A High‐Performance Top‐Gated Graphene Field‐Effect Transistor with Excellent Flexibility Enabled by an iCVD Copolymer Gate Dielectric

A high‐performance top‐gated graphene field‐effect transistor (FET) with excellent mechanical flexibility is demonstrated by implementing a surface‐energy‐engineered copolymer gate dielectric via a solvent‐free process called initiated chemical vapor deposition. The ultrathin, flexible copolymer dielectric is synthesized from two monomers composed of 1,3,5‐trimethyl‐1,3,5‐trivinyl cyclotrisiloxane and 1‐vinylimidazole (VIDZ). The copolymer dielectric enables the graphene device to exhibit excellent dielectric performance and substantially enhanced mechanical flexibility. The p‐doping level of the graphene can be tuned by varying the polar VIDZ fraction in the copolymer dielectric, and the Dirac voltage (V_Dirac) of the graphene FET can thus be systematically controlled. In particular, the V_Dirac approaches neutrality with higher VIDZ concentrations in the copolymer dielectric, which minimizes the carrier scattering and thereby improves the charge transport of the graphene device. As a result, the graphene FET with 20 nm thick copolymer dielectrics exhibits field‐effect hole and electron mobility values of over 7200 and 3800 cm² V^?1 s^?1, respectively, at room temperature. These electrical characteristics remain unchanged even at the 1 mm bending radius, corresponding to a tensile strain of 1.28%. The formed gate stack with the copolymer gate dielectric is further investigated for high‐frequency flexible device applications.     

Achieving Over 15% Efficiency in Organic Photovoltaic Cells via Copolymer Design

Ternary blending and copolymerization strategies have proven advantageous in boosting the photovoltaic performance of organic solar cells. Here, 15% efficiency solar cells using copolymerization donors are demonstrated, where the electron‐withdrawing unit, ester‐substituted thiophene, is incorporated into a PBDB‐TF polymer to downshift the molecular energy and broaden the absorption. Copolymer‐based solar cells suitable for large‐area devices can be fabricated by a blade‐coating method from a nonhalogen and nonaromatic solvent mixture. Although ternary solar cells can achieve comparable efficiencies, they are not suitable for environment‐friendly processing conditions and show relatively low photostability compared to copolymer‐based devices. These results not only demonstrate high‐efficiency organic photovoltaic cells via copolymerization strategies but also provide important insights into their applications in practical production.     

Plasticizing Silk Protein for On‐Skin Stretchable Electrodes

Soft and stretchable electronic devices are important in wearable and implantable applications because of the high skin conformability. Due to the natural biocompatibility and biodegradability, silk protein is one of the ideal platforms for wearable electronic devices. However, the realization of skin‐conformable electronic devices based on silk has been limited by the mechanical mismatch with skin, and the difficulty in integrating stretchable electronics. Here, silk protein is used as the substrate for soft and stretchable on‐skin electronics. The original high Young's modulus (5–12 GPa) and low stretchability (<20%) are tuned into 0.1–2 MPa and > 400%, respectively. This plasticization is realized by the addition of CaCl₂ and ambient hydration, whose mechanism is further investigated by molecular dynamics simulations. Moreover, highly stretchable (>100%) electrodes are obtained by the thin‐film metallization and the formation of wrinkled structures after ambient hydration. Finally, the plasticized silk electrodes, with the high electrical performance and skin conformability, achieve on‐skin electrophysiological recording comparable to that by commercial gel electrodes. The proposed skin‐conformable electronics based on biomaterials will pave the way for the harmonized integration of electronics into human.     

A Biodegradable and Stretchable Protein‐Based Sensor as Artificial Electronic Skin for Human Motion Detection

Due to the natural biodegradability and biocompatibility, silk fibroin (SF) is one of the ideal platforms for on‐skin and implantable electronic devices. However, the development of SF‐based electronics is still at a preliminary stage due to the SF film intrinsic brittleness as well as the solubility in water, which prevent the fabrication of SF‐based electronics through traditional techniques. In this article, a flexible and stretchable silver nanofibers (Ag NFs)/SF based electrode is synthesized through water‐free procedures, which demonstrates outstanding performance, i.e., low sheet resistance (10.5 Ω sq^?1), high transmittance (>90%), excellent stability even after bending cycles >2200 times, and good extensibility (>60% stretching). In addition, on the basis of such advanced (Ag NFs)/SF electrode, a flexible and tactile sensor is further fabricated, which can simultaneously detect pressure and strain signals with a large monitoring window (35 Pa–700 kPa). Besides, this sensor is air‐permeable and inflammation‐free, so that it can be directly laminated onto human skins for long‐term health monitoring. Considering the biodegradable and skin‐comfortable features, this sensor may become promising to find potential applications in on‐skin or implantable health‐monitoring devices.     

Truly Concomitant and Independently Expressed Short‐ and Long‐Term Plasticity in a Bi2O2Se‐Based Three‐Terminal Memristor

Concomitance of diverse synaptic plasticity across different timescales produces complex cognitive processes. To achieve comparable cognitive complexity in memristive neuromorphic systems, devices that are capable of emulating short‐term (STP) and long‐term plasticity (LTP) concomitantly are essential. In existing memristors, however, STP and LTP can only be induced selectively because of the inability to be decoupled using different loci and mechanisms. In this work, the first demonstration of truly concomitant STP and LTP is reported in a three‐terminal memristor that uses independent physical phenomena to represent each form of plasticity. The emerging layered material Bi₂O₂Se is used for memristors for the first time, opening up the prospects for ultrathin, high‐speed, and low‐power neuromorphic devices. The concerted action of STP and LTP allows full‐range modulation of the transient synaptic efficacy, from depression to facilitation, by stimulus frequency or intensity, providing a versatile device platform for neuromorphic function implementation. A heuristic recurrent neural circuitry model is developed to simulate the intricate “sleep–wake cycle autoregulation” process, in which the concomitance of STP and LTP is posited as a key factor in enabling this neural homeostasis. This work sheds new light on the development of generic memristor platforms for highly dynamic neuromorphic computing.     

All‐Polymer Solar Cells Based on a Conjugated Polymer Containing Siloxane‐Functionalized Side Chains with Efficiency over 10%

A novel wide‐bandgap conjugated copolymer based on an imide‐functionalized benzotriazole building block containing a siloxane‐terminated side‐chain is developed. This copolymer is successfully used to fabricate highly efficient all‐polymer solar cells (all‐PSCs) processed at room temperature with the green‐solvent 2‐methyl‐tetrahydrofuran. When paired with a naphthalene diimide‐based polymer electron‐acceptor, the all‐PSC exhibits a maximum power conversion efficiency (PCE) of 10.1%, which is the highest value so far reported for an all‐PSC. Of particular interest is that the PCE remains 9.4% after thermal annealing at 80 °C for 24 h. The resulting high efficiency is attributed to a combination of high and balanced bulky charge carrier mobility, favorable face‐on orientation, and high crystallinity. These observations indicate that the resulting copolymer can be a promising candidate toward high‐performance all‐PSCs for practical applications.     

Lithography‐Free Fabrication of Silica Nanocylinders with Suspended Gold Nanorings for LSPR‐Based Sensing

Tunable plasmonic platforms are important for a variety of applications such as photovoltaics, LED's, optoelectronics, medical research, and biosensors. In particular, development of label‐free plasmonic biosensors is one of the key research areas that utilizes plasmonic nanostructures for detection of biologically relevant molecules at low concentrations. The authors have developed a cost‐effective, fast, and lithography‐free method to fabricate transparent fused silica nanocylinders. The technique allows tuning of nanocylinder height, diameter, and density and can be scaled to large surface areas, such as 8 in. wafers. The authors demonstrate that gold coated nanocylinders support localized surface plasmon resonances (LSPR) from visible to near infrared wavelengths. The plasmonic platform can be characterized as suspended gold nanorings and exhibits a sensitivity of 658 nm RIU^–1 with a figure‐of‐merit of 10, comparable to other state‐of‐the‐art LSPR sensing platforms that utilize more complex nanofabrication pathways. It was observed that the LSPR peak positions can be controlled by varying the geometry of the nanocylinders. The authors illustrate surface functionalization, biosensing, and surface regeneration properties of the platform using thiols and detection of bovine serum albumin (BSA). The observed LSPR shifts for 11‐mercaptoundecanoic acid and BSA was 12 and 26 nm, respectively.     

3D Printing of Bioinspired Liquid Superrepellent Structures

Bioinspired re‐entrant structures have been proved to be effective in achieving liquid superrepellence (including anti‐penetration, anti‐adhesion, and anti‐spreading). However, except for a few reports relying on isotropic etching of silicon wafers, most fluorination‐dependent surfaces are still unable to repel liquids with extreme low surface energy (i.e., γ < 15 mN m^?1), especially those fluorinated solvents. Herein, triply re‐entrant structures, possessing superrepellence to water (with surface tension γ of 72.8 mN m^?1) and various organic liquids (γ = 12.0–27.1 mN m^?1), are fabricated via two‐photon polymerization based 3D printing technology. Such structures can be constructed both on rigid and flexible substrates, and the liquid superrepellent properties can be kept even after oxygen plasma treatment. Based on the prepared triply re‐entrant structures, micro open capillaries are constructed on them to realize directional liquid spreading, which may be applied in microfluidic platforms and lab‐on‐a‐chip applications. The fabricated arrays can also find potential applications in electronic devices, gas sensors, microchemical/physical reactors, high‐throughput biological sensors, and optical displays.     

Patterning of Lyotropic Chromonic Liquid Crystals by Photoalignment with Photonic Metamasks

Controlling supramolecular self‐assembly in water‐based solutions is an important problem of interdisciplinary character that impacts the development of many functional materials and systems. Significant progress in aqueous self‐assembly and templating has been demonstrated by using lyotropic chromonic liquid crystals (LCLCs) as these materials show spontaneous orientational order caused by unidirectional stacking of plank‐like molecules into elongated aggregates. In this work, it is demonstrated that the alignment direction of chromonic assemblies can be patterned into complex spatially‐varying structures with very high micrometer‐scale precision. The approach uses photoalignment with light beams that exhibit a spatially‐varying direction of light polarization. The state of polarization is imprinted into a layer of photosensitive dye that is protected against dissolution into the LCLC by a liquid crystalline polymer layer. The demonstrated level of control over the spatial orientation of LCLC opens opportunities for engineering materials and devices for optical and biological applications.     

High‐Performance Flexible Organic Nano‐Floating Gate Memory Devices Functionalized with Cobalt Ferrite Nanoparticles

Nano‐floating gate memory (NFGM) devices are transistor‐type memory devices that use nanostructured materials as charge trap sites. They have recently attracted a great deal of attention due to their excellent performance, capability for multilevel programming, and suitability as platforms for integrated circuits. Herein, novel NFGM devices have been fabricated using semiconducting cobalt ferrite (CoFe₂O₄) nanoparticles (NPs) as charge trap sites and pentacene as a p‐type semiconductor. Monodisperse CoFe₂O₄ NPs with different diameters have been synthesized by thermal decomposition and embedded in NFGM devices. The particle size effects on the memory performance have been investigated in terms of energy levels and particle–particle interactions. CoFe₂O₄ NP‐based memory devices exhibit a large memory window (≈73.84 V), a high read current on/off ratio (read I_on/I_off) of ≈2.98 × 10³_, and excellent data retention. Fast switching behaviors are observed due to the exceptional charge trapping/release capability of CoFe₂O₄ NPs surrounded by the oleate layer, which acts as an alternative tunneling dielectric layer and simplifies the device fabrication process. Furthermore, the NFGM devices show excellent thermal stability, and flexible memory devices fabricated on plastic substrates exhibit remarkable mechanical and electrical stability. This study demonstrates a viable means of fabricating highly flexible, high‐performance organic memory devices.     

Remotely Triggered Assembly of 3D Mesostructures Through Shape‐Memory Effects

3D structures that incorporate high‐performance electronic materials and allow for remote, on‐demand 3D shape reconfiguration are of interest for applications that range from ingestible medical devices and microrobotics to tunable optoelectronics. Here, materials and design approaches are introduced for assembly of such systems via controlled mechanical buckling of 2D precursors built on shape‐memory polymer (SMP) substrates. The temporary shape fixing and recovery of SMPs, governed by thermomechanical loading, provide deterministic control over the assembly and reconfiguration processes, including a range of mechanical manipulations facilitated by the elastic and highly stretchable properties of the materials. Experimental demonstrations include 3D mesostructures of various geometries and length scales, as well as 3D aquatic platforms that can change trajectories and release small objects on demand. The results create many opportunities for advanced, programmable 3D microsystem technologies.     

Remote Control over Underwater Dynamic Attachment/Detachment and Locomotion

Despite extensive efforts to mimic the fascinating adhesion capability of geckos, the development of reversible adhesives underwater has long been lagging. The appearance of mussels‐inspired dopamine chemistry has provided the feasibility to fabricate underwater adhesives; however, for such a system, imitating the reversible and fast dynamic attachment/detachment mechanism of gecko feet still remains unsolved. Here, by synthesizing a thermoresponsive copolymer of poly(dopamine methacrylamide‐co‐methoxyethyl‐acrylate‐co‐N‐isopropyl acrylamide) and then decorating it onto mushroom‐shaped poly(dimethylsiloxane) pillar arrays, a novel underwater thermoresponsive gecko‐like adhesive (TRGA) can be fabricated, yielding high adhesion during the attachment state above the lower critical solution temperature (LCST) of the copolymer, yet low adhesion during the detachment state below the LCST of the copolymer. By integrating the Fe₃O₄ nanoparticles into the TRGA, TRGAs responsive to near‐infrared laser radiation can be engineered, which can be successfully used for rapid and reversible remote control over adhesion so as to capture and release heavy objects underwater because of the contrast force change of both the normal adhesion force and the lateral friction force. It is also demonstrated that the material can be assembled on the tracks of an underwater mobile device to realize controllable movement. This opens up the door for developing intelligent underwater gecko‐like locomotion with dynamic attachment/detachment ability.     

High‐Mobility Helical Tellurium Field‐Effect Transistors Enabled by Transfer‐Free,Low‐Temperature Direct Growth

The transfer‐free direct growth of high‐performance materials and devices can enable transformative new technologies. Here, room‐temperature field‐effect hole mobilities as high as 707 cm² V^?1 s^?1 are reported, achieved using transfer‐free, low‐temperature (≤120 °C) direct growth of helical tellurium (Te) nanostructure devices on SiO₂/Si. The Te nanostructures exhibit significantly higher device performance than other low‐temperature grown semiconductors, and it is demonstrated that through careful control of the growth process, high‐performance Te can be grown on other technologically relevant substrates including flexible plastics like polyethylene terephthalate and graphene in addition to amorphous oxides like SiO₂/Si and HfO₂. The morphology of the Te films can be tailored by the growth temperature, and different carrier scattering mechanisms are identified for films with different morphologies. The transfer‐free direct growth of high‐mobility Te devices can enable major technological breakthroughs, as the low‐temperature growth and fabrication is compatible with the severe thermal budget constraints of emerging applications. For example, vertical integration of novel devices atop a silicon complementary metal oxide semiconductor platform (thermal budget <450 °C) has been theoretically shown to provide a 10× systems level performance improvement, while flexible and wearable electronics (thermal budget <200 °C) can revolutionize defense and medical applications.     

Graphene‐Based Biosensors: Going Simple

The main properties of graphene derivatives facilitating optical and electrical biosensing platforms are discussed, along with how the integration of graphene derivatives, plastic, and paper can lead to innovative devices in order to simplify biosensing technology and manufacture easy‐to‐use, yet powerful electrical or optical biosensors. Some crucial issues to be overcome in order to bring graphene‐based biosensors to the market are also underscored.     

Stoichiometric Engineering of Chalcogenide Semiconductor Alloys for Nanophotonic Applications

A variety of alternative plasmonic and dielectric material platforms—among them nitrides, semiconductors, and conductive oxides—have come to prominence in recent years as means to address the shortcomings of noble metals (including Joule losses, cost, and passive character) in certain nanophotonic and optical‐frequency metamaterial applications. Here, it is shown that chalcogenide semiconductor alloys offer a uniquely broad pallet of optical properties, complementary to those of existing material platforms, which can be controlled by stoichiometric design. Using combinatorial high‐throughput techniques, the extraordinary epsilon‐near‐zero, plasmonic, and low/high‐index characteristics of Bi:Sb:Te alloys are explored. Depending upon composition they can, for example, have plasmonic figures of merit higher than conductive oxides and nitrides across the entire UV–NIR range, and higher than gold below 550 nm; present dielectric figures of merit better than conductive oxides at near‐infrared telecommunications wavelengths; and exhibit record‐breaking refractive indices as low as 0.7 and as high as 11.5.     

High‐Performance Solution‐Processed Organo‐Metal Halide Perovskite Unipolar Resistive Memory Devices in a Cross‐Bar Array Structure

Resistive random access memories can potentially open a niche area in memory technology applications by combining the advantages of the long endurance of dynamic random‐access memory and the long retention time of flash memories. Recently, resistive memory devices based on organo‐metal halide perovskite materials have demonstrated outstanding memory properties, such as a low‐voltage operation and a high ON/OFF ratio; such properties are essential requirements for low power consumption in developing practical memory devices. In this study, a nonhalide lead source is employed to deposit perovskite films via a simple single‐step spin‐coating method for fabricating unipolar resistive memory devices in a cross‐bar array architecture. These unipolar perovskite memory devices achieve a high ON/OFF ratio up to 10⁸ with a relatively low operation voltage, a large endurance, and long retention times. The high‐yield device fabrication based on the solution‐process demonstrated here will be a step toward achieving low‐cost and high‐density practical perovskite memory devices.     

Reliability Model for Electronic Devices under Time Varying Voltage

Present reliability models, which estimate the lifetime of electronic devices, work under the assumption that the voltage level must be constant when an Accelerated Life Testing is performed. Nevertheless, in a real operational environment, electronic devices are subjected to electrical variations present in the power lines; that means the voltage has a time‐varying behavior, which breaks the assumption of reliability models. Thus, in this paper, a reliability model is presented, which describes the lifetime of electronic devices under time‐varying voltage via a parametric function. The model is based on the Cumulative Damage Model with random failure rate and the modified Inverse Power Law. In order to estimate the parameters of the proposed model, the maximum likelihood method was employed. A case study based on the time‐varying voltage induced by electrical harmonics when Alternate Current/Direct Current (AC/DC) transformer is connected to the power line is presented in this paper. Copyright © 2015 John Wiley & Sons, Ltd.     

Nanowire‐Based Sensors

Nanowires are important potential candidates for the realization of the next generation of sensors. They offer many advantages such as high surface‐to‐volume ratios, Debye lengths comparable to the target molecule, minimum power consumption, and they can be relatively easily incorporated into microelectronic devices. Accordingly, there has been an intensified search for novel nanowire materials and corresponding platforms for realizing single‐molecule detection with superior sensing performance. In this work, progress made towards the use of nanowires for achieving better sensing performance is critically reviewed. In particular, various nanowires types (metallic, semiconducting, and insulating) and their employment either as a sensor material or as a template material are discussed. Major obstacles and future steps towards the ultimate nanosensors based on nanowires are addressed.     

Shape‐Controlled Synthesis of High‐Quality Cu7S4 Nanocrystals for Efficient Light‐Induced Water Evaporation

Copper sulfides (Cu_2–xS), are a novel kind of photothermal material exhibiting significant photothermal conversion efficiency, making them very attractive in various energy conversion related devices. Preparing high quality uniform Cu_2‐xS nanocrystals (NCs) is a top priority for further energy‐and sustainability relevant nanodevices. Here, a shape‐controlled high quality Cu₇S₄ NCs synthesis strategy is reported using sulfur in 1‐octadecene as precursor by varying the heating temperature, as well as its forming mechanism. The performance of the Cu₇S₄ NCs is further explored for light‐driven water evaporation without the need of heating the bulk liquid to the boiling point, and the results suggest that as‐synthesized highly monodisperse NCs perform higher evaporation rate than polydisperse NCs under the identical morphology. Furthermore, disk‐like NCs exhibit higher water evaporation rate than spherical NCs. The water evaporation rate can be further enhanced by assembling the organic phase Cu₇S₄ NCs into a dense film on the aqueous solution surface. The maximum photothermal conversion efficiency is as high as 77.1%.     

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

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