25th Anniversary Article: Materials for High‐Performance Biodegradable Semiconductor Devices

We review recent progress in a class of silicon‐based electronics that is capable of complete, controlled dissolution when immersed in water or bio‐fluids. This type of technology, referred to in a broader sense as transient electronics, has potential applications in resorbable biomedical devices, eco‐friendly electronics, environmental sensors, secure hardware systems and others. New results reported here include studies of the kinetics of hydrolysis of nanomembranes of single crystalline silicon in bio‐fluids and aqueous solutions at various pH levels and temperatures. Evaluations of toxicity using live animal models and test coupons of transient electronic materials provide some evidence of their biocompatibility, thereby suggesting potential for use in bioresorbable electronic implants.     

Metallogels: Availability,Applicability, and Advanceability

Introducing metal components into gel matrices provides an effective strategy to develop soft materials with advantageous properties such as: optical activity, conductivity, magnetic response activity, self‐healing activity, catalytic activity, etc. In this context, a thorough overview of application‐oriented metallogels is provided. Considering that many well‐established metallogels start from serendipitous discoveries, insights into the structure–gelation relationship will offer a profound impact on the development of metallogels. Initially, design strategies for discovering new metallogels are discussed, then the advanced applications of metallogels are summarized. Finally, perspectives regarding the design of metallogels, the potential applications of metallogels and their derivative materials are briefly proposed.     

Buckled Structures: Fabrication and Applications in Wearable Electronics

Wearable electronics have attracted a tremendous amount of attention due to their many potential applications, such as personalized health monitoring, motion detection, and smart clothing, where electronic devices must conformably form contacts with curvilinear surfaces and undergo large deformations. Structural design and material selection have been the key factors for the development of wearable electronics in the recent decades. As one of the most widely used geometries, buckling structures endow high stretchability, high mechanical durability, and comfortable contact for human–machine interaction via wearable devices. In addition, buckling structures that are derived from natural biosurfaces have high potential for use in cost‐effective and high‐grade wearable electronics. This review provides fundamental insights into buckling fabrication and discusses recent advancements for practical applications of buckled electronics, such as interconnects, sensors, transistors, energy storage, and conversion devices. In addition to the incorporation of desired functions, the simple and consecutive manipulation and advanced structural design of the buckled structures are discussed, which are important for advancing the field of wearable electronics. The remaining challenges and future perspectives for buckled electronics are briefly discussed in the final section.     

Flexible electronics: 12‐GHz Thin‐Film Transistors on Transferrable Silicon Nanomembranes for High‐Performance Flexible Electronics (Small 22/2010)

Multigigahertz flexible electronics are attractive and have broad applications. A gate‐after‐source/drain fabrication process using preselectively doped single‐crystal silicon nanomembranes (SiNM) is an effective approach to realizing high device speed. However, further downscaling this approach has become difficult in lithography alignment. In this full paper, a local alignment scheme in combination with more accurate SiNM transfer measures for minimizing alignment errors is reported. By realizing 1 μm channel alignment for the SiNMs on a soft plastic substrate, thin‐film transistors with a record speed of 12 GHz maximum oscillation frequency are demonstrated. These results indicate the great potential of properly processed SiNMs for high‐performance flexible electronics.     

Dynamic and Tunable Threshold Voltage in Organic Electrochemical Transistors

In recent years, organic electrochemical transistors (OECTs) have found applications in chemical and biological sensing and interfacing, neuromorphic computing, digital logic, and printed electronics. However, the incorporation of OECTs in practical electronic circuits is limited by the relative lack of control over their threshold voltage, which is important for controlling the power consumption and noise margin in complementary and unipolar circuits. Here, the threshold voltage of OECTs is precisely tuned over a range of more than 1 V by chemically controlling the electrochemical potential at the gate electrode. This threshold voltage tunability is exploited to prepare inverters and amplifiers with improved noise margin and gain, respectively. By coupling the gate electrode with an electrochemical oscillator, single‐transistor oscillators based on OECTs with dynamic time‐varying threshold voltages are prepared. This work highlights the importance of electrochemistry at the gate electrode in determining the electrical properties of OECTs, and opens a path toward the system‐level design of low‐power OECT‐based electronics.     

High‐Density Stretchable Electrode Grids for Chronic Neural Recording

Electrical interfacing with neural tissue is key to advancing diagnosis and therapies for neurological disorders, as well as providing detailed information about neural signals. A challenge for creating long‐term stable interfaces between electronics and neural tissue is the huge mechanical mismatch between the systems. So far, materials and fabrication processes have restricted the development of soft electrode grids able to combine high performance, long‐term stability, and high electrode density, aspects all essential for neural interfacing. Here, this challenge is addressed by developing a soft, high‐density, stretchable electrode grid based on an inert, high‐performance composite material comprising gold‐coated titanium dioxide nanowires embedded in a silicone matrix. The developed grid can resolve high spatiotemporal neural signals from the surface of the cortex in freely moving rats with stable neural recording quality and preserved electrode signal coherence during 3 months of implantation. Due to its flexible and stretchable nature, it is possible to minimize the size of the craniotomy required for placement, further reducing the level of invasiveness. The material and device technology presented herein have potential for a wide range of emerging biomedical applications.     

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.     

Deformable Organic Nanowire Field‐Effect Transistors

Deformable electronic devices that are impervious to mechanical influence when mounted on surfaces of dynamically changing soft matters have great potential for next‐generation implantable bioelectronic devices. Here, deformable field‐effect transistors (FETs) composed of single organic nanowires (NWs) as the semiconductor are presented. The NWs are composed of fused thiophene diketopyrrolopyrrole based polymer semiconductor and high‐molecular‐weight polyethylene oxide as both the molecular binder and deformability enhancer. The obtained transistors show high field‐effect mobility >8 cm² V^?1 s^?1 with poly(vinylidenefluoride‐ co ‐trifluoroethylene) polymer dielectric and can easily be deformed by applied strains (both 100% tensile and compressive strains). The electrical reliability and mechanical durability of the NWs can be significantly enhanced by forming serpentine‐like structures of the NWs. Remarkably, the fully deformable NW FETs withstand 3D volume changes (>1700% and reverting back to original state) of a rubber balloon with constant current output, on the surface of which it is attached. The deformable transistors can robustly operate without noticeable degradation on a mechanically dynamic soft matter surface, e.g., a pulsating balloon (pulse rate: 40 min^?1 (0.67 Hz) and 40% volume expansion) that mimics a beating heart, which underscores its potential for future biomedical applications.     

Recent Progress in n‐Channel Organic Thin‐Film Transistors

Particular attention has been focused on n‐channel organic thin‐film transistors (OTFTs) during the last few years, and the potentially cost‐effective circuitry‐based applications in flexible electronics, such as flexible radiofrequency identity tags, smart labels, and simple displays, will benefit from this fast development. This article reviews recent progress in performance and molecular design of n‐channel semiconductors in the past five years, and limitations and practicable solutions for n‐channel OTFTs are dealt with from the viewpoint of OTFT constitution and geometry, molecular design, and thin‐film growth conditions. Strategy methodology is especially highlighted with an aim to investigate basic issues in this field.     

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.     

Skin‐Friendly Electronics for Acquiring Human Physiological Signatures

Epidermal sensing devices offer great potential for real‐time health and fitness monitoring via continuous characterization of the skin for vital morphological, physiological, and metabolic parameters. However, peeling them off can be difficult and sometimes painful especially when these skin‐mounted devices are applied on sensitive or wounded regions of skin due to their strong adhesion. A set of biocompatible and water‐decomposable “skin‐friendly” epidermal electronic devices fabricated on flexible, stretchable, and degradable protein‐based substrates are reported. Strong adhesion and easy detachment are achieved concurrently through an environmentally benign, plasticized protein platform offering engineered mechanical properties and water‐triggered, on‐demand decomposition lifetime (transiency). Human experiments show that multidimensional physiological signals can be measured using these innovative epidermal devices consisting of electro‐ and biochemical sensing modules and analyzed for important physiological signatures using an artificial neural network. The advances provide unique, versatile capabilities and broader applications for user‐ and environmentally friendly epidermal devices.     

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.     

Ultrafast Field‐Emission Electron Sources Based on Nanomaterials

The search for electron sources with simultaneous optimal spatial and temporal resolution has become an area of intense activity for a wide variety of applications in the emerging fields of lightwave electronics and attosecond science. Most recently, increasing efforts are focused on the investigation of ultrafast field‐emission phenomena of nanomaterials, which not only are fascinating from a fundamental scientific point of view, but also are of interest for a range of potential applications. Here, the current state‐of‐the‐art in ultrafast field‐emission, particularly sub‐optical‐cycle field emission, based on various nanostructures (e.g., metallic nanotips, carbon nanotubes) is reviewed. A number of promising nanomaterials and possible future research directions are also established.     

Inkjet‐Printed High‐Performance Flexible Micro‐Supercapacitors with Porous Nanofiber‐Like Electrode Structures

Flexible planar micro‐supercapacitors (MSCs) with unique loose and porous nanofiber‐like electrode structures are fabricated by combining electrochemical deposition with inkjet printing. Benefiting from the resulting porous nanofiber‐like structures, the areal capacitance of the inkjet‐printed flexible planar MSCs is obviously enhanced to 46.6 mF cm^?2, which is among the highest values ever reported for MSCs. The complicated fabrication process is successfully averted as compared with previously reported best‐performing planar MSCs. Besides excellent electrochemical performance, the resultant MSCs also show superior mechanical flexibility. The as‐fabricated MSCs can be highly bent to 180° 1000 times with the capacitance retention still up to 86.8%. Intriguingly, because of the remarkable patterning capability of inkjet printing, various modular MSCs in serial and in parallel can be directly and facilely inkjet‐printed without using external metal interconnects and tedious procedures. As a consequence, the electrochemical performance can be largely enhanced to better meet the demands of practical applications. Additionally, flexible serial MSCs with exquisite and aesthetic patterns are also inkjet‐printed, showing great potential in fashionable wearable electronics. The results suggest a feasible strategy for the facile and cost‐effective fabrication of high‐performance flexible MSCs via inkjet printing.     

Ultrasound‐Propelled Nanocups for Drug Delivery

Ultrasound‐induced bubble activity (cavitation) has been recently shown to actively transport and improve the distribution of therapeutic agents in tumors. However, existing cavitation‐promoting agents are micron‐sized and cannot sustain cavitation activity over prolonged time periods because they are rapidly destroyed upon ultrasound exposure. A novel ultrasound‐responsive single‐cavity polymeric nanoparticle (nanocup) capable of trapping and stabilizing gas against dissolution in the bloodstream is reported. Upon ultrasound exposure at frequencies and intensities achievable with existing diagnostic and therapeutic systems, nanocups initiate and sustain readily detectable cavitation activity for at least four times longer than existing microbubble constructs in an in vivo tumor model. As a proof‐of‐concept of their ability to enhance the delivery of unmodified therapeutics, intravenously injected nanocups are also found to improve the distribution of a freely circulating IgG mouse antibody when the tumor is exposed to ultrasound. Quantification of the delivery distance and concentration of both the nanocups and coadministered model therapeutic in an in vitro flow phantom shows that the ultrasound‐propelled nanocups travel further than the model therapeutic, which is itself delivered to hundreds of microns from the vessel wall. Thus nanocups offer considerable potential for enhanced drug delivery and treatment monitoring in oncological and other biomedical applications.     

Liquid Metal–Based Soft Microfluidics

Motivated by the increasing demand of wearable and soft electronics, liquid metal (LM)‐based microfluidics has been subjected to tremendous development in the past decade, especially in electronics, robotics, and related fields, due to the unique advantages of LMs that combines the conductivity and deformability all‐in‐one. LMs can be integrated as the core component into microfluidic systems in the form of either droplets/marbles or composites embedded by polymer materials with isotropic and anisotropic distribution. The LM microfluidic systems are found to have broad applications in deformable antennas, soft diodes, biomedical sensing chips, transient circuits, mechanically adaptive materials, etc. Herein, the recent progress in the development of LM‐based microfluidics and their potential applications are summarized. The current challenges toward industrial applications and future research orientation of this field are also summarized and discussed.     

How Do the Electrical Properties of Graphene Change with its Functionalization?

Functionalization of graphene is essential to interface it with other moieties to expand the scope of its electrical/electronic applications. However, chemical functionalization and/or molecular interactions on graphene sensitively modulate its electrical properties. To evaluate and take advantage of the properties of functionalized graphene, it is important to understand how its electrical attributes (such as carrier scattering, carrier concentration, charge polarity, quantum‐capacitance enhanced doping, energy levels, transport mechanisms, and orbital hybridization of energy‐bands) are influenced by a change in carbon's structural conformation, hybridization state, chemical potential, local energy levels, and dopant/interface coupling induced via functionalization or molecular interactions. Here, a detailed and integrated model describes factors influencing these electrical characteristics of functionalized graphene (covalent bonds, adsorption, π–π bonds, and lattice incorporation). The electrical properties are governed via three mechanisms: (a) conversion of carbon's hybridized state, (b) dipole interactions enhanced via quantum capacitance, and (c) orbital hybridization with an interfacing molecule. A few graphenic materials are also identified where further studies are essential to understand the effect of their functionalization.     

Materials and Designs for Wearable Photodetectors

Photodetectors (PDs), as an indispensable component in electronics, are highly desired to be flexible to meet the trend of next‐generation wearable electronics. Unfortunately, no in‐depth reviews on the design strategies, material exploration, and potential applications of wearable photodetectors are found in literature to date. Thus, this progress report first summarizes the fundamental design principles of turning “hard” photodetectors “soft,” including 2D (polymer and paper substrate‐based devices) and 1D PDs (fiber shaped devices). In short, the flexibility of PDs is realized through elaborate substrate modification, material selection, and device layout. More importantly, this report presents the current progress and specific requirements for wearable PDs according to the application: monitoring, imaging, and optical communication. Challenges and future research directions in these fields are proposed at the end. The purpose of this progress report is not only to shed light on the basic design principles of wearable PDs, but also serve as the roadmap for future exploration in wearable PDs in various applications, including health monitoring and Internet of Things.     

Supramolecular Helices: Chirality Transfer from Conjugated Molecules to Structures

Different scales of chirality endow a material with many excellent properties and potential applications. In this review, using π‐conjugated molecules as functional building blocks, recent progress on supramolecular helices inspired by biological helicity is summarized. First, induced chirality on conjugated polymers and small molecules is introduced. Molecular chirality can be amplified to nanostructures, superstructures, and even macroscopic structures by a self‐assembly process. Then, the principles for tuning the helicity of supramolecular chirality, as well as formation of helical heterojunctions, are summarized. Finally, the potential applications of chiral structures in chiral sensing and organic electronic devices are critically reviewed. Due to recent progress in chiral structures, an interdisciplinary area called “chiral electronics” is expected to gain wide popularity in the near future.     

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.