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Transition metal dichalcogenide (TMDC) nanotubes exhibit unique physical properties due to their nanotube structures. The development of techniques for synthesizing TMDC nanotubes with controlled structures is very important for their science and applications. However, structural control efforts have been made only for the homostructures of TMDC nanotubes and not for their heterostructures that provide an important platform for their two-dimensional counterparts. In this study, we synthesized heterostructures of TMDC nanotubes, MoS2/WS2 heteronanotubes, and demonstrated a technique for controlling features of their structures, such as diameters, layer numbers, and crystallinity. The diameter of the heteronanotubes could be tuned with inner nanotube templates and was reduced by using small-diameter WS2 nanotubes. The layer number and crystallinity of the MoS2 outer wall could be controlled by controlling their precursors and synthesis temperatures, resulting in the formation of high-crystallinity TMDC heteronanotubes with specific chirality. This study can expand the research of van der Waals heterostructures.
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High-harmonic generation (HHG), which is the generation of light with multiple optical harmonics, is an unconventional nonlinear optical phenomenon beyond the perturbation regime. HHG, which was initially observed in gaseous media, has recently been demonstrated in solid-state materials. Determining how to control such extreme nonlinear optical phenomena is a challenging subject. Here, we demonstrate the control of HHG through tuning the electronic structure and carrier injection using single-walled carbon nanotubes (SWCNTs). We reveal systematic changes in the high-harmonic spectra of SWCNTs with a series of electronic structures ranging from a metal structure to a semiconductor structure. We demonstrate enhancement or reduction of harmonic generation by more than 1 order of magnitude by tuning the electron and hole injection into the semiconductor SWCNTs through electrolyte gating. These results open a path toward the control of HHG in the context of field-effect transistor devices.
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Photoluminescence (PL) from single-wall carbon nanotubes (SWCNTs) enables structural identification, but to derive the content rate of the specific chirality species it is necessary to know the quantum yield of each chirality. However, in the PL of SWCNTs, because the Stokes shift is small, the photon reabsorption effect is dominant and the apparent PL spectral shape and emission intensity are greatly modified depending on the concentration. This problem makes quantitative identification of SWCNTs by PL difficult. In this study, the concentration dependence of the PL of SWCNTs separated into a few chiralities was analyzed in detail, including the effect of reabsorption. It is clear that all changes in the PL spectrum occurring in the high concentration range can be explained simply by the reabsorption effect, and additional effects such as Coulomb interactions between SWCNTs can be negligible. Furthermore, a reliable quantum yield was derived from the emission intensity corrected for the reabsorption effect. The PL quantum yield varied with SWCNT chirality and exhibited a clear "family pattern". This is consistent with the theoretical report showing that the chirality-dependent PL quantum yield is dominated mainly by relaxation by optical phonons from E22 to E11.
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Ever since the discovery of carbon nanotubes (CNTs), it has long been a challenging goal to create macroscopically ordered assemblies, or crystals, of CNTs that preserve the one-dimensional quantum properties of individual CNTs on a macroscopic scale. Recently, a simple and well-controlled method was reported for producing wafer-scale crystalline films of highly aligned and densely packed CNTs through spontaneous global alignment that occurs during vacuum filtration (Nat. Nanotechnol. 2016, 11, 633). However, a full understanding of the mechanism of such global alignment has not been achieved. Here, we report results of a series of systematic experiments that demonstrate that the CNT alignment direction can be controlled by the surface morphology of the filter membrane used in the vacuum filtration process. More specifically, we found that the direction of parallel grooves pre-existing on the surface of the filter membrane dictates the direction of the resulting CNT alignment. Furthermore, we intentionally imprinted periodically spaced parallel grooves on a filter membrane using a diffraction grating, which successfully defined the direction of the global alignment of CNTs in a precise and reproducible manner. These results are promising not only for developing novel devices based on macroscopically aligned CNTs but also for understanding the microscopic physical mechanism of the alignment process.
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Semiconductors are generally considered far superior to metals as thermoelectric materials because of their much larger Seebeck coefficients (S). However, a maximum value of S in a semiconductor is normally accompanied by a minuscule electrical conductivity (σ), and hence, the thermoelectric power factor (P = S2σ) remains small. An attempt to increase σ by increasing the Fermi energy (EF), on the other hand, decreases S. This trade-off between S and σ is a well-known dilemma in developing high-performance thermoelectric devices based on semiconductors. Here, we show that the use of metallic carbon nanotubes (CNTs) with tunable EF solves this long-standing problem, demonstrating a higher thermoelectric performance than semiconducting CNTs. We studied the EF dependence of S, σ, and P in a series of CNT films with systematically varied metallic CNT contents. In purely metallic CNT films, both S and σ monotonically increased with EF, continuously boosting P while increasing EF. Particularly, in an aligned metallic CNT film, the maximum of P was â¼5 times larger than that in the highest-purity (>99%) single-chirality semiconducting CNT film. We attribute these superior thermoelectric properties of metallic CNTs to the simultaneously enhanced S and σ of one-dimensional conduction electrons near the first van Hove singularity.
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Measurements of optical properties at a nanometer level are of central importance for the characterization of optoelectronic devices. It is, however, difficult to use conventional light-probe measurements to determine the local optical properties from a single quantum object with nanometrical inhomogeneity. Here, we successfully measured the optical gap transitions of an individual semiconducting carbon nanotube with defects by using a monochromated electron source as a probe. The optical conductivity extracted from an electron energy-loss spectrum for a certain type of defect presents a characteristic modification near the lowest excitation peak ( E11), where excitons and nonradiative transitions, as well as phonon-coupled excitations, are strongly involved. Detailed line-shape analysis of the E11 peak clearly shows different degrees of exciton lifetime shortening and electronic state modification according to the defect type.
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Although enantiomeric separation of single-wall carbon nanotubes is possible, their enantiomeric purity (EP) remains an issue due to a lack of effective evaluation methods. In this work, we report the EP of (6,5) carbon nanotube enantiomers using flavin mononucleotide (FMN) as an enantiomer-sensitive dispersant. The enantiomers (6,5) and (11,-5) were separated by a gel column chromatography method and dispersed in a FMN aqueous solution. In these solutions, (6,5) and (11,-5) showed E11 optical transitions at different wavelengths due to handedness-dependent interactions with the FMN molecule, which enabled us to estimate each concentration, namely, the EP. We prepared six intermediate-purity enantiomer samples by mixing the (6,5) and (11,-5) enantiomers and measured their circular dichroism (CD) spectra. The CD signal was confirmed to change linearly with the EP. Using this relationship, we can estimate the EP of any mixture of (6,5) and (11,-5) from its CD intensity.
Asunto(s)
Mononucleótido de Flavina/química , Nanotubos de Carbono/química , Cromatografía Líquida de Alta Presión , Dicroismo Circular , Nanotecnología , EstereoisomerismoRESUMEN
Molybdenum disulfide (MoS(2)) thin-film transistors were fabricated with ion gel gate dielectrics. These thin-film transistors exhibited excellent band transport with a low threshold voltage (<1 V), high mobility (12.5 cm(2)/(V·s)) and a high on/off current ratio (10(5)). Furthermore, the MoS(2) transistors exhibited remarkably high mechanical flexibility, and no degradation in the electrical characteristics was observed when they were significantly bent to a curvature radius of 0.75 mm. The superior electrical performance and excellent pliability of MoS(2) films make them suitable for use in large-area flexible electronics.
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Monolayers of transition metal dichalcogenides (TMDs) are an ideal 2D platform for studying a wide variety of electronic properties and potential applications due to their chemical diversity. Similarly, single-walled TMD nanotubes (SW-TMDNTs)-seamless cylinders of rolled-up TMD monolayers-are 1D materials that can exhibit tunable electronic properties depending on both their chirality and composition. However, much less has been explored about their geometrical structures and chemical variations due to their instability under ambient conditions. Here, the structural diversity of SW-TMDNTs templated by boron nitride nanotubes (BNNTs) is reported. The outer surfaces and inner cavities of the BNNTs promote and stabilize the coaxial growth of SW-TMDNTs with various diameters, including few-nanometers-wide species. The chiral indices (n,m) of individual SW-MoS2 NTs are assigned by high-resolution transmission electron microscopy, and statistical analyses reveals a broad chirality distribution ranging from zigzag to armchair configurations. Furthermore, this methodology can be applied to the synthesis of various TMDNTs, such as selenides and alloyed Mo1- x Wx S2 . Comprehensive microscopic and spectroscopic analyses also suggest the partial formation of Janus MoS2(1- x ) Se2 x nanotubes. The BNNT-templated reaction provides a universal platform to characterize the chirality-dependent properties of 1D nanotubes with various electronic structures.
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The covalent functionalization of single-walled carbon nanotubes (SWCNTs) with luminescent quantum defects enables their application as near-infrared single-photon sources, as optical sensors, and for in vivo tissue imaging. Tuning the emission wavelength and defect density is crucial for these applications. While the former can be controlled by different synthetic protocols and is easily measured, defect densities are still determined as relative rather than absolute values, limiting the comparability between different nanotube batches and chiralities. Here, we present an absolute and unified quantification metric for the defect density in SWCNT samples based on Raman spectroscopy. It is applicable to a range of small-diameter semiconducting nanotubes and for arbitrary laser wavelengths. We observe a clear inverse correlation of the D/G+ ratio increase with nanotube diameter, indicating that curvature effects contribute significantly to the defect activation of Raman modes. Correlation of intermediate frequency modes with defect densities further corroborates their activation by defects and provides additional quantitative metrics for the characterization of functionalized SWCNTs.
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Carbon nanotubes (CNTs) possess extremely anisotropic electronic, thermal, and optical properties owing to their 1D character. While their linear optical properties have been extensively studied, nonlinear optical processes, such as harmonic generation for frequency conversion, remain largely unexplored in CNTs, particularly in macroscopic CNT assemblies. In this work, macroscopic films of aligned and type-separated (semiconducting and metallic) CNTs are synthesized and polarization-dependent third-harmonic generation (THG) from the films with fundamental wavelengths ranging from 1.5 to 2.5 µm is studied. Both films exhibited strongly wavelength-dependent, intense THG signals, enhanced through exciton resonances, and third-order nonlinear optical susceptibilities of 2.50 × 10-19 m2 V-2 (semiconducting CNTs) and 1.23 × 10-19 m2 V-2 (metallic CNTs), respectively are found, for 1.8 µm excitation. Further, through systematic polarization-dependent THG measurements, the values of all elements of the susceptibility tensor are determined, verifying the macroscopically 1D nature of the films. Finally, polarized THG imaging is performed to demonstrate the nonlinear anisotropy in the large-size CNT film with good alignment. These findings promise applications of aligned CNT films in mid-infrared frequency conversion, nonlinear optical switching, polarized pulsed lasers, polarized long-wave detection, and high-performance anisotropic nonlinear photonic devices.
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Tungsten disulfide (WS2) nanotubes exhibit various unique properties depending on their structures, such as their diameter and wall number. The development of techniques to prepare WS2 nanotubes with the desired structure is crucial for understanding their basic properties. Notably, the synthesis and characterization of multi-walled WS2 nanotubes with small diameters are challenging. This study reports the synthesis and characterization of small-diameter WS2 nanotubes with an average inner diameter of 6 nm. The optical absorption and photoluminescence (PL) spectra of the as-prepared nanotubes indicate that a decrease in the nanotube diameter induces a red-shift in the PL, suggesting that the band gap narrowed due to a curvature effect, as suggested by theoretical calculations.
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Creating artificial matter with controllable chirality in a simple and scalable manner brings new opportunities to diverse areas. Here we show two such methods based on controlled vacuum filtration - twist stacking and mechanical rotation - for fabricating wafer-scale chiral architectures of ordered carbon nanotubes (CNTs) with tunable and large circular dichroism (CD). By controlling the stacking angle and handedness in the twist-stacking approach, we maximize the CD response and achieve a high deep-ultraviolet ellipticity of 40 ± 1 mdeg nm-1. Our theoretical simulations using the transfer matrix method reproduce the experimentally observed CD spectra and further predict that an optimized film of twist-stacked CNTs can exhibit an ellipticity as high as 150 mdeg nm-1, corresponding to a g factor of 0.22. Furthermore, the mechanical rotation method not only accelerates the fabrication of twisted structures but also produces both chiralities simultaneously in a single sample, in a single run, and in a controllable manner. The created wafer-scale objects represent an alternative type of synthetic chiral matter consisting of ordered quantum wires whose macroscopic properties are governed by nanoscopic electronic signatures and can be used to explore chiral phenomena and develop chiral photonic and optoelectronic devices.
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The presence of hopping carriers and grain boundaries can sometimes lead to anomalous carrier types and density overestimation in Hall-effect measurements. Previous Hall-effect studies on carbon nanotube films reported unreasonably large carrier densities without independent assessments of the carrier types and densities. Here, we have systematically investigated the validity of Hall-effect results for a series of metallic, semiconducting, and metal-semiconductor-mixed single-wall carbon nanotube films. With carrier densities controlled through applied gate voltages, we were able to observe the Hall effect both in the n- and p-type regions, detecting opposite signs in the Hall coefficient. By comparing the obtained carrier types and densities against values derived from simultaneous field-effect-transistor measurements, we found that, while the Hall carrier types were always correct, the Hall carrier densities were overestimated by up to four orders of magnitude. This significant overestimation indicates that thin films of one-dimensional SWCNTs are quite different from conventional hopping transport systems.
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Rolling two-dimensional (2D) materials into 1D nanotubes allows for greater functionality. Boron-nitride nanotubes (BNNTs) can serve as insulating 1D templates for the coaxial growth of guest nanotubes, without interfering with property characterization. However, their application as 1D templates has been greatly hindered by their poor dispersibility, inevitably resulting in the formation of thick bundles. Here we present the facile preparation of well-dispersed BNNT templates via surfactant dispersions and synthesis of 1D van der Waals heterostructures based on the BNNTs. Comprehensive microscopic analyses show the isolation of clean, high-quality BNNTs. Statistical analyses revealed that small-diameter double-walled BNNTs are highly enriched by chemical peeling of BN sidewalls through the sonication process. We further demonstrate that the isolated BNNTs can template the coaxial growth of carbon and MoS2 nanotubes by using chemical vapor deposition. The present strategy can be applied to the synthesis of a variety of nanotubes, thereby allowing for their characterization.
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A comprehensive understanding of the roles of various nanointerfaces in thermal transport is of critical significance but remains challenging. A two-dimensional van der Waals (vdW) heterostructure with tunable interface lattice mismatch provides an ideal platform to explore the correlation between thermal properties and nanointerfaces and achieve controllable tuning of heat flow. Here, we demonstrate that interfacial engineering is an efficient strategy to tune thermal transport via systematic investigation of the thermal conductance (G) across a series of large-area four-layer stacked vdW materials using an improved polyethylene glycol-assisted time-domain thermoreflectance method. Owing to its rich interfacial mismatch and weak interfacial coupling, the vertically stacked MoSe2-MoS2-MoSe2-MoS2 heterostructure demonstrates the lowest G of 1.5 MW m-2 K-1 among all vdW structures. A roadmap to tune G via homointerfacial mismatch, interfacial coupling, and heterointerfacial mismatch is further demonstrated for thermal tuning. Our work reveals the roles of various interfacial effects on heat flow and highlights the importance of the interfacial mismatch and coupling effects in thermal transport. The design principle is also promising for application in other areas, such as the electrical tuning of energy storage and conversion and the thermoelectricity tuning of thermoelectronics.
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Low-dimensional materials have recently attracted much interest as thermoelectric materials because of their charge carrier confinement leading to thermoelectric performance enhancement. Carbon nanotubes are promising candidates because of their one-dimensionality in addition to their unique advantages such as flexibility and light weight. However, preserving the large power factor of individual carbon nanotubes in macroscopic assemblies has been challenging, primarily due to poor sample morphology and a lack of proper Fermi energy tuning. Here, we report an ultrahigh value of power factor (14 ± 5 mW m-1 K-2) for macroscopic weavable fibers of aligned carbon nanotubes with ultrahigh electrical and thermal conductivity. The observed giant power factor originates from the ultrahigh electrical conductivity achieved through excellent sample morphology, combined with an enhanced Seebeck coefficient through Fermi energy tuning. We fabricate a textile thermoelectric generator based on these carbon nanotube fibers, which demonstrates high thermoelectric performance, weavability, and scalability. The giant power factor we observe make these fibers strong candidates for the emerging field of thermoelectric active cooling, which requires a large thermoelectric power factor and a large thermal conductivity at the same time.
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Recent demonstration of room temperature, telecommunication wavelength single photon generation by sp3 defects of single wall carbon nanotubes established these defects as a new class of quantum materials. However, their practical utilization in development of quantum light sources calls for a significant improvement in their imperfect quantum yield (QYâ¼10-30%). PL intensity fluctuations observed with some defects also need to be eliminated. Aiming toward attaining fundamental understanding necessary for addressing these critical issues, we investigate PL intensity fluctuation and PL decay dynamics of aryl sp3 defects of (6,5), (7,5), and (10,3) single wall carbon nanotubes (SWCNTs) at temperatures ranging from 300 to 4 K. By correlating defect-state PL intensity fluctuations with change (or lack of change) in PL decay dynamics, we identified random variations in the trapping efficiency of E11 band-edge excitons (likely resulting from the existence of a fluctuating potential barrier in the vicinity of the defect) as the mechanism mainly responsible for the defect PL intensity fluctuations. Furthermore, by analyzing the temperature dependence of PL intensity and decay dynamics of individual defects based on a kinetic model involving the trapping and detrapping of excitons by optically allowed and forbidden (bright and dark) defect states, we estimate the height of the potential barrier to be in the 3-22 meV range. Our analysis also provides further confirmation of recent DFT simulation results that the emissive sp3 defect state is accompanied by an energetically higher-lying optically forbidden (dark) exciton state.
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Tungsten disulfide (WS2) nanotubes are cylindrical, multiwall nanotubes with various diameters and wall numbers. They can exhibit various unique properties depending on their structures and thus preparing samples with uniform structures is important for understanding their basic properties and applications. However, most synthesis methods have difficulty to prepare uniform samples, and thus, a purification method to extract nanotubes with a selected diameter and wall number must be developed. Here, we demonstrate a solution-based purification of WS2 nanotubes using a surfactant solution. Stable dispersions of nanotubes were prepared using nonionic surfactants, which enabled us to sort the diameters and wall numbers of the nanotubes through a centrifugation process. By optimizing the conditions, we successfully obtained thin nanotubes with a mean diameter of 32 nm and mean wall number of 13 with relatively small distributions. Finally, we clarified the relationships between the structure and optical properties of the nanotubes.
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Brown adipose tissue (BAT), which is composed of thermogenic brown adipocytes (BA) and non-parenchymal components including vasculatures and extracellular matrix, contribute to the maintenance of body temperature. BAT distribution is detected by positron emission tomography-computed tomography (PET/CT) using 18F-fluorodeoxy glucose (18F-FDG) or single-photon-emission computed tomography-computed tomography (SPECT/CT) using [123/125I]-beta-methyl-p-iodophenyl-pentadecanoic acid. Although sympathetic nerve activity and thermogenic capacity of BA is downregulated under fasting conditions in mice, fasting-dependent structural changes and fluid kinetics of BAT remain unknown. Here we show that the fasting induces fine and reversible structural changes in the non-parenchymal region in murine BAT with widened intercellular spaces and deformed collagen bands as revealed by electron microscopy. Interestingly, a newly introduced near infrared fluorescent probe of single-walled carbon nanotubes (CNTs) coated with phospholipid polyethylene glycol (PLPEG) easily demonstrated enhanced vascular permeability in BAT by the fasting. PLPEG-CNTs extravasated and remained in intercellular spaces or further redistributed in parenchymal cells in fasted mice, which is a previously unknown phenomenon. Thus, PLPEG-CNTs provide a powerful tool to trace fluid kinetics in sub-tissue levels.