Semiconducting Carbon Nanotubes Research Articles

Selective oxidation and removal of hydrocarbons from carbon nanotubes using reactive yttrium films

Wrapping polymers are useful for sorting high purity suspensions of semiconducting carbon nanotubes (CNTs) in organic solvents, but for many microelectronic applications the wroapping polymer needs to be removed. Coating wrapped CNTs with yttrium metal, followed by oxidation and removal with dilute aqueous acid, has been used to etch wrapping polymer, but the mechanism, selectivity, extent of etching, and range of conditions over which etching occurs have not been reported. We use spectroscopic and physical measurements to characterize this process on thin films of an archetypical conjugated wrapping polymer (PFO-BPy), its amorphous char residue, CNTs (average diameter 1.5 nm), graphene, and other organic films. Exposure of a yttrium overcoated film of PFO-BPy to ambient air at 20 °C oxidizes a ∼0.5 nm layer of polymer, forming carbonate, carboxylate, and/or carbonyl groups that dissolve in dilute acid. Thicker layers of polymer are removed by repeated cycles. Similar results are observed for other organic films at 20 °C whereas CNTs and graphene are unaltered, providing the selectivity needed to remove carbon-based contaminants from sp2 carbon based nanostructures. Increasing temperature to 250 °C increases polymer oxidation and removal to ∼2.5 nm per cycle; however, the CNTs and graphene are damaged.

Carrier Doping in Semiconducting Carbon Nanotubes with Fluorosumanenes

Carrier Doping in Semiconducting Carbon Nanotubes with Fluorosumanenes

Multiphoton ionization in a photonic crystal based on carbon nanotubes under the action of a few cycle optical pulse

We considered a theoretical model of the interaction of a one-dimensional few cycles optical pulse with a nonlinear medium of semiconductor carbon nanotubes, which has a spatial modulation of the refractive index in the direction of pulse propagation (a one-dimensional photonic crystal). The results of the dependence of the rate of one- and two-photon ionization on the intensity of the short-wavelength pulse are shown. The effect of additional external electric and magnetic fields on the photoionization rate is considered.

Reproducible, Accurate, and Sensitive Food Toxin On-Site Detection with Carbon Nanotube Transistor Biosensors.

Field-effect transistor (FET) biosensors based on nanomaterials are promising in the areas of food safety and early disease diagnosis due to their ultrahigh sensitivity and rapid response. However, most academically developed FET biosensors lack real-world reproducibility and comprehensive methodological validation to meet the standards of regulatory bodies. Here, highly uniform and well-packaged semiconducting carbon nanotube (CNT) FET biosensor chips were developed and assessed for the plug-and-play sensing for the rapid and highly sensitive detection of aflatoxin B1 (AFB1) in real food samples to meet international standards. In order to meet the requirements for reproducibility and stability, a scalable residual-free passivation and packaging process was developed for CNT FET biosensors. Portable detection systems were then constructed for on-site detection. The resulting packaged chips were functionalized with nucleic aptamers to enable highly selective detection of AFB1 in food samples with a detection limit (LOD) of 0.55 fg/mL (standard) for AFB1 and cross-reactivity coefficients to interferences as low as 1.8 × 10-7 in simulated solutions. Utilizing the portable detection system, on-site real food detection was achieved with a rapid response time less than 60 s, and LOD of 0.25 pg/kg (standard) in complex corn sample matrices. Single-blind tests demonstrated the ability of the chips to detect AFB1-positive food with 100% accuracy, using a set of 30 peanut samples. Validation experiments confirmed that the detection range, stability, and repeatability met international standards. This study showcased the accuracy, reliability, and potential practical applications of CNT FET biosensor chips in areas such as food safety and rapid biomedical testing.

Investigation on Junction Contacts of Semiconducting Carbon Nanotube Networks Using Conductive Atomic Force Microscopy.

Semiconductor single-walled carbon nanotube (s-SWNT) networks have gained prominence in electronic devices due to their cost-effectiveness, relatively production-naturality, and satisfactory performance. Configuration, density, and resistance of SWNT-SWNT junctions are considered crucial factors influencing the overall conductivity of s-SWNT networks. In this study, we present a method for inferring the lower bounds of the SWNT-SWNT junction resistance in s-SWNT networks based on conductive atomic force microscopy TUNA images. This method further enables the proposal of a classification for SWNT-SWNT junctions based on the current behavior relative to their surroundings. The three types of SWNT-SWNT junctions are denoted as (i) true contact (T), (ii) poor contact (P), and (iii) false contact (F). Of them, the true and poor contacts, respectively, represent good and poor electrical contact for the subject SWNT-SWNT junctions whose electrical conductivity hardly improves under external tip pressure, while that of the false contact can be further improved by external pressure. Statistical analysis demonstrates that while T-type junctions make a significant contribution to network conductivity, their proportion accounts for only approximately 40%. The P-type and F-type junctions, which constitute over 60% of the total, may be a contributing factor that constrains the overall conductivity of the s-SWNT networks. The height ratio of the junction to the sum of two SWNTs was also observed to exhibit variations among the three types. Finally, we propose a three-dimensional model to elucidate the formation mechanism underlying each type of junction. The present study provides insights into the performance of spontaneous contacts between s-SWNTs in the networks, and the systematic image acquisition and junction classification processes may provide support for future advancements in these networks.

High-Performance Semiconducting Carbon Nanotube Transistors Using Naphthalene Diimide-Based Polymers with Biaxially Extended Conjugated Side Chains.

Polymer-wrapped single-walled carbon nanotubes (SWNTs) are a potential method for obtaining high-purity semiconducting (sc) SWNT solutions. Conjugated polymers (CPs) can selectively sort sc-SWNTs with different chiralities, and the structure of the polymer side chains influences this sorting capability. While extensive research has been conducted on modifying the physical, optical, and electrical properties of CPs through side-chain modifications, the impact of these modifications on the sorting efficiency of sc-SWNTs remains underexplored. This study investigates the introduction of various conjugated side chains into naphthalene diimide-based CPs to create a biaxially extended conjugation pattern. The CP with a branched conjugated side chain (P3) exhibits reduced aggregation, resulting in improved wrapping ability and the formation of larger bundles of high-purity sc-SWNTs. Grazing incidence X-ray diffraction analysis confirms that the potential interaction between sc-SWNTs and CPs occurs through π-π stacking. The field-effect transistor device fabricated with P3/sc-SWNTs demonstrates exceptional performance, with a significantly enhanced hole mobility of 4.72 cm2 V-1 s-1 and high endurance/bias stability. These findings suggest that biaxially extended side-chain modification is a promising strategy for improving the sorting efficiency and performance of sc-SWNTs by using CPs. This achievement can facilitate the development of more efficient and stable electronic devices.

Mass Production of Carbon Nanotube Transistor Biosensors for Point-of-Care Tests.

Low-dimensional semiconductor-based field-effect transistor (FET) biosensors are promising for label-free detection of biotargets while facing challenges in mass fabrication of devices and reliable reading of small signals. Here, we construct a reliable technology for mass production of semiconducting carbon nanotube (CNT) film and FET biosensors. High-uniformity randomly oriented CNT films were prepared through an improved immersion coating technique, and then, CNT FETs were fabricated with coefficient of performance variations within 6% on 4-in. wafers (within 9% interwafer) based on an industrial standard-level process. The CNT FET-based ion sensors demonstrated threshold voltage standard deviations within 5.1 mV at each ion concentration, enabling direct reading of the concentration information based on the drain current. By integrating bioprobes, we achieved detection of biosignals as low as 100 aM through a plug-and-play portable detection system. The reliable technology will contribute to commercial applications of CNT FET biosensors, especially in point-of-care tests.

Enhancing durable electrical conductivity in multi‐walled carbon nanotubes‐epoxy composites via laser repetition rate nanojoining for flexible electronics

AbstractWith the development of nanotechnology, laser matter interaction has become intriguing for many applications, including the manufacturing of flexible electronics to improve interface behaviors. Employing high laser repetition rate nanojoining transfer patterning, this study ensures the robust and consistent stability of electrical properties of MWCNTs. This procedure meticulously eliminates contaminants from the interface between flexible PET substrates and carbon nanotube‐containing epoxy, significantly influencing the degree of alteration in composite material and interface behaviors. By increasing the laser repetition rate from the original sample to the sample irradiated by a laser with a repetition rate of 80 kHz, the defect concentration in carbon nanotubes decreases from 0.448 × 106/nm2 to 0.39376 × 106/nm2, respectively. The relationship between defect concentration and electrical conductivity in semiconductor carbon nanotubes under laser irradiation is multifaceted and context‐dependent. Optimizing the laser repetition rate is crucial in defining the kind and density of semiconductor carbon nanotubes. This study found an electrical conductivity of 3.6799 × 10−4 S/m at a laser repetition rate of 80 kHz. Laser ablation nanojoining with a high laser repetition rate is poised to become a key recycling method for plastic materials in future industries. When MWCNTs are used in processing new materials, this method not only enhances the electrical and mechanical properties of recycled plastics but also creates high‐performance composites with added value. Additionally, the quick nature of this process helps minimize toxicity in material processing by reducing exposure time and the need for harmful chemicals. These composites exhibit superior properties suitable for advanced applications such as flexible electronics, sensors, and nanocomposite materials, contributing to both sustainability and economic value in various industrial sectors.

Achieving High-Performance Polymer-Wrapper-Free Aligned Carbon Nanotube Field-Effect Transistors Through Degradable Polymer Wrapping and Efficient Removal Techniques.

Semiconducting carbon nanotubes (s-CNTs) have emerged as a promising alternative to traditional silicon for ultrascaled field-effect transistors (FETs), owing to their exceptional properties. Aligned s-CNTs (A-CNTs) are particularly favored for practical applications due to their ability to provide higher driving current and lower contact resistance compared with individual s-CNTs or random networks. Achieving high-semiconducting-purity A-CNTs typically involves conjugated polymer wrapping for selective separation of s-CNTs, followed by self-assembly techniques. However, the presence of the polymer wrapper on A-CNTs can adversely impact electrical contact, gating efficiency, carrier transport, and device-to-device variations, necessitating its complete removal. While various methods have been explored for polymer removal, accurately characterizing the extent of removal remains a challenge. Traditional techniques such as absorption spectroscopy and X-ray photoelectron spectroscopy (XPS) may not accurately depict the remaining polymer content on A-CNTs due to their inherent detection limits. Consequently, the performance of FETs based on pure polymer-wrapper-free A-CNTs is unclear. In this study, we present an approach for preparing high-semiconducting-purity and polymer-wrapper-free A-CNTs using poly[(9,9-dioctylfluorenyl-2,7-dinitrilomethine)-(9,9-dioctylfluorenyl-2,7-dimethine)] (PFO-N-PFO), a degradable polymer, in conjunction with a modified dimension-limited self-alignment process (m-DLSA). Comprehensive transmission electron microscopy (TEM) characterizations, complemented by absorption and XPS characterizations, provide robust evidence of the successful near-complete removal of the polymer wrapper via a cleaning procedure involving acidic degradation, hot solvent rinsing, and vacuum annealing. Furthermore, top-gated FETs based on these high-semiconducting-purity and polymer-wrapper-free A-CNTs exhibit good performance metrics, including an on-current (Ion) of 2.2 mA/μm, peak transconductance (gm) of 1.1 mS/μm, low contact resistance (Rc) of 191 Ω·μm, and negligible hysteresis, representing a significant advancement in the CNT-based FET technology.

(Invited) 2D Liquid Crystals of Aligned Semiconducting Carbon Nanotubes at Liquid-Liquid Interfaces

Carbon nanotubes transport more electricity per area than silicon and more easily switch between on and off states with lower voltage, making them exciting for future, fast, low-energy logic and high-speed, linear RF devices. For nanotubes to offer the highest performance, they must be aligned in one direction in a single layer so that electricity can quickly and efficiently flow through them. This has been a long-standing challenge.This talk will present on recent, yet-to-be published advances at the University of Wisconsin on assembling and aligning dense arrays of polymer wrapped semiconducting carbon nanotubes via 2D liquid crystal (2D-LC) phenomena at liquid-liquid interfaces. Topics will include: (1) the direct visualization of 2D-LCs of nanotubes at liquid-liquid interfaces via in situ polarized optical microscopy; (2) the assembly of nanotubes at density of > 250 nanotubes μm-1 at liquid-liquid interfaces; (3) the post-alignment and post-deposition removal of polymer wrapper via oxidation at room-temperature; and (4) field effect transistor studies incorporating all of the above.

(Invited) Tackling Leakage, Drift, and Variation in Printed Carbon Nanotube-Based Electronic Biosensors

Semiconducting carbon nanotubes (CNTs) have been pursued for use in electronic biosensors for decades. Their all-surface molecular structure, sizeable semiconducting bandgap, and solution-phase compatibility make them highly sensitive and versatile options for transducing target bioelectrical signals. However, amid the thousands of reports on CNT-based electronic biosensors, very little attention has been given to identifying (let alone addressing) the impact of leakage current, signal drift, and device-to-device variation. This talk will present recent results focused on tackling these issues with specific emphasis on printed CNT-based biosensors. For instance, a variety of passivation strategies were studied to determine the role of leakage current for CNT transistor-based biosensors (i.e., bioFETs or ion-sensitive FETs), revealing that a bilayer epoxy/high-k dielectric stack was most effective at minimizing unwanted leakage current. The influence of signal drift will also be demonstrated, likely playing a significant role in many previous reports of CNT-based biosensors characterized by sequential concentration spikes. Finally, strategies for addressing device-to-device variation in these biosensors will be discussed, including the motivation for a printed thin-film device rather than a single-CNT configuration. Two things seem certain about this field: 1) the promise of CNT-based biosensors continues to suggest they are worth ongoing pursuit, and 2) there is much work remaining towards achieving a reproducible, reliable electronic biosensing technology from CNTs.

Aligned Semiconducting Carbon Nanotubes for Commercial Logic and RF Electronics

Carbon nanotubes are exceptional semiconductors that offer larger current densities and faster switching than conventional Si and GaAs devices, making nanotubes promising for meeting the performance and energy efficiency needs of next-generation electronics. However, the successful commercialization of carbon nanotubes necessitates the control over semiconducting purity, alignment, packing density, and scalability. The simultaneous control of these characteristics has been a major challenge preventing the integration of nanotubes in industrial electronics and the full exploitation of their electronic properties. This talk will present an overview of recent technological developments and methods that progress towards these goals.In these methods, semiconducting (purity of >99.99%) carbon nanotubes are deposited on target substrates via scalable alignment methods at room temperatures. These individual methods separately enable the deposition of quasi-aligned (±28°) nanotube arrays (~50 nanotubes µm-1) demonstrated across 100 mm substrates, highly-aligned (±6°) nanotube arrays (~100 nanotubes µm-1) demonstrated across 100 mm substrates, and the selective-area deposition of highly-aligned nanotube (±7°) arrays (~up to 250 nanotubes µm-1). The nanotube arrays with high packing density (~250 nanotubes μm-1) yield exceptional current densities of 2 mA μm-1 and transconductances of 1 mS μm-1 at VD of -0.6V. Importantly, due to the low-temperature nature of the deposition processes, these techniques offer a direct path towards the alignment of carbon nanotubes directly on Si and other materials, such as GaN or plastics, to enable high-performance 3D integrated circuits.

Research on channel-exposed carbon-based FET humidity sensor

Abstract The ability to detect humidity is crucial for a variety of sectors, including industrial manufacturing, meteorological surveillance, and the preservation of materials, among others. Field effect transistor (FET) based sensor, renowned for its signal amplification effect, plays a pivotal role in detecting trace-level analytes with high sensitivity. Our work demonstrates the preparation of a humidity sensor based on carbon-based FET architecture, employing micro-nano processing techniques. In this work, semiconducting carbon nanotubes serve as the sensing material and channel at the same time. The outcomes indicate that the sensor exhibits a linear response ranging from 0% to 80% relative humidity (RH) and good repeatability. It also shows long-term stability in a 40-day test, proving potential applications in FET-type humidity sensors.

Delocalized Charge Transport in Thermoelectric Composites of Semiconducting Carbon Nanotubes Wrapped with a P‐Type Polymer

Delocalized Charge Transport in Thermoelectric Composites of Semiconducting Carbon Nanotubes Wrapped with a P‐Type Polymer

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.

Label-Free and Ultrasensitive Detection of Cartilage Acidic Protein 1 in Osteoarthritis Using a Single-Walled Carbon Nanotube Field-Effect Transistor Biosensor.

Osteoarthritis (OA), a prevalent degenerative joint disease, significantly affects the well-being of afflicted individuals and compromises the standard functionality of human joints. The emerging biomarker, Cartilage acidic protein 1 (CRTAC1), intricately associates with OA initiation and serves as a prognostic indicator for the trajectory toward joint replacement. However, existing diagnostic methods for CRTAC1 are hampered by the limited abundance, thus restricting the precision and specificity. Herein, a novel approach utilizing a single-walled carbon nanotube field-effect transistor (SWCNTs FET) biosensor is reported for the direct label-free detection of CRTAC1. High-purity semiconducting carbon nanotube films, functionalized with antibodies of CRTAC1, provide excellent electrical and sensing properties. The SWCNTs FET biosensor exhibits high sensitivity, notable reproducibility, and a wide linear detection range (1 fg/mL to 100 ng/mL) for CRTAC1 with a theoretical limit of detection (LOD) of 0.2 fg/mL. Moreover, the SWCNTs FET biosensor is capable of directly detecting human serum samples, showing excellent sensing performance in differentiating clinical samples from OA patients and healthy populations. Comparative analysis with traditional enzyme-linked immunosorbent assay (ELISA) reveals that the proposed biosensor demonstrates faster detection speeds, higher sensitivity/accuracy, and lower errors, indicating high potential for the early OA diagnosis. Furthermore, the SWCNTs FET biosensor has good scalability for the combined diagnosis and measurement of multiple disease markers, thereby significantly expanding the application of SWCNTs FETs in biosensing and clinical diagnostics.

Inner Doping of Carbon Nanotubes with Perovskites for Ultralow Power Transistors.

Semiconducting carbon nanotubes (CNTs) are considered as the most promising channel material to construct ultrascaled field-effect transistors, but the perfect sp2 C─C structure makes stable doping difficult, which limits the electrical designability of CNT devices. Here, an inner doping method is developed by filling CNTs with 1D halide perovskites to form a coaxial heterojunction, which enables a stable n-type field-effect transistor for constructing complementary metal-oxide-semiconductor electronics. Most importantly, a quasi-broken-gap (BG) heterojunction tunnel field-effect transistor (TFET) is first demonstrated based on an individual partial-filling CsPbBr3/CNT and exhibits a subthreshold swing of 35mV dec-1 with a high on-state current of up to 4.9µA per tube and an on/off current ratio of up to 105 at room temperature. The quasi-BG TFET based on the CsPbBr3/CNT coaxial heterojunction paves the way for constructing high-performance and ultralow power consumption integrated circuits.

Semiconducting Carbon Nanotube Extraction Enabled by Alkylated Cellulose Wrapping.

With the growing demand for postsilicon electronics, the purification of single-walled carbon nanotubes (SWCNTs) in terms of their chirality, which defines their atomic and electronic structure, is becoming increasingly important. Herein, we demonstrate the selective extraction of high-quality semiconducting SWCNTs using alkyl cellulose as a dispersant in organic solvents. We investigated the separation factors of dispersant structures, such as the degree of substitution (DS) and molecular weight, and clarified the appropriate dispersant structures, such as moderately substituted hexyl cellulose, for selective semiconducting SWCNT extraction. Due to the improved purity and quality of the semiconducting SWCNTs obtained by this method, their films exhibit excellent thermoelectric power factors, outperforming not only unsorted SWCNTs but also conducting polymer-sorted SWCNTs. This sorting technology paves the way for supplying high-quality semiconducting SWCNTs in a viable manner.

Molecular transport enhancement in pure metallic carbon nanotube porins.

Nanofluidic channels impose extreme confinement on water and ions, giving rise to unusual transport phenomena strongly dependent on the interactions at the channel-wall interface. Yet how the electronic properties of the nanofluidic channels influence transport efficiency remains largely unexplored. Here we measure transport through the inner pores of sub-1 nm metallic and semiconducting carbon nanotube porins. We find that water and proton transport are enhanced in metallic nanotubes over semiconducting nanotubes, whereas ion transport is largely insensitive to the nanotube bandgap value. Molecular simulations using polarizable force fields highlight the contributions of the anisotropic polarizability tensor of the carbon nanotubes to the ion-nanotube interactions and the water friction coefficient. We also describe the origin of the proton transport enhancement in metallic nanotubes using deep neural network molecular dynamics simulations. These results emphasize the complex role of the electronic properties of nanofluidic channels in modulating transport under extreme nanoscale confinement.

Dopant-Inherent Mechanisms of Atmospheric Stability in Chemically N-Doped Semiconducting Carbon Nanotubes Revealed by Tracking Optical Absorption

Dopant-Inherent Mechanisms of Atmospheric Stability in Chemically N-Doped Semiconducting Carbon Nanotubes Revealed by Tracking Optical Absorption