices, bionics, prosthesis, and robotics. However, most stretchable devices are currently based on inorganic electronics, whose high cost of fabrication and limited processing area make it difficult to produce inexpensive, large‐area devices. Therefore, organic stretchable electronics are highly attractive due to many advantages over their inorganic counterparts, such as their light weight, flexibility, low cost and large‐area solution‐processing, the reproducible semiconductor resources, and the easy tuning of their properties via molecular tailoring. Among them, stretchable organic semiconductor devices have become a hot and fast‐growing research field, in which great advances have been made in recent years. These fantastic advances are summarized here, focusing on stretchable organic field‐effect transistors, light‐emitting devices, solar cells, and memory devices.     

Materials and Structures for Stretchable Energy Storage and Conversion Devices

Stretchable energy storage and conversion devices (ESCDs) are attracting intensive attention due to their promising and potential applications in realistic consumer products, ranging from portable electronics, bio‐integrated devices, space satellites, and electric vehicles to buildings with arbitrarily shaped surfaces. Material synthesis and structural design are core in the development of highly stretchable supercapacitors, batteries, and solar cells for practical applications. This review provides a brief summary of research development on the stretchable ESCDs in the past decade, from structural design strategies to novel materials synthesis. The focuses are on the fundamental insights of mechanical characteristics of materials and structures on the performance of the stretchable ESCDs, as well as challenges for their practical applications. Finally, some of the important directions in the areas of material synthesis and structural design facing the stretchable ESCDs are discussed.     

Recent Advances in Transparent Electronics with Stretchable Forms

Advances in materials science and the desire for next‐generation electronics have driven the development of stretchable and transparent electronics in the past decade. Novel applications, such as smart contact lenses and wearable sensors, have been introduced with stretchable and transparent form factors, requiring a deeper and wider exploration of materials and fabrication processes. In this regard, many research efforts have been dedicated to the development of mechanically stretchable, optically transparent materials and devices. Recent advances in stretchable and transparent electronics are discussed herein, with special emphasis on the development of stretchable and transparent materials, including substrates and electrodes. Several representative examples of applications enabled by stretchable and transparent electronics are presented, including sensors, smart contact lenses, heaters, and neural interfaces. The current challenges and opportunities for each type of stretchable and transparent electronics are also discussed.     

Stretchable Thin‐Film Electrodes for Flexible Electronics with High Deformability and Stretchability

Flexible and stretchable electronics represent today's cutting‐edge electronic technologies. As the most‐fundamental component of electronics, the thin‐film electrode remains the research frontier due to its key role in the successful development of flexible and stretchable electronic devices. Stretchability, however, is generally more challenging to achieve than flexibility. Stretchable electronic devices demand, above all else, that the thin‐film electrodes have the capacity to absorb a large level of strain (>>1%) without obvious changes in their electrical performance. This article reviews the progress in strategies for obtaining highly stretchable thin‐film electrodes. Applications of stretchable thin‐film electrodes fabricated via these strategies are described. Some perspectives and challenges in this field are also put forward.     

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.     

Metal Deposition on a Self‐Generated Microfibril Network to Fabricate Stretchable Tactile Sensors Providing Analog Position Information

Stretchable conductors and sensors have attracted great attention for use in electronic skin and healthcare monitoring. Despite the development of many stretchable conductors, there are still very few studies that utilize the conventional methods making electrodes and circuits used in current industry. A method is proposed to fabricate a stretchable electrode pattern and a stretchable tactile sensor by simply depositing linear metal lines through a mask on a stretchable substrate. A method is developed of a self‐generating microfibril network on the surface of stretchable block copolymer substrates. The formation mechanism of the microfibril network is studied with finite element method simulations. Metals (Au and Ag nanowires) are deposited directly on the substrate through a patterned mask. This study shows that strain‐insensitive circuit and strain‐sensitive sensor can be fabricated in a controlled way by adjusting the thickness of the deposited metal, which makes it easy to fabricate a tactile sensor by metal deposition. Also, by using the characteristic that the sensor has different sensitivity depending on the line pattern width, a novel sensor structure simultaneously providing analog‐type position information and pressure value is proposed.     

Fabrication of Highly Stretchable Conductors via Morphological Control of Carbon Nanotube Network

Stretchable conductors, which can keep their excellent electrical conductivity while highly stretched, have been investigated extensively due to their wide range of applications in flexible and stretchable electronics, wearable displays, etc.; however, their preparation is often complicated and expensive. Herein, an efficient method to prepare high performance stretchable conductors through morphological control of conductive networks formed with carbon nanotubes (CNTs) in an elastomer matrix is reported. It is observed that an interface‐mediated method could be used to align randomly oriented filler during stretching and to induce buckling of CNTs during relaxation. Further morphological studies indicate the possible formation of a wavy CNT structure induced by cyclic pre‐straining. Subsequent thermal annealing is observed to collapse the oriented network and improve the local contacts between conductive networks. Through such a simple procedure, a conductivity of nearly 1000 S m^?1 and a stretchability of 200% can be achieved for composites containing 20 wt% CNTs. CNTs are observed to buckle over a large area in polymer bulk, and the combination of pre‐straining and thermal annealing modifies the conductive network in the elastomer matrix. As a general method, this could be used for easy fabrication of high‐performance stretchable conductors for arbitrary‐shaped objects on a large scale.     

Energy Harvesters for Wearable and Stretchable Electronics: From Flexibility to Stretchability

The rapid advancements of wearable electronics have caused a paradigm shift in consumer electronics, and the emerging development of stretchable electronics opens a new spectrum of applications for electronic systems. Playing a critical role as the power sources for independent electronic systems, energy harvesters with high flexibility or stretchability have been the focus of research efforts over the past decade. A large number of the flexible energy harvesters developed can only operate at very low strain level (≈0.1%), and their limited flexibility impedes their application in wearable or stretchable electronics. Here, the development of highly flexible and stretchable (stretchability >15% strain) energy harvesters is reviewed with emphasis on strategies of materials synthesis, device fabrication, and integration schemes for enhanced flexibility and stretchability. Due to their particular potential applications in wearable and stretchable electronics, energy‐harvesting devices based on piezoelectricity, triboelectricity, thermoelectricity, and dielectric elastomers have been largely developed and the progress is summarized. The challenges and opportunities of assembly and integration of energy harvesters into stretchable systems are also discussed.     

Recent Advances in 1D Stretchable Electrodes and Devices for Textile and Wearable Electronics: Materials,Fabrications, and Applications

Research on wearable electronic devices that can be directly integrated into daily textiles or clothes has been explosively grown holding great potential for various practical wearable applications. These wearable electronic devices strongly demand 1D electronic devices that are light–weight, weavable, highly flexible, stretchable, and adaptable to comport to frequent deformations during usage in daily life. To this end, the development of 1D electrodes with high stretchability and electrical performance is fundamentally essential. Herein, the recent process of 1D stretchable electrodes for wearable and textile electronics is described, focusing on representative conductive materials, fabrication techniques for 1D stretchable electrodes with high performance, and designs and applications of various 1D stretchable electronic devices. To conclude, discussions are presented regarding limitations and perspectives of current materials and devices in terms of performance and scientific understanding that should be considered for further advances.     

Auxetic Mechanical Metamaterials to Enhance Sensitivity of Stretchable Strain Sensors

Stretchable strain sensors play a pivotal role in wearable devices, soft robotics, and Internet‐of‐Things, yet these viable applications, which require subtle strain detection under various strain, are often limited by low sensitivity. This inadequate sensitivity stems from the Poisson effect in conventional strain sensors, where stretched elastomer substrates expand in the longitudinal direction but compress transversely. In stretchable strain sensors, expansion separates the active materials and contributes to the sensitivity, while Poisson compression squeezes active materials together, and thus intrinsically limits the sensitivity. Alternatively, auxetic mechanical metamaterials undergo 2D expansion in both directions, due to their negative structural Poisson's ratio. Herein, it is demonstrated that such auxetic metamaterials can be incorporated into stretchable strain sensors to significantly enhance the sensitivity. Compared to conventional sensors, the sensitivity is greatly elevated with a 24‐fold improvement. This sensitivity enhancement is due to the synergistic effect of reduced structural Poisson's ratio and strain concentration. Furthermore, microcracks are elongated as an underlying mechanism, verified by both experiments and numerical simulations. This strategy of employing auxetic metamaterials can be further applied to other stretchable strain sensors with different constituent materials. Moreover, it paves the way for utilizing mechanical metamaterials into a broader library of stretchable electronics.     

Adsorbed Eutectic GaIn Structures on a Neoprene Foam for Stretchable MRI Coils

Stretchable conductors based on eutectic gallium–indium (eGaIn) alloy are patterned on a polychloroprene substrate (neoprene foam) using stencil printing. By tuning the amount of eGaIn on the neoprene substrate, different strain‐sensitivity of electrical resistance is achieved. Conductors with a layer of eGaIn, which adsorbs to the walls of 60–100 µm wide neoprene cells, change their electrical resistance for 5% at 100% strain. When the amount of eGaIn is increased, the cells are filled with eGaIn and the strain‐sensitivity of the electrical resistance rises to 300% at 100% strain. The developed conductors are patterned as stretchable on‐body coils for receiving magnetic signals in a clinical magnetic resonance imaging setup. First images with a stretchable coil are acquired on an orange and compared to the images that are recorded using a rigid copper coil of the same size.     

Material Design and Fabrication Strategies for Stretchable Metallic Nanocomposites

Stretchable conductive nanocomposites fabricated by integrating metallic nanomaterials with elastomers have become a vital component of human‐friendly electronics, such as wearable and implantable devices, due to their unconventional electrical and mechanical characteristics. Understanding the detailed material design and fabrication strategies to improve the conductivity and stretchability of the nanocomposites is therefore important. This Review discusses the recent technological advances toward high performance stretchable metallic nanocomposites. First, the effect of the filler material design on the conductivity is briefly discussed, followed by various nanocomposite fabrication techniques to achieve high conductivity. Methods for maintaining the initial conductivity over a long period of time are also summarized. Then, strategies on controlled percolation of nanomaterials are highlighted, followed by a discussion regarding the effects of the morphology of the nanocomposite and postfabricated 3D structures on achieving high stretchability. Finally, representative examples of applications of such nanocomposites in biointegrated electronics are provided. A brief outlook concludes this Review.     

A Highly Stretchable Liquid Metal Polymer as Reversible Transitional Insulator and Conductor

Materials with a temperature‐controlled reversible electrical transition between insulator and conductor are attracting huge attention due to their promising applications in many fields. However, most of them are intrinsically rigid and require complicated fabrication processes. Here, a highly stretchable (680% strain) liquid metal polymer composite as a reversible transitional insulator and conductor (TIC), which is accompanied with huge resistivity changes (more than 4 × 10⁹ times) reversibly through a tuning temperature in a few seconds is introduced. When frozen, the insulated TIC becomes conductive and recovers after warming. Both the phase change of the liquid metal droplets and the rigidity change of the polymer contribute directly to transition between insulator and conductor. A simplified model is established to predict the expansion and connection of liquid metal droplets. Along with high stretchability, straightforward fabrication methods, rapid triggering time, large switching ratio, good repeatability, the TIC offers tremendous possibilities for numerous applications, like stretchable switches, semiconductors, temperature sensors, and resistive random‐access memory. Accordingly, a system that can display numbers and letters via converting alternative TIC temperature to a binary signal on a computer is conceived and demonstrated. The present discovery suggests a general strategy for fabricating and stimulating a stretchable transitional insulator and conductor based on liquid metal and allied polymers.     

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.     

Stretchable,Large‐area Organic Electronics

Stretchability will significantly expand the application scope of electronics, particularly large‐area electronics—displays, sensors, and actuators. If arbitrary surfaces and movable parts could be covered with stretchable electronics, which is impossible with conventional electronics, new classes of applications are expected to emerge. A large hurdle is manufacturing electrical wiring with high conductivity, high stretchability, and large‐area compatibility. This Review describes stretchable, large‐area electronics based on organic field‐effect transistors for applications to sensors and displays. First, novel net‐shaped organic transistors are employed to realize stretchable, large‐area sensor networks that detect distributions of pressure and temperature simultaneously. The whole system is functional even when it is stretched by 25%. In order to further improve stretchability, printable elastic conductors are developed by dispersing single‐walled carbon nanotubes (SWNTs) as dopants uniformly in rubbers. Further, we describe integration of printable elastic conductors with organic transistors to construct a rubber‐like stretchable active matrix for large‐area sensor and display applications. Finally, we will discuss the future prospects of stretchable, large‐area electronics with delineating a picture of the next‐generation human/machine interfaces from the aspect of materials science and electronic engineering.