Evaluating the Efficiency of Boron Nitride Coating in Single-Walled Carbon-Nanotube-Based 1D Heterostructure Films by Optical Spectroscopy.

Single-walled carbon nanotube (SWCNT) films exhibit exceptional optical and electrical properties, making them highly promising for scalable integrated devices. Previously, we employed SWCNT films as templates for the chemical vapor deposition (CVD) synthesis of one-dimensional heterostructure films where boron nitride nanotubes (BNNTs) and molybdenum disulfide nanotubes (MoS2NTs) were coaxially nested over the SWCNT networks. In this work, we have further refined the synthesis method to achieve precise control over the BNNT coating in SWCNT@BNNT heterostructure films. The resulting structure of the SWCNT@BNNT films was thoroughly characterized using a combination of electron microscopy, UV-vis-NIR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and Raman spectroscopy. Specifically, we investigated the pressure effect induced by BNNT wrapping on the SWCNTs in the SWCNT@BNNT heterostructure film and demonstrated that the shifts of the SWCNT's G and 2D (G') modes in Raman spectra can be used as a probe of the efficiency of BNNT coating. In addition, we studied the impact of vacuum annealing on the removal of the initial doping in SWCNTs, arising from exposure to ambient atmosphere, and examined the effect of MoO3 doping in SWCNT films by using UV-vis-NIR spectroscopy and Raman spectroscopy. We show that through correlation analysis of the G and 2D (G') modes in Raman spectra, it is possible to discern distinct types of doping effects as well as the influence of applied pressure on the SWCNTs within SWCNT@BNNT heterostructure films. This work contributes to a deeper understanding of the strain and doping effect in both SWCNTs and SWCNT@BNNTs, thereby providing valuable insights for future applications of carbon-nanotube-based one-dimensional heterostructures.

Horizontal Arrays of One-Dimensional van der Waals Heterostructures as Transistor Channels.

The nanotube/dielectric interface plays an essential role in achieving superb switching characteristics of carbon nanotube-based transistors for energy-efficient computation. Formation of van der Waals heterostructures with hexagonal boron nitride nanotubes could be an effective means to reduce interface state density, but the need for isolating nanotubes during the formation of coaxial outer layers has hindered the fabrication of their horizontal arrays. Here, we develop a strategy to create isolated heterostructure arrays using aligned carbon nanotubes grown on a quartz substrate as starting materials. Air-suspended arrays of carbon nanotubes are prepared by a dry transfer technique and then used as templates for the coaxial wrapping of boron nitride nanotubes. We then fabricate the transistors, where boron nitride serves as interfacial layers between carbon nanotube channels and conventional gate dielectrics, showing hysteresis-free characteristics owing to the improved interfaces. We have also gained a deeper understanding of the strain applied on inner carbon nanotubes, as well as the inhomogeneity of the outer coating, by characterizing individual heterostructures over trenches and on a substrate surface. The device fabrication and characterization presented here essentially do not require elaborate electron microscopy, thus paving the way for the practical use of one-dimensional van der Waals heterostructures for nanoelectronics.

Universal Map of Gas-Dependent Kinetic Selectivity in Carbon Nanotube Growth.

Single-walled carbon nanotubes have been a candidate for outperforming silicon in ultrascaled transistors, but the realization of nanotube-based integrated circuits requires dense arrays of purely semiconducting species. In order to directly grow such nanotube arrays on wafers, control over kinetics and thermodynamics in tube-catalyst systems plays a key role, and further progress requires a comprehensive understanding of seemingly contradictory reports on the growth kinetics. Here, we propose a universal kinetic model that decomposes the growth rates of nanotubes into the adsorption and removal of carbon atoms on the catalysts, and we provide its quantitative verification by ethanol-based isotope labeling experiments. While the removal of carbon from catalysts dominates the growth kinetics under a low supply of precursors, resulting in chirality-independent growth rates, our kinetic model and experiments demonstrate that chiral angle-dependent growth rates emerge when sufficient amounts of carbon and etching agents are cosupplied. The kinetic maps, as a product of generalizing the model, include five types of kinetic selectivity that emerge depending on the absolute quantities of gases with opposing effects. Our findings not only resolve discrepancies existing in the literature but also offer rational strategies to control the chirality, length, and density of nanotube arrays for practical applications.

One-dimensional van der Waals heterostructures: Growth mechanism and handedness correlation revealed by nondestructive TEM.

We recently synthesized one-dimensional (1D) van der Waals heterostructures in which different atomic layers (e.g., boron nitride or molybdenum disulfide) seamlessly wrap around a single-walled carbon nanotube (SWCNT) and form a coaxial, crystalized heteronanotube. The growth process of 1D heterostructure is unconventional-different crystals need to nucleate on a highly curved surface and extend nanotubes shell by shell-so understanding the formation mechanism is of fundamental research interest. In this work, we perform a follow-up and comprehensive study on the structural details and formation mechanism of chemical vapor deposition (CVD)-synthesized 1D heterostructures. Edge structures, nucleation sites, and crystal epitaxial relationships are clearly revealed using transmission electron microscopy (TEM). This is achieved by the direct synthesis of heteronanotubes on a CVD-compatible Si/SiO2 TEM grid, which enabled a transfer-free and nondestructive access to many intrinsic structural details. In particular, we have distinguished different-shaped boron nitride nanotube (BNNT) edges, which are confirmed by electron diffraction at the same location to be strictly associated with its own chiral angle and polarity. We also demonstrate the importance of surface cleanness and isolation for the formation of perfect 1D heterostructures. Furthermore, we elucidate the handedness correlation between the SWCNT template and BNNT crystals. This work not only provides an in-depth understanding of this 1D heterostructure material group but also, in a more general perspective, serves as an interesting investigation on crystal growth on highly curved (radius of a couple of nanometers) atomic substrates.

Photoluminescence from Single-Walled MoS2 Nanotubes Coaxially Grown on Boron Nitride Nanotubes.

Single-walled and multiwalled molybdenum disulfide (MoS2) nanotubes have been coaxially synthesized on small-diameter boron nitride nanotubes (BNNTs) that are obtained from removing single-walled carbon nanotubes (SWCNTs) in heteronanotubes of SWCNTs coated by BNNTs. The photoluminescence (PL) from single-walled MoS2 nanotubes supported by core BNNTs is observed in this work, which evidences the direct bandgap structure of single-walled MoS2 nanotubes with a diameter around 6-7 nm. The observation is consistent with our DFT results that the single-walled MoS2 nanotube changes from an indirect-gap to a direct-gap semiconductor when the diameter of a nanotube is more than around 5.2 nm. On the other hand, when there are SWCNTs inside the heteronanotubes of BNNTs and single-walled MoS2 nanotubes, the PL signal from MoS2 nanotubes is considerably quenched. The charge transfer and energy transfer between SWCNTs and single-walled MoS2 nanotubes were examined through characterizations by PL, X-ray photoelectron spectroscopy, and Raman spectroscopy. Moreover, the PL signal from multiwalled MoS2 nanotubes is significantly quenched. Single-walled and multiwalled MoS2 nanotubes exhibit different Raman features in both resonant and nonresonant Raman spectra.

One-Dimensional van der Waals Heterojunction Diode.

The synthesis of one-dimensional van der Waals heterostructures was realized recently, which offers alternative possibilities for prospective applications in electronics and optoelectronics. The even reduced dimension will enable different properties and further miniaturization beyond the capabilities of their two-dimensional counterparts. The natural doping results in p-type electrical characteristics for semiconducting single-walled carbon nanotubes and n-type for molybdenum disulfide with conventional noble metal contacts. Therefore, we demonstrate here a one-dimensional heterostructure nanotube, 11 nm wide, with the coaxial assembly of a semiconducting single-walled carbon nanotube, insulating boron nitride nanotube, and semiconducting molybdenum disulfide nanotube, which induces a radial semiconductor-insulator-semiconductor heterojunction. When opposite potential polarity was applied on a semiconducting single-walled carbon nanotube and molybdenum disulfide nanotube, respectively, the rectifying effect was materialized.

Phenomenological model of thermal transport in carbon nanotube and hetero-nanotube films.

The thermal properties of individual single-walled carbon nanotubes (SWCNTs) have been well documented in the literature following decades of intensive study. However, when SWCNTs form a macroscale assembly, the thermal transport in these complex structures usually not only depends on the properties of the individual tubes, but also is affected and sometimes dominated by inner structural details, e.g. bundles and junctions. In this work, we first performed an experimental measurement of the thermal conductivities of individual SWCNT bundles of different sizes using a suspended micro-thermometer. The results, together with the data that we obtained from a previous work, give a complete experimental understanding of the effect of bundling on the thermal conductivity of SWCNTs. With these quantitative understandings, we propose a phenomenological model to describe the thermal transport in two-dimensional (2D) SWCNT films. The term 'line density' is defined to describe the effective thermal transport channels in this complex 2D network. Along with experimentally obtained geometric statistics and film transparency, the thermal conductance of SWCNTs is estimated, and the effects of bundle length, diameter, and contact conductance are systematically discussed. Finally, we extend this model to explain thermal transport in 2D networks of one-dimensional van der Waals heterostructures, which are coaxial hetero-nanotubes we recently synthesized using SWCNTs as the template. This extended model suggests that the contribution of boron nitride nanotubes (BNNTs) to the overall performance of a SWCNT-BNNT heterostructured film depends on the transparency of the original SWCNT film. The increase in the thermal conductance of a highly transparent film is estimated to be larger than that of a less transparent film, which shows a good agreement with our experimental observations and proves the validity of the proposed phenomenological model.

Heat diffusion-related damping process in a highly precise coarse-grained model for nonlinear motion of SWCNT.

Second sound and heat diffusion in single-walled carbon nanotubes (SWCNT) are well-known phenomena which is related to the high thermal conductivity of this material. In this paper, we have shown that the heat diffusion along the tube axis affects the macroscopic motion of SWCNT and adapting this phenomena to coarse-grained (CG) model can improve the precision of the coarse-grained molecular dynamics (CGMD) exceptionally. The nonlinear macroscopic motion of SWCNT in the free thermal vibration condition in adiabatic environment is demonstrated in the most simplified version of CG modeling as maintaining finite temperature and total energy with suggested dissipation process derived from internal heat diffusion. The internal heat diffusion related to the cross correlated momentum from different potential energy functions is considered, and it can reproduce the nonlinear dynamic nature of SWCNTs without external thermostatting in CG model. Memory effect and thermostat with random noise distribution are not included, and the effect of heat diffusion on memory effect is quantified through Mori-Zwanzig formalism. This diffusion shows perfect syncronization of the motion between that of CGMD and MD simulation, which is started with initial conditions from the molecular dynamics (MD) simulation. The heat diffusion related to this process has shown the same dispersive characteristics to second wave in SWCNT. This replication with good precision indicates that the internal heat diffusion process is the essential cause of the nonlinearity of the tube. The nonlinear dynamic characteristics from the various scale of simple beads systems are examined with expanding its time step and node length.

Ultrafast saturable absorption of large-diameter single-walled carbon nanotubes for passive mode locking in the mid-infrared.

We study the saturable absorption properties of single-walled carbon nanotubes (SWCNTs) with a large diameter of 2.2 nm and the corresponding exciton resonance at a wavelength of 2.4 µm. At resonant excitation, a large modulation depth of approximately 30 % and a small saturation fluence of a few tens of µJ/cm2 are evaluated. The temporal response is characterized by an instantaneous rise and a subpicosecond recovery. We also utilize the SWCNTs to realize sub-50 fs, self-start mode locking in a Cr:ZnS laser, revealing that the film thickness is an important parameter that affects the possible pulse energy and duration. The results prove that semiconductor SWCNTs with tailored diameters exceeding 2 nm are useful for passive mode locking in the mid-infrared range.

Non-catalytic heteroepitaxial growth of aligned, large-sized hexagonal boron nitride single-crystals on graphite.

Although van der Waals heterostructures composed of graphene and hexagonal boron nitride (h-BN) have attracted wide interest, it is still challenging to prepare them with high quality and controllability. Since contamination induced by transfer cannot be avoided in the case of growth on a metal catalyst, the non-catalytic growth of graphene and h-BN is highly desired. However, unlike graphene, few studies have reported the non-catalytic growth of h-BN, and the lack of controllability in terms of crystal orientation and nucleation density, and size of h-BN has hindered the practical applications of the heterostructures. In this work, we demonstrate the heteroepitaxial growth of aligned monolayer h-BN single-crystals on exfoliated graphite by chemical vapour deposition (CVD) without a metal catalyst. Triangular shaped domains were aligned with each other, which suggests the epitaxy between h-BN and the underlying graphite. Characterisation by Raman spectroscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy also confirmed that the h-BN/graphite samples were of high quality. A growth kinetics study over different temperatures indicated an increase in the growth rate at high temperature. Control of nucleation density was realised by changing the hydrogen pressure during CVD or by the heating temperature in air before CVD. Under the optimised growth conditions, the edge length of h-BN single-crystals grew to ∼1 µm, which is the largest size to date for non-catalytic growth. These results will help to obtain structure-controlled, large-area, and impurity-free heterostructures based on h-BN and graphene.

Enhanced In-Plane Thermal Conductance of Thin Films Composed of Coaxially Combined Single-Walled Carbon Nanotubes and Boron Nitride Nanotubes.

Carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs) are one-dimensional materials with high thermal conductivity and similar crystal structures. Additionally, BNNTs feature higher thermal stability in air than CNTs. In this work, a single-walled carbon nanotube (SWCNT) film was used as a template to synthesize a BNNT coating by the chemical vapor deposition (CVD) method to form a coaxial heterostructure. Then, a contact-free steady-state infrared (IR) method was adopted to measure the in-plane sheet thermal conductance of the as-synthesized film. The heterostructured SWCNT-BNNT film demonstrates an enhanced sheet thermal conductance compared with the bare SWCNT film. The increase in sheet thermal conductance shows a reverse relationship with SWCNT film transparency. An enhancement of over 80% (from ∼3.6 to ∼6.4 µW·K-1·sq-1) is attained when the BNNT coating is applied to an SWCNT film with a transparency of 87%. This increase is achieved by BNNTs serving as an additional thermal conducting path. The relationship between the thermal conductance increase and transparency of the SWCNT film is studied by a structured modeling of the SWCNT film. We also discuss the effect of annealing on the thermal conductance of SWCNTs before BNNT growth. Along with the preservation of high electrical conductance, the enhanced thermal conductance of the heterostructured SWCNT-BNNT films makes them a promising building block for thermal and optoelectronic applications.

Ultrafast Optoelectronic Processes in 1D Radial van der Waals Heterostructures: Carbon, Boron Nitride, and MoS2 Nanotubes with Coexisting Excitons and Highly Mobile Charges.

Heterostructures built from 2D, atomically thin crystals are bound by the van der Waals force and exhibit unique optoelectronic properties. Here, we report the structure, composition and optoelectronic properties of 1D van der Waals heterostructures comprising carbon nanotubes wrapped by atomically thin nanotubes of boron nitride and molybdenum disulfide (MoS2). The high quality of the composite was directly made evident on the atomic scale by transmission electron microscopy, and on the macroscopic scale by a study of the heterostructure's equilibrium and ultrafast optoelectronics. Ultrafast pump-probe spectroscopy across the visible and terahertz frequency ranges identified that, in the MoS2 nanotubes, excitons coexisted with a prominent population of free charges. The electron mobility was comparable to that found in high-quality atomically thin crystals. The high mobility of the MoS2 nanotubes highlights the potential of 1D van der Waals heterostructures for nanoscale optoelectronic devices.

One-dimensional van der Waals heterostructures.

We present the experimental synthesis of one-dimensional (1D) van der Waals heterostructures, a class of materials where different atomic layers are coaxially stacked. We demonstrate the growth of single-crystal layers of hexagonal boron nitride (BN) and molybdenum disulfide (MoS2) crystals on single-walled carbon nanotubes (SWCNTs). For the latter, larger-diameter nanotubes that overcome strain effect were more readily synthesized. We also report a 5-nanometer-diameter heterostructure consisting of an inner SWCNT, a middle three-layer BN nanotube, and an outer MoS2 nanotube. Electron diffraction verifies that all shells in the heterostructures are single crystals. This work suggests that all of the materials in the current 2D library could be rolled into their 1D counterparts and a plethora of function-designable 1D heterostructures could be realized.

Atomic-scale structural identification and evolution of Co-W-C ternary SWCNT catalytic nanoparticles: High-resolution STEM imaging on SiO2.

Recently, W-based catalysts have provided a promising route to synthesize single-walled carbon nanotubes (SWCNTs) with specific chirality, but the mechanism of the growth selectivity is vaguely understood. We propose a strategy to identify the atomic structure as well as the structure evolution of the Co-W-C ternary SWCNT catalyst. The key is to use a thin SiO2 film as the catalyst support and observation window. As the catalyst is uniformly prepared on this SiO2 film and directly used for the SWCNT synthesis, this method has an advantage over conventional methods: it creates an opportunity to obtain original, statistical, and dynamic understanding of the catalyst. As a technique, atomic-scale imaging directly on SiO2 serves as a powerful and versatile tool to investigate nanocrystals and high-temperature reactions; for the synthesis of SWCNTs, this work successfully visualizes the structure and evolution of the catalyst and illuminates the possible nucleation sites of the chirality-specific growth.

Molecular Dynamics of Chirality Definable Growth of Single-Walled Carbon Nanotubes.

In order to achieve the chirality-specific growth of single-walled carbon nanotubes (SWCNTs), it is crucial to understand the growth mechanism. Even though many molecular dynamics (MD) simulations have been employed to analyze the SWCNT growth mechanism, it has been difficult to discuss the chirality determining kinetics because of the defects remaining on the SWCNTs grown in simulations. In this study, we demonstrate MD simulations of defect-free SWCNTs, that is, chirality definable SWCNTs, under the optimized carbon supply rate and temperature. The chiralities of the SWCNTs were assigned as (14,1), (15,2), and (9,0), indicating the preference of near-zigzag and pure-zigzag SWCNTs. The SWCNTs contained at least one complete row of defect-free walls consisting of only hexagons. The near-zigzag SWCNTs grew via a kink-running process, in which bond formation between a carbon atom at a kink and a neighboring carbon chain led to formation of a hexagon with a new kink at the SWCNT edge. Defects including pentagons and heptagons were sometimes formed but effectively healed into hexagons on metal surfaces. The pure-zigzag SWCNTs grew by the kink-running and the hexagon nucleation processes. In addition, chirality change events along SWCNTs with incorporation of pentagon-heptagon pair defects were observed in the MD simulations. Here, pentagons and heptagons were frequently observed as adjacent pairs, resulting in ( n, m) chirality changes by (±1,0), (0,±1), (1,-1), or (-1,1).

Self-starting mode-locked Cr:ZnS laser using single-walled carbon nanotubes with resonant absorption at 2.4 µm.

We develop a mode-locked Cr:ZnS polycrystalline laser using single-walled carbon nanotubes (SWCNTs) that have resonant absorption at the wavelength of 2.4 µm. The laser generates ultrashort pulses of 49 fs duration, a 2.4 µm center wavelength, and a 9.2 THz (176 nm) spectral span at a repetition rate of 76 MHz. We also confirm self-starting of the mode-locked operation. SWCNTs, if appropriately controlled in terms of their diameters, prove to be useful as ultrafast saturable absorbers in the mid-infrared region.

Confinement Effect of Sub-nanometer Difference on Melting Point of Ice-Nanotubes Measured by Photoluminescence Spectroscopy.

Melting point is independent of size and shape in bulk materials, but it exhibits a size dependence when the material size is extremely small. In this study, we measured the melting point of water confined in single-walled carbon nanotubes (SWCNTs) with 16 different chiralities, which ranged from 0.95 to 1.26 nm in diameter, and revealed the details of the SWCNT diameter dependence on the melting points. The melting points were probed by utilizing the change of photoluminescence (PL) emission wavelength of SWCNTs, which encapsulated water, and the relation between the emission wavelength, and the water phase was confirmed by first-principles calculations. The periodicity of the melting point variation with SWCNT diameter came from the discrete change of ice-nanotube (ice-NT) diameter, and in addition, even ice-NT with an identical diameter exhibited different melting points due to the slight difference of the inner space size of the encapsulating SWCNTs. The present results agreed with those of the molecular dynamics simulation (Takaiwa, D.; et al., Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 39-43). It was elucidated that the melting point of the nanomaterial changed sensitively to the atomic structure and the confinement space size.

Digital Isotope Coding to Trace the Growth Process of Individual Single-Walled Carbon Nanotubes.

Single-walled carbon nanotubes (SWCNTs) are attracting increasing attention as an ideal material for high-performance electronics through the preparation of arrays of purely semiconducting SWCNTs. Despite significant progress in the controlled synthesis of SWCNTs, their growth mechanism remains unclear due to difficulties in analyzing the time-resolved growth of individual SWCNTs under practical growth conditions. Here we present a method for tracing the diverse growth profiles of individual SWCNTs by embedding digitally coded isotope labels. Raman mapping showed that, after various incubation times, SWCNTs elongated monotonically until their abrupt termination. Ex situ analysis offered an opportunity to capture rare chirality changes along the SWCNTs, which resulted in sudden acceleration/deceleration of the growth rate. Dependence on growth parameters, such as temperature and carbon concentration, was also traced along individual SWCNTs, which could provide clues to chirality control. Systematic growth studies with a variety of catalysts and conditions, which combine the presented method with other characterization techniques, will lead to further understanding and control of chirality, length, and density of SWCNTs.

Fabrication, characterization, and high temperature surface enhanced Raman spectroscopic performance of SiO2 coated silver particles.

We present a systematic study on the fabrication, characterization and high temperature surface enhanced Raman spectroscopy (SERS) performance of SiO2 coated silver nanoparticles (Ag@SiO2) on a flat substrate, aiming to obtain a thermally robust SERS substrate for monitoring high temperature reactions. We confirm that a 10-15 nm SiO2 coating provides a structure stability up to 900 °C without significantly sacrificing the enhancement factor, while the uncoated particle cannot retain the SERS effect above 500 °C. The finite difference time domain (FDTD) simulation results supported that the SiO2 coating almost has no influence on the distribution of the electric field but only physically trapped the most enhanced spot inside the coating layer. On this thermally robust substrate, we confirmed that the SERS of horizontally aligned single walled carbon nanotubes is stable at elevated temperatures, and demonstrate an in situ Raman monitoring of the atmosphere of the annealing process of nanodiamonds, in which the interconverting process of C-C bonds is unambiguously observed. We claim that this is a first experimental proof that the high temperature SERS effect can be preserved and applied in a chemical reaction at temperature above 500 °C. This versatile substrate also enables novel opportunities for observing growth, etching, and structure transformation of many 0D and 2D nano-materials.

Temperature Distribution and Thermal Conductivity Measurements of Chirality-Assigned Single-Walled Carbon Nanotubes by Photoluminescence Imaging Spectroscopy.

It is expected that single-walled carbon nanotubes (SWCNTs) have high thermal conductivity along the tube axis and that the thermal conductivities depend on their structure, such as length, diameter, chirality (n, m), and so forth. Although many experimental measurements of the thermal conductivity have been reported, the SWCNT structure was not characterized sufficiently. In particular, the chirality was not assigned, and it was not confirmed whether SWCNT was isolated or not (bundled with multiplicate SWCNTs). Therefore, measured values widely vary (101 to 104 W/(m·K)) so far. Here, we measured the thermal conductivity of chirality-assigned SWCNTs, which were individually suspended, by using photoluminescence (PL) imaging spectroscopy. The temperature distribution along the tube axis was obtained, and the temperature dependence of the thermal conductivity was measured in a wide-temperature range (from 350 to 1000 K). For (9, 8) SWCNTs with 10-12 µm in length, the thermal conductivity was 1166 ± 243 W/(m·K) at 400 K. The proposed PL imaging spectroscopy enables to measure the thermal conductivity of SWCNTs with high precision and without any contacts, and it is an effective method in the temperature distribution measurements of nanomaterials.