All‐Carbon Nanotube‐Based Flexible Field‐Emission Devices: From Cathode to Anode

The fabrication of a flexible field‐emission device (FED) using single‐walled carbon nanotube (SWNT) network films as the conducting electrodes (anode and cathode) and thin multi‐walled CNT/TEOS hybrid films as the emitters is reported. P‐type doping with gold ions and passivation with tetraethylorthosilicate (TEOS) made the SWNT network film highly conductive and environmentally stable, and hence a good alternative to conventional indium tin oxide electrodes. CNT/TEOS hybrid emitters showed high current density, low turn‐on field, and long‐term emission stability, compared with CNT emitters; these characteristics can be attributed to the TEOS sol, acting both as a protective layer surrounding the nanotube tip, and as an adhesive layer enhancing the nanotube adhesion to the substrate. All‐CNT‐based flexible FEDs fabricated by this approach showed high flexibility in field emission characteristics and extremely bright electron emission patterns.     

Carbon‐Nanotube‐Templated Microfabrication of Porous Silicon‐Carbon Materials with Application to Chemical Separations

Carbon‐nanotube‐templated microfabrication (CNT‐M) of porous materials is demonstrated. Partial chemical infiltration of 3D carbon‐nanotube structures with silicon results in a mechanically robust material, structured from the 10 nm scale to the 100 μm scale. The nanoscale dimensions are determined by the diameter and spacing of the resulting silicon/carbon nanotubes, while the microscale dimensions are controlled by the lithographic patterning of the CNT growth catalyst. We demonstrate the utility of this hierarchical structuring approach by using CNT‐M to fabricate thin‐layer‐chromatography (TLC) separations media with precise microscale channels for fluid‐flow control and nanoscale porosity for high analyte capacity. Chemical separations done on the CNT‐M‐structured media outperform commercial high‐performance TLC media.     

Laser‐Induced Rapid Carbon Nanotube Micro‐Actuators

Laser‐induced rapid actuating microstructures made of aligned carbon nanotube (CNT) arrays are achieved. Desirable operational features of the CNT micro‐actuators include low laser power activation, rapid response, elastic and reversible motion, and robust durability. Experimental evidence suggests a laser‐induced electrostatic interaction mechanism as the primary cause of the optomechanical phenomenon. Oscillating CNT micro‐actuators up to 40 kHz are achieved by driving them with a modulated laser beam. The micro‐actuators are utilized in exerting a sub‐micro‐Newton force to bend nanowires. Electrical coupling of the micro‐actuator and feasibilities of multi‐actuator systems made entirely out of CNTs are also demonstrated.     

Versatile,High‐Power,Flexible, Stretchable Carbon Nanotube Sheet Heating Elements Tolerant to Mechanical Damage and Severe Deformation

A macroscopic carbon nanotube (CNT) sheet‐based heating element having flexible, stretchable, and damage‐tolerant features, and wide applicability in harsh environments, is introduced. Because of the intrinsic connection of extremely flexible CNT bundles throughout the sample by van der Waals interactions without use of a binder, the electrical resistance variation of the CNT sheet on elastomer heating element as a function of strain is completely suppressed to some extent, even when stretched under up to 400% strain, which guarantees electrical stability under severe mechanical deformation. In addition, the spatial uniformity of the heat generated from the microaligned CNT bundles reduces the temperature variation inside the sample, which also guarantees thermal stability and operation at a higher average temperature. Such exceptional performance is achieved by the passivation of the elastomer layer on the CNT sheets. Furthermore, the mechanical robustness of this flexible, stretchable heating element is demonstrated by stable heater operation, even when the heating element is damaged. In addition, this design concept of CNT sheet on elastomer is extended to transparent flexible heaters and electric‐thermochromic windows.     

Impact of Morphology on Printed Contact Performance in Carbon Nanotube Thin‐Film Transistors

Silver nanoparticles (NPs) are the most widely used conductive material throughout the printed electronics space due to their high conductivity and low cost. However, when interfacing with other prominent printed materials, such as semiconducting carbon nanotubes (CNTs) in thin‐film transistors (TFTs), silver is suboptimal when compared to more expensive or less conductive materials. Consequently, there would be significant value to improving the interface of printed silver to CNT films. In this work, the impact of nanostructure morphology on the electrical properties of printed silver and nanotube junctions in CNT‐TFTs is investigated. Three distinct silver morphologies (NPs, nanoflakes – NFs, and nanowires – NWs) are explored with top‐ and bottom‐contact configurations for each. The NF morphology in a top‐contact configuration is found to yield the best electrical interface to CNTs, resulting in an average contact resistance of 1.2 MΩ ? µm. Beyond electrical performance, several trade‐offs in morphology selection are revealed, including print resolution and process temperature. While NF inks produce the best interfaces, NP inks produce the smallest features, and NW inks are compatible with low processing temperatures (<80 °C). These results outline the trade‐offs between silver contact morphologies in CNT‐TFTs and show that contact morphology selection can be tailored for specific applications.     

Flexible Multifunctionalized Carbon Nanotubes‐Based Hybrid Nanowires

In this work, flexible multifunctionalized carbon nanotube (CNT)‐based hybrid nanowires are synthesized through surface modification processes. The good dispersability of the hybrid nanowire in polar solvents facilitates directly making fine patterns with a minimum width of 40 μm for applications of flexible and stretchable circuits (FSCs). The hybrid nanowire possesses a flexible and highly conductive structure which demonstrates stable electro‐mechanical properties on polydimethylsiloxane (PDMS) substrates under large structural deformation. FSCs fabricated from the hybrid nanowires show a constant resistance of 0.096 Ω □^?1 (equivalent of a resistivity 0.96 Ω μm) under repeated bending cycles. The FSCs also have a low and stable sheet resistance of 0.4 Ω □^?1 for strains up to 30%, which is almost four orders of magnitude lower than that of pure CNT samples (1316 Ω □^?1). Further improved stretchability and electro‐mechanical properties (0.1 Ω □^?1, at the strain of 100%) are achieved with a prestrain PDMS substrate. Repeated deformation tests demonstrate the high reliability of FSCs. The observed stable and reliable electro‐mechanical performance of FSCs suggests the potential use of the material in wearable and portable electronics.     

用于OLED的碳纳米管

首先,介绍了传统柔性有机发光二极管(FOLED)的基本结构及缺点.其次,对氧化铟锡(ITO)玻璃应用于FOLED生产的局限性进行了阐述.然后将碳纳米管(CNT)与ITO薄膜进行了对比,对碳纳米管应用于FOLED制备的可行性进行了分析,并对碳纳米管生产及器件的制备进行了说明.对碳纳米管的分类以及分离进行了简要阐述,着重分...     

Highly Conductive Carbon Nanotube‐Graphene Hybrid Yarn

An efficient procedure for the fabrication of highly conductive carbon nanotube/graphene hybrid yarns has been developed. To start, arrays of vertically aligned multi‐walled carbon nanotubes (MWNT) are converted into indefinitely long MWNT sheets by drawing. Graphene flakes are then deposited onto the MWNT sheets by electrospinning to form a composite structure that is transformed into yarn filaments by twisting. The process is scalable for yarn fabrication on an industrial scale. Prepared materials are characterized by electron microscopy, electrical, mechanical, and electrochemical measurements. It is found that the electrical conductivity of the composite MWNT‐graphene yarns is over 900 S/cm. This value is 400% and 1250% higher than electrical conductivity of pristine MWNT yarns or graphene paper, respectively. The increase in conductivity is asssociated with the increase of the density of states near the Fermi level by a factor of 100 and a decrease in the hopping distance by an order of magnitude induced by grapene flakes. It is found also that the MWNT‐graphene yarn has a strong electrochemical response with specific capacitance in excess of 111 Fg^?1. This value is 425% higher than the capacitance of pristine MWNT yarn. Such substantial improvements of key properties of the hybrid material can be associated with the synergy of MWNT and graphene layers in the yarn structure. Prepared hybrid yarns can benefit such applications as high‐performance supercapacitors, batteries, high current capable cables, and artificial muscles.     

Catalytic Twist‐Spun Yarns of Nitrogen‐Doped Carbon Nanotubes

The treatment of free‐standing sheets of multiwalled carbon nanotubes (MWNTs) with a NH₃/He plasma results in self‐supporting sheets of aligned N‐doped MWNTs (CN_x). These CN_x sheets can be easily twist spun in the solid state to provide strong CN_x yarns that are knottable, weavable, and sewable. The CN_x yarns exhibit tunable catalytic activity for electrochemically driven oxygen reduction reactions (ORR), as well as specific capacitances (up to 39 F·g^?1) that are 2.6 times higher than for the parent MWNTs. Due to a high degree of nanotube alignment, the CN_x yarns exhibit specific strengths (451 ± 61 MPa·cm³·g^?1) that are three times larger than observed for hybrid CN_x/MWNT biscrolled yarns containing 70 wt.% CN_x in the form of a powder. This difference in mechanical strength arises from substantial differences in yarn morphology, revealed by electron microscopy imaging of yarn cross‐ sections, as well as the absence of a significant strength contribution from CN_x nanotubes in the biscrolled yarns. Finally, the chemical nature and abundance of the incorporated nitrogen within the CN_x nanotubes is studied as function of plasma exposure and annealing processes using X‐ray photoelectron spectroscopy and correlated with catalytic activity.     

A General Electrochemical Strategy for Synthesizing Charge‐Transfer Complex Micro/Nanowires

Universal strategies for synthesizing one‐dimensional organic nanomaterials are of fundamental importance in the development of more flexible, cheaper and lighter electronics. Charge‐transfer (CT) complexes, the major kind of organic conductors, are in the long‐term attractive materials owing to their unique crystal structures and conductive properties. In this article, a general strategy for the synthesis of CT complex micro/nanowires based on the localized nanoelectrochemistry using tiny carbon nanotube (CNT) electrodes is presented. This strategy is successfully demonstrated over 12 typical CT complexes, and a general rule for the preparation of various kinds of CT complex micro/nanowires is summarized. The CT complex micro/nanowires thus synthesized have high aspect ratios and long lengths as compared with traditional macroscopic planar electrodes, originating from the one‐dimensional structural feature with fewer or no defects and the ultrasmall surface area of the CNT. This work provides a more versatile material basis for the fundamental and application studies of low‐dimensional organic conductor materials.     

Efficiency Enhancement of Single‐Walled Carbon Nanotube‐Silicon Heterojunction Solar Cells Using Microwave‐Exfoliated Few‐Layer Black Phosphorus

Carbon nanotube‐silicon (CNT‐Si)‐based heterojunction solar cells (HJSCs) are a promising photovoltaic (PV) system. Herein, few‐layer black phosphorus (FL‐BP) sheets are produced in N‐methyl‐2‐pyrrolidone (NMP) using microwave‐assisted liquid‐phase exfoliation and introduced into the CNTs‐Si‐based HJSCs for the first time. The NMP‐based FL‐BP sheets remain stable after mixing with aqueous CNT dispersion for device fabrication. Due to their unique 2D structure and p‐type dominated conduction, the FL‐BP/NMP incorporated CNT‐Si devices show an impressive improvement in the power conversion efficiency from 7.52% (control CNT‐Si cell) to 9.37%. Our density‐functional theory calculation reveals that lowest unoccupied molecular orbital (LUMO) of FL‐BP is higher in energy than that of single‐walled CNT. Therefore, we observed a reduction in the orbitals localized on FL‐BP upon highest occupied molecular orbital to LUMO transition, which corresponds to an improved charge transport. This study opens a new avenue in utilizing 2D phosphorene nanosheets for next‐generation PVs.     

Carbon‐Nanotube‐Reinforced Zr‐Based Bulk Metallic Glass Composites and Their Properties

In this paper, we systematically report the preparation of carbon‐nanotube (CNT)‐reinforced Zr‐based bulk metallic glass (BMG) composites. The physical and mechanical properties of the composites were investigated. Compressive testing shows that the composites still display high fracture strength. Investigation also shows that the composites have strong ultrasonic attenuation characteristics and excellent wave absorption ability. The strong wave absorption implies that CNT‐reinforced Zr‐based BMG composites, besides their excellent mechanical properties, may also have significant potential for applications in shielding acoustic sound or environmental noise.     

In vivo Imaging and Drug Storage by Quantum‐Dot‐Conjugated Carbon Nanotubes

A specially designed carbon nanotube (CNT) is developed for use in the early detection and treatment of cancer. The key functionalities for biomedical diagnosis and drug delivery are incorporated into the CNTs. In vivo imaging of live mice is achieved by intravenously injecting quantum dot (QD)‐conjugated CNT for the first time. With near infrared emission around 752 nm, the CNT with surface‐conjugated QD (CNT‐QD) exhibit a strong luminescence for non‐invasive optical in vivo imaging. CNT surface modification is achieved by a plasma polymerization approach that deposited ultra‐thin acrylic acid or poly(lactic‐co‐glycolic acid) (PLGA) films (∼3 nm) onto the nanotubes. The anticancer agent paclitaxel is loaded at 112.5 ± 5.8 µg mg⁻¹ to PLGA‐coated CNT. Cytotoxicity of this novel drug delivery system is evaluated in vitro using PC‐3MM2 human prostate carcinoma cells and quantified by the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay. The in vivo distribution determined by inductively coupled plasma mass spectrometry (ICP‐MS) indicates CNT‐QD uptake in various organs of live animals.     

Atomistic Investigation of Load Transfer Between DWNT Bundles “Crosslinked” by PMMA Oligomers

The production of carbon nanotube (CNT) yarns possessing high strength and toughness remains a major challenge due to the intrinsically weak interactions between “bare” CNTs. To this end, nanomechanical shear experiments between functionalized bundles of CNTs are combined with multiscale simulations to reveal the mechanistic and quantitative role of nanotube surface functionalization on CNT‐CNT interactions. Notably, the in situ chemical vapor deposition (CVD) functionalization of CNT bundles by poly(methyl methacrylate) (PMMA)‐like oligomers is found to enhance the shear strength of bundle junctions by about an order of magnitude compared with “bare” van der Waals interactions between pristine CNTs. Through multiscale simulations, the enhancement of the shear strength can be attributed to an interlocking mechanism of polymer chains in the bundles, dominated by van der Waals interactions, and stretching and alignment of chains during shearing. Unlike covalent bonds, such synergistic weak interactions can re‐form upon failure, resulting in strong, yet robust fibers. This work establishes the significance of engineered weak interactions with appropriate structural distribution to design CNT yarns with high strength and toughness, similar to the design paradigm found in many biological materials.     

Temperature Performance of Doping‐Free Top‐Gate CNT Field‐Effect Transistors: Potential for Low‐ and High‐Temperature Electronics

High‐performance top‐gate carbon nanotube (CNT) field‐effect transistors (FETs) have been fabricated via a doping‐free fabrication process in which the polarity of the CNT FET is controlled by the injection of carriers from the electrodes, instead of using dopants. The performance of the doping‐free CNT FETs is systemically investigated over a wide temperature range, from very low temperatures of down to 4.3 K up to 573 K, and analyzed using several temperature‐dependent key device parameters including the ON/OFF state current and ratio, carrier mobility, and subthreshold swing. It is demonstrated that for ballistic and quasi‐ballistic CNT FETs, the operation of the CNT FETs is largely independent of the presence of dopant, thus avoiding detrimental effects due to dopant freeze‐out at low temperature and dopant diffusion at high temperature, and making it possible to use doping‐free CNT FETs in both low‐ and high‐temperature electronics. A new method is also proposed for extracting the band‐gap and diameter of a semiconducting CNT from the temperature dependent OFF‐state current and shown to yield results that are consistent with AFM measurements.     

Flexible Solid‐State Supercapacitor Based on Graphene‐based Hybrid Films

A flexible solid‐state asymmetric supercapacitor based on bendable film electrodes with 3D expressway‐like architecture of graphenes and “hard nano‐spacer” is fabricated via an extended filtration assisted method. In the designed structure of the positive electrode, graphene sheets are densely packed, and Ni(OH)₂ nanoplates are intercalated in between the densely stacked graphenes. The 3D expressway‐like electrodes exhibit superior supercapacitive performance including high gravimetric capacitance (≈573 F g^‐1), high volumetric capacitance (≈655 F cm^‐3), excellent rate capability, and superior cycling stability. In addition, another hybrid film of graphene and carbon nanotubes (CNT) is fabricated as the negative electrodes for the designed asymmetric device. In the obtained graphene@CNT films, CNTs served as the hard spacer to prevent restacking of graphene sheets but also as a conductive and robust network to facilitate the electrons collection/transport in order to fulfill the demand of high‐rate performance of the asymmetric supercapacitor. Based on these two hybrid electrode films, a solid‐state flexible asymmetric supercapacitor device is assembled, which is able to deliver competitive volumetric capacitance of 58.5 F cm^‐3 and good rate capacity. There is no obvious degradation of the supercapacitor performance when the device is in bending configuration, suggesting the excellent flexibility of the device.     

Capacitively Coupled Hybrid Ion Gel and Carbon Nanotube Thin‐Film Transistors for Low Voltage Flexible Logic Circuits

The lamination of a high‐capacitance ion gel dielectric layer onto semiconducting carbon nanotube (CNT) thin‐film transistors (TFTs) that are bottom‐gated with a low‐capacitance polymer dielectric layer drastically reduces the operating voltage of the devices resulting from the capacitive coupling effect between the two dielectric layers sandwiching the CNT channel. As the CNT channel has a network structure, only a compact area of ion gel is required to make the capacitive coupling effect viable, unlike the planar channels of previously reported transistors that required a substantially larger area of ion gel dielectric layer to induce the coupling effect. The capacitively coupled CNT TFTs possess superlative electrical characteristics such as high carrier mobilities (42.0 cm² (Vs)^?1 for holes and 59.1 cm² (Vs)^?1 for electrons), steep subthreshold swings (160 mV dec^?1 for holes and 100 mV dec^?1 for electrons), and low gate leakage currents (<1 nA). These devices can be further integrated to form complex logic circuits on flexible substrates with high mechanical resilience. The layered geometry of the device coupled with scalable solution‐based fabrication has significant potential for large‐scale flexible electronics.     

Tailoring the Mechanical Properties of High‐Aspect‐Ratio Carbon Nanotube Arrays using Amorphous Silicon Carbide Coatings

The porous nature of carbon nanotube (CNT) arrays allows for the unique opportunity to tailor their mechanical response by the infiltration and deposition of nanoscale conformal coatings. Here, we fabricate novel photo‐lithographically defined CNT pillars that are conformally coated with amorphous silicon carbide (a‐SiC) to strengthen the interlocking of individual CNTs at junctions using low pressure chemical vapor deposition (LPCVD). We further quantify the mechanical response by performing flat‐punch nanoindentation measurements on coated CNT pillars with various high‐aspect‐ratios. We discovered new mechanical failure modes of coated CNT pillars, such as “bamboo” and brittle‐like composite rupture as coating thickness increases. Furthermore, a significant increase in strength and modulus is achieved. For CNT pillars with high aspect ratio (1:10) and coating thickness of 21.4 nm, the compressive strength increases by an order of magnitude of 3, towards 1.8 GPa (from below 1 MPa for uncoated CNT pillars) and the elastic modulus increases towards 125 GPa. These results show that our coated CNT pillars, which can serve as vertical interconnects and 3D super‐capacitors, can be transformed into robust high‐aspect‐ratio 3D‐micro architectures with semiconductor device compatible processes.     

A Low‐Cost,Self‐Standing NiCo2O4@CNT/CNT Multilayer Electrode for Flexible Asymmetric Solid‐State Supercapacitors

The demand for a new generation of flexible, portable, and high‐capacity power sources increases rapidly with the development of advanced wearable electronic devices. Here we report a simple process for large‐scale fabrication of self‐standing composite film electrodes composed of NiCo₂O₄@carbon nanotube (CNT) for supercapacitors. Among all composite electrodes prepared, the one fired in air displays the best electrochemical behavior, achieving a specific capacitance of 1,590 F g^?1 at 0.5 A g^?1 while maintaining excellent stability. The NiCo₂O₄@CNT/CNT film electrodes are fabricated via stacking NiCo₂O₄@CNT and CNT alternately through vacuum filtration. Lightweight, flexible, and self‐standing film electrodes (≈24.3 µm thick) exhibit high volumetric capacitance of 873 F cm^?3 (with an areal mass of 2.5 mg cm^?2) at 0.5 A g^?1. An all‐solid‐state asymmetric supercapacitor consists of a composite film electrode and a treated carbon cloth electrode has not only high energy density (≈27.6 Wh kg^?1) at 0.55 kW kg^?1 (including the weight of the two electrodes) but also excellent cycling stability (retaining ≈95% of the initial capacitance after 5000 cycles), demonstrating the potential for practical application in wearable devices.