Individual Nanotubes Research Articles

(Invited) High Temperature Exciton Properties in Aggregated Single-Walled Carbon Nanotubes

Individual single-walled carbon nanotubes (SWCNTs) at high temperatures have been reported to generate narrow-band thermal radiation in the near-infrared region due to thermally robust excitonic effects [1,2]. This phenomenon potentially offers a new opportunity for utilizing exciton properties in thermal engineering such as thermophotovoltaic energy harvesting requiring excellent wavelength selective near-infrared thermal emitter. However, for its realistic applications in macroscale, it is necessary to make the distinct exciton effect available under high temperature conditions in macroscopic assemblies of SWCNTs. As a first step toward this goal, we have recently determined broadband complex refractive index spectra of single-chirality SWCNT membranes in which SWCNTs are aligned two-dimensionally in a plane [3] and reported their birefringent properties [4]. In the presentation, we will discuss the change in the optical spectra of SWCNT assemblies with increasing temperature, as well as how the aggregation states affect the exciton properties. [1] T. Nishihara, A. Takakura, Y. Miyauchi, and K. Itami, Nat. Commun. 9, 3144 (2018). [2] S. Konabe, T. Nishihara, and Y. Miyauchi, Opt. Lett. 46, 3021 (2021). [3] T. Nishihara, A. Takakura, M. Shimasaki, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Nanophotonics 11, 1011 (2022). [4] H. Wu, T. Nishihara, A. Takakura, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Carbon, in press.

(Invited) Correlation Measurements for Carbon Nanotubes with Quantum Defects

Single-photon sources are one of the essential building blocks for the development of photonic quantum technology. In terms of potential practical application, an on-demand electrically driven quantum-light emitter on a chip is notably crucial for integrating photonic integrated circuits. Here, we propose functionalized single-walled carbon nanotube field-effect transistors as a promising solid-state quantum-light source by demonstrating photon antibunching behavior via electrical excitation. The sp3 quantum defects were formed on the surface of (7, 5) carbon nanotubes by 3,5-dichlorophenyl functionalization, and individual carbon nanotubes were wired to graphene electrode pairs. Filtered electroluminescent defect-state emission at 77 K was coupled into a Hanbury Brown and Twiss experiment setup, and single-photon emission was observed by performing second-order correlation function measurements. We discuss the dependence of the intensity correlation measurement on excitation power and emission wavelength highlighting the challenges of performing such measurements while simultaneously analyzing acquired data. Our results indicate a route toward room-temperature electrically-triggered single-photon emission.

Programmable Carbon Nanotube Networks: Controlling Optical Properties Through Orientation and Interaction.

The lattice geometry of natural materials and the structural geometry of artificial materials are crucial factors determining their physical properties. Most materials have predetermined geometries that lead to fixed physical characteristics. Here, the demonstration of a carbon nanotube network serves as an example of a system with controllable orientation achieving on-demand optical properties. Such a network allows programming their optical response depending on the orientation of the constituent carbon nanotubes and leads to the switching of its dielectric tensor from isotropic to anisotropic. Furthermore, it also allows for the achievement of wavelength-dispersion for their principal optical axes - a recently discovered phenomenon in van der Waals triclinic crystals. The results originate from two unique carbon nanotubes features: uniaxial anisotropy from the well-defined cylindrical geometry and the intersection interaction among individual carbon nanotubes. The findings demonstrate that shaping the relative orientations of carbon nanotubes or other quasi-one-dimensional materials of cylindrical symmetry within a network paves the way to a universal method for the creation of systems with desired optical properties.

Carbon nanotube fibers with dynamic strength up to 14 GPa.

High dynamic strength is of fundamental importance for fibrous materials that are used in high-strain rate environments. Carbon nanotube fibers are one of the most promising candidates. Using a strategy to optimize hierarchical structures, we fabricated carbon nanotube fibers with a dynamic strength of 14 gigapascals (GPa) and excellent energy absorption. The dynamic performance of the fibers is attributed to the simultaneous breakage of individual nanotubes and delocalization of impact energy that occurs during the high-strain rate loading process; these behaviors are due to improvements in interfacial interactions, nanotube alignment, and densification therein. This work presents an effective strategy to utilize the strength of individual carbon nanotubes at the macroscale and provides fresh mechanism insights.

Enhancing structural integrity and adsorption performance of carbon nanotube buckypaper for water remediation through innovative densification strategy

The transformation of individual carbon nanotubes (CNTs) into buckypaper often results in random organization, leading to gaps or pores between them. These gaps act as flaws, reducing the overall properties of the bulk CNT structure. This study presents an advanced technique for densifying the structure by filling the gaps to tackle this issue. To achieve this, smaller multi-walled carbon nanotubes (MWCNTs) were employed to fill the gaps in the buckypaper composed of larger MWCNTs. This approach resulted in a significant improvement in the physical properties of the structure. The resulting hybrid buckypaper was thoroughly characterized using various techniques, including scanning electron microscopy, Raman spectroscopy, BET, XRD, and thermogravimetric analysis. The findings of this study demonstrated notable enhancements in the packing density, specific surface area, and tensile strength of the hybrid buckypaper, with improvements of 31.38 %, 63 %, and 20 %, respectively. Furthermore, the hybrid buckypaper proved to be an effective adsorbent for removing methylene blue dye from wastewater, exhibiting an impressive adsorption efficiency of 99.53 %. The absence of sludge impurities due to its high mechanical strength, combined with its superior rejuvenation capacity during multiple uses encourages cleaner and efficient water treatment system.

Porous Organic Nanotubes: Chemistry of One-Dimensional Space.

ConspectusOne-dimensional organic nanotubes feature unique properties, such as confined chemical environments and transport channels, which are highly desirable for many applications. Advances in synthetic methods have enabled the creation of different types of organic nanotubes, including supramolecular, hydrogen-bonded, and carbon nanotube analogues. However, challenges associated with chemical and mechanical stability along with difficulties in controlling aspect ratios remain a significant bottleneck. The fascination with structured porous materials has paved the way for the emergence of reticular solids such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and organic cages. Reticular materials with tubular morphology promise architectural stability with the additional benefit of permeant porosity. Despite this, the current synthetic approaches to these reticular nanotubes focus more on structural design resulting in less reliable morphological uniformity. This Account, highlights the design motivation behind various classes of organic nanotubes, emphasizing their porous interior space. We explore the strategic assembly of organic nanotubes based on their bonding characteristics, from weak supramolecular to robust covalent interactions. Special attention is given to reticular nanotubes, which have gained prominence over the past two decades due to their distinctive micro and mesoporous structures. We examine the synergy of covalent and noncovalent interactions in constructing assembly of these nanotube structures.This Account furnishes a comprehensive overview of our efforts and advancements in developing porous covalent organic nanotubes (CONTs). We describe a general synthetic approach for creating robust imine-linked nanotubes based on the reticular chemistry principles. The use of spatially oriented tetratopic triptycene-based amine and linear ditopic aldehyde building blocks facilitates one-dimensional nanotube growth. The interplay between directional covalent bonds and solvophobic interactions is crucial for forming uniform, well-defined, and high aspect ratio nanotubes. The nanotubes derive their permeant porosity and thermal and chemical stability from their covalent architecture. We also highlight the adaptability of our synthetic methodology to guide the transformation of one-dimensional nanotubes to toroidal superstructures and two-dimensional thin fabrics. Such morphological transformation can be directed by tuning the reaction time or incorporating additional intermolecular interactions to control the intertwining behavior of individual nanotubes. The cohesion of covalent and noncovalent interactions in the tubular nanostructures manifests superior viscoelastic mechanical properties in the assembled CONT fabrics. We establish a strong correlation between structural framework design and nanostructures by translating reticular synthesis to morphological space and gaining insights into the assembly processes. We anticipate that the present Account will lay the foundation for exploring new designs and chemistry of organic nanotubes for many application platforms.

Experimental determination of the Young’s modulus of individual single-walled carbon nanotubes with single chirality

Experimental determination of the Young’s modulus of individual single-walled carbon nanotubes with single chirality

Nucleation of disclinations in carbon nanotube bundle structures under twisting loads

Twisting is a simple and effective method for assembling individual carbon nanotubes (CNTs) into high-strength, tough, and continuous CNT yarns. However, the unexpectedly low stretching performance of the resulting carbon nanotube bundle (CNTB) structures is a problem that must be resolved. In this study, we investigated the impact of twisting on the structure and stretching performance of CNTBs through molecular dynamics (MD) simulations while considering the presence of disclinations within the CNTB structure. We found that disclinations nucleate in twisted CNTBs, and the longer the disclination line in CNTBs, the lower the Young's modulus. The presence of disclination lines in the twisted CNTBs may be an important reason for the decrease in the tensile properties of the CNT yarns. Although the theoretical equations in textile field can be applied to describe the mechanical properties of CNT yarns, there are significant relative errors between the equations and the MD simulation results presented herein. Therefore, we revised the equations based on the simulation results to reduce the relative error for seven-layer CNTBs to less than 10 %. This paper provides new insights into the low tensile performance of CNT yarns and offers potential guidance for the production of high-performance CNT yarns through twisting.

Revealing operando surface defect–dependent electrocatalytic performance of Pt at the subparticle level

Understanding the operando defect-tuning performance of catalysts is critical to establish an accurate structure-activity relationship of a catalyst. Here, with the tool of single-molecule super-resolution fluorescence microscopy, by imaging intermediate CO formation/oxidation during the methanol oxidation reaction process on individual defective Pt nanotubes, we reveal that the fresh Pt ends with more defects are more active and anti-CO poisoning than fresh center areas with less defects, while such difference could be reversed after catalysis-induced step-by-step creation of more defects on the Pt surface. Further experimental results reveal an operando volcano relationship between the catalytic performance (activity and anti-CO ability) and the fine-tuned defect density. Systematic DFT calculations indicate that such an operando volcano relationship could be attributed to the defect-dependent transition state free energy and the accelerated surface reconstructing of defects or Pt-atom moving driven by the adsorption of the CO intermediate. These insights deepen our understanding to the operando defect-driven catalysis at single-molecule and subparticle level, which is able to help the design of highly efficient defect-based catalysts.

Cavity-enhanced photon indistinguishability at room temperature and telecom wavelengths

Indistinguishable single photons in the telecom-bandwidth of optical fibers are indispensable for long-distance quantum communication. Solid-state single photon emitters have achieved excellent performance in key benchmarks, however, the demonstration of indistinguishability at room-temperature remains a major challenge. Here, we report room-temperature photon indistinguishability at telecom wavelengths from individual nanotube defects in a fiber-based microcavity operated in the regime of incoherent good cavity-coupling. The efficiency of the coupled system outperforms spectral or temporal filtering, and the photon indistinguishability is increased by more than two orders of magnitude compared to the free-space limit. Our results highlight a promising strategy to attain optimized non-classical light sources.

Space confinement effect of carbon nanotube-alumina strip support on the Cu-Co catalysts for CO2 methanation

The present work reported the space confinement effect of carbon nanotube-alumina strip (CAS) support on the Cu-Co bimetallic catalyst or the single Cu, Co catalysts for the CO2 methanation. CAS, made by extrusion of nanotubes and Al-based sol and high temperature calcination, was a macroscopic support with sufficient mesopores and hydrophobic property. Cu-Co/CAS catalysts exhibited high catalytic activity for methanation of CO2 (H2/CO2=3:1), where CO2 conversion was 49.62% and CH4 selectivity was 95.98% at temperature as low as 250 ℃ and 1.5 MPa, and showed advantage significantly over those with the supports of individual nanotube or pure Alumina support. The comparison suggested the hydrophobicity of carbon nanotubes can effectively remove water from the metal active sites, enhancing the equilibrium of reverse water gas shift and CO methanation reactions, as compared to alumina support. Additionally, CAS support had a spatial confinement effect that increased the contact time of CO2 or intermediates with the active sites, compared with individual nanotube support. XPS and Raman spectroscopy validated the presence of oxygen vacancies of CAS, promoting the CO2 methanation. H2-TPR results, in combination with DFT calculations, confirmed that the CAS supports enabled the Cu-Co active phase by changing their electronic structures, to possess a strong adsorption activation capacity for H2 at low temperatures with high performance for CO2 methanation.

Identification of Early Stage Liver Fibrosis by Modifications in the Interstitial Space Diffusive Microenvironment Using Fluorescent Single-Walled Carbon Nanotubes.

During liver fibrosis, recurrent hepatic injuries lead to the accumulation of collagen and other extracellular matrix components in the interstitial space, ultimately disrupting liver functions. Early stages of liver fibrosis may be reversible, but opportunities for diagnosis at these stages are currently limited. Here, we show that the alterations of the interstitial space associated with fibrosis can be probed by tracking individual fluorescent single-walled carbon nanotubes (SWCNTs) diffusing in that space. In a mouse model of early liver fibrosis, we find that nanotubes generally explore elongated areas, whose lengths decrease as the disease progresses, even in regions where histopathological examination does not reveal fibrosis yet. Furthermore, this decrease in nanotube mobility is a purely geometrical effect as the instantaneous nanotube diffusivity stays unmodified. This work establishes the promise of SWCNTs both for diagnosing liver fibrosis at an early stage and for more in-depth studies of the biophysical effects of the disease.

Microstructural evolution effects on the density of carbon nanotube fibers

In this study, we investigate structural change in wet-spun carbon nanotube (CNT) fibers and explore the resulting changes in density and tensile strength. Given the presence of chlorosulfonic acid (CSA) inside the fiber and the evolution of tubular shape, the difference between the experimental density of CNT fibers and the theoretical density of individual CNTs can be reasonably approximated. During the heat treatment of pristine CNT fibers at 1400 °C, the capillary force induced by removal of CSA between or inside CNTs leads to the polygonization of the circumference of individual nanotubes. This morphological transformation results in the improved tensile strength and increased density by enlarging the contact area between CNTs and reducing the occupied volume. The demonstration of correlation between CNT structure and density can offer insights into the manufacturing and applications of high-performance CNT fibers.

Correlation Measurements for Carbon Nanotubes with Quantum Defects.

Single-photon sources are essential building blocks for the development of photonic quantum technology. Regarding potential practical application, an on-demand electrically driven quantum-light emitter on a chip is notably crucial for photonic integrated circuits. Here, we propose functionalized single-walled carbon nanotube field-effect transistors as a promising solid-state quantum-light source by demonstrating photon antibunching behavior via electrical excitation. The sp3 quantum defects were formed on the surface of (7, 5) carbon nanotubes by 3,5-dichlorophenyl functionalization, and individual carbon nanotubes were wired to graphene electrode pairs. Filtered electroluminescent defect-state emission at 77 K was coupled into a Hanbury Brown and Twiss experiment setup, and single-photon emission was observed by performing second-order correlation function measurements. We discuss the dependence of the intensity correlation measurement on electrical power and emission wavelength, highlighting the challenges of performing such measurements while simultaneously analyzing acquired data. Our results indicate a route toward room-temperature electrically triggered single-photon emission.

Locally controlled MOF growth on functionalized carbon nanotubes

Metal-organic frameworks (MOFs) are highly versatile materials because of their tunable properties. However, the typically poor electrical conductivity of MOFs presents challenges for their integration into electrical devices. By adding carbon nanotubes to MOF synthesis, a highly intergrown material with increased conductivity and chemiresistive sensing properties can be obtained. Here, we present a patterning technique to control MOF growth on predefined areas of one particular carbon nanotube. We found that electron beam pretreatment of -COOH functionalized multi-walled carbon nanotubes inhibits the growth of UiO-66 MOF on these multi-walled carbon nanotubes. By irradiating individual multi-walled carbon nanotubes, we show that MOF growth can be inhibited in predefined tube areas, creating MOF-free spaces on the nanotube. In this way, our method shows a possibility to pattern MOF growth on individual nanotubes.

Field emission characterization of field-aligned carbon nanotubes synthesized in an environmental transmission electron microscope

Optimizing the synthesis of carbon nanotubes (CNTs) for applications like field emission (FE) sources requires a fundamental understanding of the growth kinetics of individual CNTs. In this article, we explore how applying electric fields during CNT synthesis influences the as-grown nanotubes and their FE performance. We observe growth and undertake FE measurements in real time using an environmental transmission electron microscope. This is achieved through a polarizable capacitor gap within a microchip sample heater specifically designed for this purpose. Individual nanotubes are easily resolved and are predominantly single-wall CNTs. At low-applied fields, the growing nanotubes can span the gap and link with the opposite electrode, albeit with some loss due to mechanical failure. With a high-applied field and positive bias for FE, we continue to observe the oriented growth of nanotubes. However, this growth is constrained within the gap due to the possibility of FE occurring during the growth process, which can result in either saturation or damage. At any given time, we have the flexibility to halt the growth process and conduct in situ FE experiments. This approach enables us to comprehensively track the complete development of the CNTs and gain insights into the various mechanisms responsible for limiting the performance of CNT cathodes. Interestingly, we report an original self-oscillation induced destruction mechanism that has not been reported before.

Molecular-level network engineering of crosslinker towards high-performance carbon nanotube fiber

Intensive efforts are underway to integrate the distinct properties of individual carbon nanotubes (CNTs) into their assemblies and meet the growing demand for lightweight and strong materials. This study achieved CNT fibers (CNTFs) with high specific tensile strength (4.97 N/tex) and specific modulus (206.8 N/tex) by designing all-ring type bridges between CNTs. This reinforcement strategy involves suppressing the distortion of CNTs and promoting effective crosslinks within the fiber structure to increase the total inter-bundle interactions. The molecular-level network within the linking segment reduces vulnerability at the typically weak connection points and enhances load-transfer efficiency between crosslinked CNTs. In addition to improvements in mechanical properties, incorporating dopant groups in the bridge enhanced the electrical conductivity, reaching up to 2086 S m2/kg. This strategy provides straightforward access to multifunctional fibers beyond those of commercially accessible or literature-reported benchmark fibers.

Wavelength-tunable ultrafast two arm fiber laser system for transient interferometric scattering microscopy on nanoscopic objects

Ultrafast time-resolved microscopy of single nano-objects is particularly challenging because of minute sample volumes and correspondingly small signal levels together with the possibility of photobleaching. We present a compact pulsed two arm fiber laser-based system suited for highly sensitive transient interferometric scattering (TiSCAT) microscopy of nanomaterials. A continuously tunable probe arm is used for spectrally resolved detection of the transient sample response in the range between 810 and 960 nm upon pulsed excitation at 780 nm by the pump arm. Coupled to a scanning confocal microscope with high numerical aperture objective, the system provides spectral maps with sub-300 nm spatial and 300 fs temporal resolution. We tested the platform using monolayer MoSe2 and individual (6,4) single-walled carbon nanotubes as model samples. Confocal microscopy images recorded for an exfoliated monolayer MoSe2 reveal spatially varying excited state decay, highlighting the need for local probing. Spectrally resolved TiSCAT measurements on individual (6,4) single-walled carbon nanotubes show that the transient response is dominated by ground-state bleaching with picosecond recovery times. The obtained data illustrate the excellent noise properties and stability of the newly developed laser system, which allow for nearly shot-noise limited TiSCAT detection at the low probe fluences required for avoiding photodegradation of sensitive nanomaterials.

Optical coupling of individual air-suspended carbon nanotubes to silicon microcavities.

Carbon nanotubes are a telecom band emitter compatible with silicon photonics, and when coupled to microcavities, they present opportunities for exploiting quantum electrodynamical effects. Microdisk resonators demonstrate the feasibility of integration into the silicon platform. Efficient coupling is achieved using photonic crystal air-mode nanobeam cavities. The molecular screening effect on nanotube emission allows for spectral tuning of the coupling. The Purcell effect of the coupled cavity-exciton system reveals near-unity radiative quantum efficiencies of the excitons in carbon nanotubes.

Electrochemical treatment in KOH improves carbon nanomaterial performance to multiple neurochemicals.

Carbon-fiber microelectrodes (CFMEs) are primarily used to detect neurotransmitters in vivo with fast-scan cyclic voltammetry (FSCV) but other carbon nanomaterial electrodes are being developed. CFME sensitivity to dopamine is improved by applying a constant 1.5 V vs. Ag/AgCl for 3 minutes while dipped in 1 M KOH, which etches the surface and adds oxygen functional groups. However, KOH etching of other carbon nanomaterials and applications to other neurochemicals have not been investigated. Here, we explored KOH etching of CFMEs and carbon nanotube yarn microelectrodes (CNTYMEs) to characterize sensitivity to dopamine, epinephrine, norepinephrine, serotonin, and 3,4-dihydroxyphenylacetic acid (DOPAC). With CNTYMEs, the potential was applied in KOH for 1 minute because the electrode surface cracked with the longer time. KOH treatment increased electrode sensitivity to each cationic neurotransmitter roughly 2-fold for CFMEs, and 2- to 4-fold for CNTYMEs. KOH treatment decreased the background current of the CFMEs by etching the surface carbon; however, KOH-treatment increased the CNTYME background current because the potential separates individual nanotubes. For DOPAC, the current increase was smaller at CNTYMEs because it is anionic and was repelled by the negative holding potential and did not access the crevices. XPS and Raman spectroscopy showed that KOH treatment changed the CNTYME surface chemistry by increasing defect sites and adding oxide functional groups. KOH-treated CNTYMEs had less fouling to serotonin than normal CNTYMEs. Therefore, KOH treatment activates both CFMEs and CNTYMEs and could be used in biological measurements to increase the sensitivity and decrease fouling for neurochemical measurements.