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.

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 = S 2σ) remains small. An attempt to increase σ by increasing the Fermi energy (E F), 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 E F solves this long-standing problem, demonstrating a higher thermoelectric performance than semiconducting CNTs. We studied the E F 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 E F, continuously boosting P while increasing E F. Particularly, in an aligned metallic CNT film, the maximum of P was ∼5 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.

Confined electrons collectively oscillate in response to light, resulting in a plasmon resonance whose frequency is determined by the electron density and the size and shape of the confinement structure. Plasmons in metallic particles typically occur in the classical regime where the characteristic quantum level spacing is negligibly small compared to the plasma frequency. In doped semiconductor quantum wells, quantum plasmon excitations can be observed, where the quantization energy exceeds the plasma frequency. Such intersubband plasmons occur in the mid- and far-infrared ranges and exhibit a variety of dynamic many-body effects. Here, we report the observation of intersubband plasmons in carbon nanotubes, where both the quantization and plasma frequencies are larger than those of typical quantum wells by three orders of magnitude. As a result, we observed a pronounced absorption peak in the near-infrared. Specifically, we observed the near-infrared plasmon peak in gated films of aligned single-wall carbon nanotubes only for probe light polarized perpendicular to the nanotube axis and only when carriers are present either in the conduction or valence band. Both the intensity and frequency of the peak were found to increase with the carrier density, consistent with the plasmonic nature of the resonance. Our observation of gate-controlled quantum plasmons in aligned carbon nanotubes will not only pave the way for the development of carbon-based near-infrared optoelectronic devices but also allow us to study the collective dynamic response of interacting electrons in one dimension.

How the morphology of a macroscopic assembly of nanoobjects affects its properties is a longstanding question in nanomaterials science and engineering. Here, we examine how the thermoelectric properties of a flexible thin film of carbon nanotubes depend on macroscopic nanotube alignment. Specifically, we have investigated the anisotropy of the Seebeck coefficient of aligned and gated single-wall carbon nanotube thin films. We varied the Fermi level in a wide range, covering both the p-type and n-type regimes, using electrolyte gating. While we found the electrical conductivity along the nanotube alignment direction to be several times larger than that in the perpendicular direction, the Seebeck coefficient was found to be fully isotropic, irrespective of the Fermi level position. We provide an explanation for this striking difference in anisotropy between the conductivity and the Seebeck coefficient using Mott's theory of hopping conduction. Our experimental evidence for an isotropic Seebeck coefficient in an anisotropic nanotube assembly suggests a route toward controlling the thermoelectric performance of carbon nanotube thin films through morphology control.

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.

Optical properties of single-wall carbon nanotubes (SWCNTs) for light polarized parallel to the nanotube axis have been extensively studied, whereas their response to light polarized perpendicular to the nanotube axis has not been well explored. Here, by using a macroscopic film of highly aligned single-chirality (6,5) SWCNTs, we performed a systematic polarization-dependent optical absorption spectroscopy study. In addition to the commonly observed angular-momentum-conserving interband absorption of parallel-polarized light, which generates E11 and E22 excitons, we observed a small but unambiguous absorption peak whose intensity is maximum for perpendicular-polarized light. We attribute this feature to the lowest-energy cross-polarized interband absorption processes that change the angular momentum along the nanotube axis by ±1, generating E12 and E21 excitons. The energy difference between the E12 and E21 exciton peaks, expected from asymmetry between the conduction and valence bands, was smaller than the observed linewidth. Unlike previous observations of cross-polarized excitons in polarization-dependent photoluminescence and circular dichroism spectroscopy experiments, our direct observation using absorption spectroscopy allowed us to quantitatively analyze this resonance. Specifically, we determined the energy and oscillator strength of this resonance to be 1.54 and 0.05, respectively, compared with the values for the E11 exciton peak. These values, in combination with comparison with theoretical calculations, in turn led to an assessment of the environmental effect on the strength of Coulomb interactions in this aligned single-chirality SWCNT film.PACS numbers:

The preparation of single-chirality single-walled carbon nanotubes (SWCNTs) is of great importance to comprehensively understand their physical properties and applications. The high-purity separation of single-chirality SWCNTs has been reported using gel chromatography with a mixed surfactant system, but further improvements are necessary to enhance the purity of the resulting single-chirality SWCNTs. In this study, we focused on using pH as a parameter to improve the separation purity and investigated its influence on mixed surfactant-based purification. The pH of the mixed surfactant solution was precisely controlled with carbon dioxide bubbling with an accuracy of approximately 0.1. Using this eluent with a series of different pH values, we achieved diameter-selective separation of the SWCNTs. Moreover, we found that the residual metallic SWCNTs could be completely removed under the proper pH condition. Finally, on the basis of these findings, we produced single-chirality SWCNTs with a purity of more than 99% without residual metallic SWCNTs.

Tungsten disulfide (WS 2 ) 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 WS 2 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.