Interface States in Gate Stack of Carbon Nanotube Array Transistors.

A deep understanding of the interface states in metal-oxide-semiconductor (MOS) structures is the premise of improving the gate stack quality, which sets the foundation for building field-effect transistors (FETs) with high performance and high reliability. Although MOSFETs built on aligned semiconducting carbon nanotube (A-CNT) arrays have been considered ideal energy-efficient successors to commercial silicon (Si) transistors, research on the interface states of A-CNT MOS devices, let alone their optimization, is lacking. Here, we fabricate MOS capacitors based on an A-CNT array with a well-designed layout and accurately measure the capacitance-voltage and conductance-voltage (C-V and G-V) data. Then, the gate electrostatics and the physical origins of interface states are systematically analyzed and revealed. In particular, targeted improvement of gate dielectric growth in the A-CNT MOS device contributes to suppressing the interface state density (Dit) to 6.1 × 1011 cm-2 eV-1, which is a record for CNT- or low-dimensional semiconductors-based MOSFETs, boosting a record transconductance (gm) of 2.42 mS/µm and an on-off ratio of 105. Further decreasing Dit below 1 × 1011 cm-2 eV-1 is necessary for A-CNT MOSFETs to achieve the expected high energy efficiency.

Integration of Functional Human Auditory Neural Circuits Based on a 3D Carbon Nanotube System.

The physiological interactions between the peripheral and central auditory systems are crucial for auditory information transmission and perception, while reliable models for auditory neural circuits are currently lacking. To address this issue, mouse and human neural pathways are generated by utilizing a carbon nanotube nanofiber system. The super-aligned pattern of the scaffold renders the axons of the bipolar and multipolar neurons extending in a parallel direction. In addition, the electrical conductivity of the scaffold maintains the electrophysiological activity of the primary mouse auditory neurons. The mouse and human primary neurons from peripheral and central auditory units in the system are then co-cultured and showed that the two kinds of neurons form synaptic connections. Moreover, neural progenitor cells of the cochlea and auditory cortex are derived from human embryos to generate region-specific organoids and these organoids are assembled in the nanofiber-combined 3D system. Using optogenetic stimulation, calcium imaging, and electrophysiological recording, it is revealed that functional synaptic connections are formed between peripheral neurons and central neurons, as evidenced by calcium spiking and postsynaptic currents. The auditory circuit model will enable the study of the auditory neural pathway and advance the search for treatment strategies for disorders of neuronal connectivity in sensorineural hearing loss.

Efficient Emission of Highly Polarized Thermal Radiation from a Suspended Aligned Carbon Nanotube Film.

A polarized light source covering a wide wavelength range is required in applications across diverse fields, including optical communication, photonics, spectroscopy, and imaging. For practical applications, high degrees of polarization and thermal performance are needed to ensure the stability of the radiation intensity and low energy consumption. Here, we achieved efficient emission of highly polarized and broadband thermal radiation from a suspended aligned carbon nanotube film. The anisotropic nature of the film, combined with the suspension, led to a high degree of linear polarization (∼0.9) and great thermal performance. Furthermore, we performed time-resolved measurements of thermal emission from the film, revealing a fast time response of approximately a few microseconds. We also obtained visible light emission from the device and analyzed the film's mechanical breakdown behavior to improve the emission intensity. Finally, we demonstrated that suspended devices with a constriction geometry can enhance the heating performance. These results show that carbon nanotube film-based devices, as electrically driven thermal emitters of polarized radiation, can play an important role for future development in optoelectronics and spectroscopy.

High-Speed Modulation of Polarized Thermal Radiation from an On-Chip Aligned Carbon Nanotube Film.

Spectroscopic analysis with polarized light has been widely used to investigate molecular structure and material behavior. A broadband polarized light source that can be switched on and off at a high speed is indispensable for reading faint signals, but such a source has not been developed. Here, using aligned carbon nanotube (CNT) films, we have developed broadband thermal emitters of polarized infrared radiation with switching speeds of ≲20 MHz. We found that the switching speed depends on whether the electrical current is parallel or perpendicular to the CNT alignment direction with a significantly higher speed achieved in the parallel case. Together with detailed theoretical simulations, our experimental results demonstrate that the contact thermal conductance to the substrate and the conductance to the electrodes are important factors that determine the switching speed. These emitters can lead to advanced spectroscopic analysis techniques with polarized radiation.

Highly Efficient Visible-Blind Ultraviolet Photodetector Based on Scalably Produced Titanium Dioxide Nanowire Arrays.

Here, we report a novel, feasible, and cost-effective method for the preparation of one-dimensional TiO2 nanowire arrays using a super-aligned carbon nanotube film as a template. Pure-anatase-phase TiO2 nanowires were scalably prepared in a suspended manner, and a high-performance ultraviolet (UV) photodetector was realized on a flexible substrate. The large surface area and one-dimensional nanostructure of the TiO2 nanowire array led to a high detectivity (1.35 × 1016 Jones) and an ultrahigh photo gain (2.6 × 104), respectively. A high photoresponsivity of 7.7 × 103 A/W was achieved under 7 µW/cm2 UV (λ = 365 nm) illumination at a 10 V bias voltage, which is much higher than those of commercial UV photodetectors. Additionally, by taking advantage of its anisotropic geometry, we found the TiO2 nanowire array showed polarized photodetection. The concept of using nanomaterial systems shows the potential for realization of nanostructured photodetectors for practical applications.

Disrupting Density-Dependent Property Scaling in Hierarchically Architected Foams.

Creating lightweight architected foams as strong and stiff as their bulk constituent material has been a long-standing effort. Typically, the strength, stiffness, and energy dissipation capabilities of materials severely degrade with increasing porosity. We report nearly constant stiffness-to-density and energy dissipation-to-density ratios─a linear scaling with density─in hierarchical vertically aligned carbon nanotube (VACNT) foams with a mesoscale architecture of hexagonally close-packed thin concentric cylinders. We observe a transformation from an inefficient higher-order density-dependent scaling of the average modulus and energy dissipated to a desirable linear scaling as a function of the increasing internal gap between the concentric cylinders. From the scanning electron microscopy of the compressed samples, we observe an alteration in the deformation modality from local shell buckling at a smaller gap to column buckling at a larger gap, governed by an enhancement in the number density of CNTs with the increasing internal gap, leading to better structural stiffness at low densities. This transformation simultaneously improves the foams' damping capacity and energy absorption efficiency as well and allows us to access the ultra-lightweight regime in the property space. Such synergistic scaling of material properties is desirable for protective applications in extreme environments.

Improving the Performance of Aligned Carbon Nanotube-Based Transistors by Refreshing the Substrate Surface.

An aligned semiconducting carbon nanotube (A-CNT) array has been considered an excellent channel material to construct high-performance field-effect transistors (FETs) and integrated circuits (ICs). The purification and assembly processes to prepare a semiconducting A-CNT array require conjugated polymers, introducing stubborn residual polymers and stress at the interface between A-CNTs and substrate, which inevitably affects the fabrication and performance of the FETs. In this work, we develop a process to refresh the Si/SiO2 substrate surface underneath the A-CNT film by wet etching to clean the residual polymers and release the stress. Top-gated A-CNT FETs fabricated with this process show significant performance improvement especially in terms of saturation on-current, peak transconductance, hysteresis, and subthreshold swing. These improvements are attributed to the increase in carrier mobility from 1025 to 1374 cm2/Vs by 34% after the substrate surface refreshing process. Representative 200 nm gate-length A-CNT FETs exhibit an on-current of 1.42 mA/µm and a peak transconductance of 1.06 mS/µm at a drain-to-source bias of 1 V, subthreshold swing (SS) of 105 mV/dec, and negligible hysteresis and drain-induced barrier lowering (DIBL) of 5 mV/V.

High Ampacity On-Chip Wires Implemented by Aligned Carbon Nanotube-Cu Composite.

With the size of electronic devices shrinking to the nanometer scale, it is of great importance to develope new wire materials with higher current carrying capacity than traditional materials such as gold (Au) and copper (Cu). This is urgently needed for more efficient, compact and functional integrated chips and microsystems. To meet the needs of an atom chip, here we report a new solution by introducing super-aligned carbon nanotubes (SACNTs) into Cu thin films. The microwires exhibit an ultra-high current carrying capacity beyond the limit of the traditional Cu wires, reaching (1.7~2.6) × 107 A·cm-2. The first-principles calculation is used to obtain the band structural characteristics of the CNT-Cu composite material, and the principle of its I-V characteristic curve is analyzed. Driven by the bias voltage, a large number of carriers are injected into the CNT layer from Cu by the strong tunneling effect. Moreover, a variety of microwires can be designed and fabricated on demand for high compatibility with conventional microelectronics technology. The composite structures have great potential in high-power electronic devices, high-performance on-chip interconnecting, as well as other applications that have long-term high-current demands, in addition to atom chips.

Beam Trajectory Analysis of Vertically Aligned Carbon Nanotube Emitters with a Microchannel Plate.

Vertically aligned carbon nanotubes (CNTs) are essential to studying high current density, low dispersion, and high brightness. Vertically aligned 14 × 14 CNT emitters are fabricated as an island by sputter coating, photolithography, and the plasma-enhanced chemical vapor deposition process. Scanning electron microscopy is used to analyze the morphology structures with an average height of 40 µm. The field emission microscopy image is captured on the microchannel plate (MCP). The role of the microchannel plate is to determine how the high-density electron beam spot is measured under the variation of voltage and exposure time. The MCP enhances the field emission current near the threshold voltage and protects the CNT from irreversible damage during the vacuum arc. The high-density electron beam spot is measured with an FWHM of 2.71 mm under the variation of the applied voltage and the exposure time, respectively, which corresponds to the real beam spot. This configuration produces the beam trajectory with low dispersion under the proper field emission, which could be applicable to high-resolution multi-beam electron microscopy and high-resolution X-ray imaging technology.

Electrochemical Immunosensor for Early Detection of ß-Amyloid Alzheimer's Disease Biomarker Based on Aligned Carbon Nanotubes Gold Nanocomposites.

Beta-amyloid (ßA) peptides accompanying the physiological change in brain induce Alzheimer's disease. In this work, a highly sensitive electrochemical (EC) immunosensor platform has been developed for the quantitative detection of ßA peptides, using the gold nanoparticle functionalized chitosan-aligned carbon nanotube (CS-aCNT-Au) nanocomposites on glassy carbon electrodes (GCE). The immunosensor has been fabricated by immobilization of the anti-ßA antibody upon CS-aCNT-Au/GCE. In the CS-aCNT nanocomposite, CS has high biocompatibility. Hydroxy and amine functionalities favor the antibody immobilization and prevent the leaching of nanocomposites of the modified electrode due to the adhesive environment. Moreover, aCNT offers high conductivity, stability, and a large surface area (the calculated effective surface area of the CS-aCNT/GCE is 8.594 × 10-2 cm2). However, the incorporation of AuNPs further enhances the conductivity of the CS-aCNT-Au nanocomposite based on differential pulse voltammetry (DPV) results, and also improves the effective surface area (9.735 × 10-2 cm2). The surface morphology and electrochemical studies of the nanocomposite, as well as its modifications by the anti-ßA antibody and BSA, were carried out through field emission scanning electron microscope (FESEM), cyclic voltammetry (CV), and DPV. The quantitative immunosensing of the ßA in phosphate-buffered saline (PBS) solution is accomplished via DPV, which reveals that the immunosensor has a high sensitivity of 157.60 µA pg-1 mL cm-2 and a broad detection range of 10.0 pg mL-1-100.0 µg mL-1, with a limit of detection (LOD) of 0.87 pg mL-1. Subsequently, we detected the spiked ßA in diluted serum with a linear detection range of 10.0 pg mL-1-1.0 ng mL-1 and LOD of 0.95 pg mL-1. Moreover, a selectivity study exhibited a high affinity of immunosensors towards ßA. Thus, we propose that this highly efficient immunosensor can potentially be applied for the point-of-care (POC) sensing of ßA in clinical samples.

Distribution of Iron Nanoparticles in Arrays of Vertically Aligned Carbon Nanotubes Grown by Chemical Vapor Deposition.

Arrays of aligned carbon nanotubes (CNTs) are anisotropic nanomaterials possessing a high length-to-diameter aspect ratio, channels passing through the array, and mechanical strength along with flexibility. The arrays are produced in one step using aerosol-assisted catalytic chemical vapor deposition (CCVD), where a mixture of carbon and metal sources is fed into the hot zone of the reactor. Metal nanoparticles catalyze the growth of CNTs and, during synthesis, are partially captured into the internal cavity of CNTs. In this work, we considered various stages of multi-walled CNT (MWCNT) growth on silicon substrates from a ferrocene-toluene mixture and estimated the amount of iron in the array. The study showed that although the mixture of precursors supplies evenly to the reactor, the iron content in the upper part of the array is lower and increases toward the substrate. The size of carbon-encapsulated iron-based nanoparticles is 20-30 nm, and, according to X-ray diffraction data, most of them are iron carbide Fe3C. The reasons for the gradient distribution of iron nanoparticles in MWCNT arrays were considered, and the possibilities of controlling their distribution were evaluated.

Mechanical characterization of reinforced vertically-aligned carbon nanotube array synthesized by shock-induced partial phase transition: insight from molecular dynamics simulations.

Despite intriguing mechanical properties of carbon nanotubes (CNTs), vertically-aligned carbon nanotube (VACNT) array does not possess a high strength against compression along the CNT axis and also the loadings perpendicular to the CNT axis. Here in this study, shock compression is introduced as a means for partial phase transition (PPT) in the VACNT array to reinforce the structure against the mentioned loadings. Molecular dynamics simulations are exploited to investigate the synthesis of a novel nanostructure from a VACNT array with 10 nm long (5, 5) CNTs. Employing Hugoniostat method, shockwave pressures of 6.6 GPa and 55 GPa are extracted from Hugoniot curves as the instability limit and the PPT point, respectively. Coordination analysis reveals the nucleation of carbon atoms in sp3hybridization while preserving the dominant nature of CNT due to the high percent of sp2hybridization. Recovery of the shocked samples yields the final structure to be tested for mechanical characteristics. Tensile and compression tests on the samples reveal that for the shockwave pressures below the PPT point, an increase of the shock strength leads to higher compliance in the VACNT array. However, beyond the PPT point the novel nanostructure shows an extraordinary strong behavior against loading along all directions.

Anisotropic, Wrinkled, and Crack-Bridging Structure for Ultrasensitive, Highly Selective Multidirectional Strain Sensors.

Flexible multidirectional strain sensors are crucial to accurately determining the complex strain states involved in emerging sensing applications. Although considerable efforts have been made to construct anisotropic structures for improved selective sensing capabilities, existing anisotropic sensors suffer from a trade-off between high sensitivity and high stretchability with acceptable linearity. Here, an ultrasensitive, highly selective multidirectional sensor is developed by rational design of functionally different anisotropic layers. The bilayer sensor consists of an aligned carbon nanotube (CNT) array assembled on top of a periodically wrinkled and cracked CNT-graphene oxide film. The transversely aligned CNT layer bridge the underlying longitudinal microcracks to effectively discourage their propagation even when highly stretched, leading to superior sensitivity with a gauge factor of 287.6 across a broad linear working range of up to 100% strain. The wrinkles generated through a pre-straining/releasing routine in the direction transverse to CNT alignment is responsible for exceptional selectivity of 6.3, to the benefit of accurate detection of loading directions by the multidirectional sensor. This work proposes a unique approach to leveraging the inherent merits of two cross-influential anisotropic structures to resolve the trade-off among sensitivity, selectivity, and stretchability, demonstrating promising applications in full-range, multi-axis human motion detection for wearable electronics and smart robotics.

A 3D electrochemical biosensor based on Super-Aligned Carbon NanoTube array for point-of-care uric acid monitoring.

Uric acid analysis is extremely important for gout prognosis, diagnosis and treatment. Previous technologies either lack specificity or exhibit poor performance, and thus could not meet the need of Point-of-Care (POC) uric acid monitoring. Here we present for the first time, a novel electrochemical biosensor based on 3D Super-Aligned Carbon NanoTube (SACNT) array to facilitate POC uric acid monitoring. The working electrode of the biosensor is composed of an orderly 3D SACNT array immobilized with uricase through a precipitation and crosslinking procedure. Such biosensor possesses a higher enzyme density, significantly larger contact area with reactants and could maintain the intact SACNT structure and its excellent conductivity after modification. The developed 3D SACNT array electrochemical biosensor benefits from high specific surface area, high electro-catalytic activity and large contact area with analytes, and demonstrates high sensitivity of 518.8 µA/(mM⋅cm2), wide linear range of 100-1000 µM and low limit of detection of 1 µM for uric acid. Dynamic uric acid monitoring has been achieved using the presented biosensor. And the obtained results in serum samples had no significant difference compared with those obtained using the FDA-approved electrochemical analyzer (Paired T-test, p > 0.05). These demonstrated that the technology can potentially be applied in POC monitoring of other biomolecules to improve prognosis, diagnosis and treatment outcomes of metabolic diseases.

Vertically Aligned Carbon Nanotube Membranes: Water Purification and Beyond.

Vertically aligned carbon nanotube (VACNT) membranes have attracted significant attention for water purification owing to their ultra-high water permeability and antibacterial properties. In this paper, we critically review the recent progresses in the synthesis of VACNT arrays and fabrication of VACNT membrane methods, with particular emphasis on improving water permeability and anti-biofouling properties. Furthermore, potential applications of VACNT membranes other than water purification (e.g., conductive membranes, electrodes in proton exchange membrane fuel cells, and solar electricity-water generators) have been introduced. Finally, future outlooks are provided to overcome the limitations of commercialization and desalination currently faced by VACNT membranes. This review will be useful to researchers in the broader scientific community as it discusses current and new trends regarding the development of VACNT membranes as well as their potential applications.

Asymmetric Modification of Carbon Nanotube Arrays with Thermoresponsive Hydrogel for Controlled Delivery.

In this work, bipolar electrochemistry is used to perform wireless indirect electrodeposition of two different polymer coatings on both sides of carbon nanotube arrays. Using a thermoresponsive hydrogel on one side and an inert insoluble polymer on the other side, it is possible to generate, in a single step, a nanoporous reservoir with Janus character closed on one side by a thermoresponsive membrane. The thermoresponsive polymer, poly(N-isopropylacrylamide) (pNIPAM), is generated by the local reduction of persulfate ions, which initiates radical polymerization of NIPAM. Electrophoretic paint (EP) is chosen as an inert polymer. It is deposited by precipitation because of a local decrease in pH during water oxidation. Both polymers can be deposited simultaneously on opposite sides of the bipolar electrode during the application of the electric field, yielding a double-modified Janus object. Moreover, the length and thickness of the polymer layers can be controlled by varying the electric field and the deposition time. This concept is applied to vertically aligned carbon nanotube arrays (VACNTs), trapped inside an anodic aluminum oxide membrane, which can further be used as a smart reservoir for chemical storage and release. A fluorescent dye is loaded in the VACNTs and its release is studied as a function of temperature. Low temperature, when the hydrogel layer is in the swollen state, allows diffusion of the molecule. Dye release occurs on the hydrogel-modified side of the VACNTs. At high temperatures, when the hydrogel layer is in the collapsed state, dye release is blocked because of the impermeability of the pNIPAM layer. This concept paves the way toward the design of advanced devices in the fields of drug storage and directed delivery.

Rapid Size-Based Isolation of Extracellular Vesicles by Three-Dimensional Carbon Nanotube Arrays.

Recent discoveries reveal that extracellular vesicles (EVs) play an important role in transmitting signals. Although this emerging transcellular pathway enables a better understanding of neural communication, the lack of techniques for effectively isolating EVs impedes their studies. Herein, we report an emergent high-throughput platform consisting of three-dimensional carbon nanotube arrays that rapidly capture different EVs based on their sizes, without any labels. More importantly, this label-free capture maintains the integrity of the EVs when they are excreted from a host cell, thus allowing comprehensive downstream analyses using conventional approaches. To study neural communication, we developed a stamping technique to construct a gradient of nanotube herringbone arrays and integrated them into a microdevice that allowed us processing of a wide range of sample volumes, microliters to milliliters, in several minutes through a syringe via manual hand pushing and without any sample preparation. This microdevice successfully captured and separated EVs excreted from glial cells into subgroups according to their sizes. During capture, this technology preserved the structural integrity and originality of the EVs that enabled us to monitor and follow internalization of EVs of different sizes by neurons and cells. As a proof of concept, our results showed that smaller EVs (∼80 nm in diameter) have a higher uptake efficiency compared to larger EVs (∼300 nm in diameter). In addition, after being internalized, small EVs could enter endoplasmic reticulum and Golgi but not the largest ones. Our platform significantly shortens sample preparation, allows the profiling of the different EVs based on their size, and facilitates the understanding of extracellular communication. Thus, it leads to early diagnostics and the development of novel therapeutics for neurological diseases.

MoSe2 nanoflakes-decorated vertically aligned carbon nanotube film on nickel foam as a binder-free supercapacitor electrode with high rate capability.

A new type of composite electrode material, MoSe2 nanoflakes grown on the vertically aligned carbon nanotube array film (VACNTF) with binder-free nickel foam as current collector (VACNTF@MoSe2/NF), was fabricated by a simple spraying chemical vapor deposition method combined with the solvothermal technique. Owing to the introduction of the VACNTF with ordered channels and appropriate intertube spacing, which facilitate electrolyte ions quickly transferring and alleviate the volume changes in the electrochemical measurements, the VACNTF@MoSe2/NF sample presents superior electrochemical performance compared to pure MoSe2/NF sample. The VACNTF@MoSe2/NF sample exhibits high specific capacitance of 435 F·g-1 at 1 A·g-1, remarkable cycling stability (92% of the original capacitance maintaining over 5000 cycles) and especially excellent rate capability (84.1% capacitance retention with the current density changed from 1 to 15 A·g-1). Moreover, the VACNTF@MoSe2/NF based asymmetric supercapacitor exhibits a high energy density with 22 Wh·kg-1 for a power density of 330 W·kg-1. This paper offers a new strategy to prepare transition metal dichalcogenides based electrode materials with high rate performance.

Gd-Enhanced Growth of Multi-Millimeter-Tall Forests of Single-Wall Carbon Nanotubes.

Multi-millimeter-tall vertically aligned single-wall carbon nanotube (VA-SWCNT) forests were grown using Fe/Gd/Al2Ox catalyst with high initial growth rate of ∼2 µm s-1 and long catalyst lifetime of ∼70 min at 800 °C. The addition of Gd with a nominal thickness of 0.3 nm drastically prolonged the catalyst lifetime. The analysis of the VA-SWCNT forests by a transmission electron microscope showed that the average diameter of the SWCNTs grown with Gd is constant from the top to the bottom of the forests, while it monotonically increased without Gd. This indicated that Gd suppresses the structure change of the Fe nanoparticles in the lateral direction during the CNT growth. By X-ray photoelectron spectroscopy, it was found that the longer catalyst lifetime with Gd stems from the suppression of the interaction between Fe and C resulting in the smaller structure change of the Fe nanoparticles.

Applying Aluminum⁻Vertically-Aligned Carbon Nanotube Forests Composites for Heat Dissipation.

Vertically-aligned carbon nanotube forests (VACNTs) with excellent axial heat dissipation properties were formed on aluminum foil to dissipate heat. In addition, the heat dissipation efficiency of aluminum-VACNTs composites in this work was compared with that of commercially available mainstream thermal sheets under the same natural cooling conditions. Chemical vapor deposition (CVD) was employed as a synthesis method using a three-segment high-temperature furnace. Subsequently, the temperature changes in a heating body with the aluminum-VACNTs composites was measured over time subject to natural cooling. In addition, the performance was compared with copper and pyrolytic graphite sheets. The experimental results revealed that the heat dissipation efficiency of the flexible aluminum-VACNTs composites was higher than that of clean aluminum foil, a copper sheet, and a pyrolytic graphite sheet by up to 56%, 40%, and 20%, respectively. Moreover, this work also verified the height of the carbon nanotube (CNT) did not influence the heat dissipation efficiency, indicating that the time cost of synthesis could be reduced.