Catalyst-free synthesis of sub-5 nm silicon nanowire arrays with massive lattice contraction and wide bandgap.

The need for miniaturized and high-performance devices has attracted enormous attention to the development of quantum silicon nanowires. However, the preparation of abundant quantities of silicon nanowires with the effective quantum-confined dimension remains challenging. Here, we prepare highly dense and vertically aligned sub-5 nm silicon nanowires with length/diameter aspect ratios greater than 10,000 by developing a catalyst-free chemical vapor etching process. We observe an unusual lattice reduction of up to 20% within ultra-narrow silicon nanowires and good oxidation stability in air compared to conventional silicon. Moreover, the material exhibits a direct optical bandgap of 4.16 eV and quasi-particle bandgap of 4.75 eV with the large exciton binding energy of 0.59 eV, indicating the significant phonon and electronic confinement. The results may provide an opportunity to investigate the chemistry and physics of highly confined silicon quantum nanostructures and may explore their potential uses in nanoelectronics, optoelectronics, and energy systems.

Chirality Distributions for Semiconducting Single-Walled Carbon Nanotubes Determined by Photoluminescence Spectroscopy.

To realize single-walled carbon nanotube (SWCNT) chiral selective growth, elucidating the mechanism of SWCNT chirality (n,m) selectivity is important. For this purpose, an accurate evaluation method for evaluating the chirality distribution of grown SWCNTs without post-growth processing or liquid-dispersion of SWCNTs is indispensable. Here, we used photoluminescence spectroscopy to directly measure the chirality distributions of individual semiconducting SWCNTs suspended on a pillar-patterned substrate. The number of chirality-assigned SWCNTs was up to 332 and 17 chirality types with the chiral angles ranging from 0° to 28.05° were detected. The growth yield of SWCNTs was confirmed to primarily depends on the chiral angle in accordance with the screw dislocation model. Furthermore, when higher-yield chiralities are selected, the chiral angle distribution with a peak corresponding to near-armchair SWCNTs is well fitted with a model that incorporates the thermodynamic effect at the SWCNT-catalyst interface into the kink growth-based kinetic model. Our quantitative and statistical data provide new insights into SWCNT growth mechanism as well as experimental confirmation of theoretical predictions.

Quantitative Detection of the Disappearance of the Antioxidant Ability of Catechin by Near-Infrared Absorption and Near-Infrared Photoluminescence Spectra of Single-Walled Carbon Nanotubes.

We succeeded in quantitatively detecting the disappearance of catechin antioxidant ability as a function of time using near-infrared (NIR) absorbance and NIR photoluminescence (PL) spectra of single-walled carbon nanotubes (SWNTs) wrapped with DNA molecules (DNA-SWNT hybrids). When 15 µg/mL of catechin was added to the oxidized hybrid suspension, the absorbance of SWNTs increased, according to the antioxidant ability of catechin, and the effect was maintained at least for 30 min. When catechin concentrations were less than 0.3 µg/mL, SWNT absorbance gradually decreased, although it increased when catechin is added. The results revealed that disappearance of the catechin effects could be quantitatively detected by NIR absorbance spectra. When NIR PL was employed, the disappearance of PL intensity was also observed in the case of low catechin concentrations. However, time-lapse measurement of the disappearance was difficult because the PL intensity was rapidly quenched. In addition, the optical responses were different due to different chirality of SWNTs. Our results suggested that both NIR absorbance and PL can detect disappearance of catechin antioxidant effects; in particular, slow response of NIR absorbance was effective to detect time dependence of the disappearance of the catechin effects. Contrarily, PL revealed huge and rapid responses in contrast to NIR absorbance. PL might be effective for reversible use of DNA-SWNT hybrids as a nanobiosensor.

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.

Terahertz Spectroscopy of Individual Carbon Nanotube Quantum Dots.

We have investigated the electronic structures of metallic carbon nanotube quantum dots (CNT QDs) by terahertz-induced photocurrent spectroscopy. Sharp peaks due to intersublevel transitions in the CNT QDs are observed at the sublevel energy spacings expected from the linear band dispersion. The line width of the photocurrent peak is as narrow as 0.3 meV and is governed by the tunnel coupling with the electrodes, indicating that the scattering time of electrons in the present CNTs is comparable to or longer than 10 ps. The observation of a sharp absorption peak at the bare quantization energy was not consistent with the Tomonaga-Luttinger liquid theory.

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.

A fundamental study of photoluminescence modulation from DNA-wrapped single-walled carbon nanotubes.

In this study, we investigated the interaction of base sequence-assigned single-stranded DNA (ssDNA) molecules with the surfaces of single-walled carbon nanotube (SWNT)-thymine (T30)/cytosine (C30) hybrids (T30/C30-SWNT), by measuring the modulation of near-infrared (NIR) photoluminescence (PL). Significant PL shifts were observed when T30/C30-SWNTs were reacted with 30-mers of adenine (A30)/guanine (G30). In contrast, when non-complementary ssDNA was used, no significant energy shift was observed in the PL modulation except when T30-SWNTs were reacted with G30. Furthermore, atomic force microscopy (AFM) measurements revealed that the average heights of the T30-SWNTs and C30-SWNTs, after reaction with A30 were 2 ± 0.6 and 1.1 ± 0.3 nm, respectively. This result was in good agreement with the results of PL measurements. Our data reveal that DNA hybridization could be detected by measuring PL from SWNTs, without the use of fluorescent molecules. This leads to the possibility of developing nanotube-based photoelectric conversion or optical switch devices driven by organic molecules.

Monitoring the antioxidant effects of catechin using single-walled carbon nanotubes: Comparative analysis by near-infrared absorption and near-infrared photoluminescence.

We measured the optical responses of single-walled carbon nanotubes (SWNTs) after adding Japanese green tea or catechin. SWNTs were covered with DNA in aqueous solution, and tea or catechin solution was added to the DNA-SWNT suspension. The antioxidant effects of tea and catechin were detected as changes in the near-infrared (NIR) absorption (ABS) and NIR-photoluminescence (PL) spectra of the SWNTs. Commercial Japanese tea, diluted 100 times and containing 15µg/mL catechin, was sufficient for recovering NIR-ABS and NIR-PL spectra when the DNA-SWNT suspension was pre-treated with 0.03% hydrogen peroxide(H2O2). Similar results were obtained with 15µg/mL of pure catechin solution. SWNTs with specific chirality were sensitive to the NIR-ABS and NIR-PL changes. The (10, 5)/(8, 7) and (9, 4) SWNTs showed the highest recovery in NIR-ABS and NIR-PL, respectively. NIR-PL recovery was higher than that of NIR-ABS for (10, 5)/(8, 7) and (9, 4). Spectral changes could be monitored thoroughly at pH 8.0, contrary to pH 6.0 and 7.3. However, the most dynamic recovery of NIR-ABS and NIR-PL was observed at pH 6.0. Furthermore, time-lapse measurements revealed that recovery was faster with tea or catechin addition than H2O2-induced oxidation.

Formation Mechanism of Secondary Electron Contrast of Graphene Layers on a Metal Substrate.

Scanning electron microscopy (SEM) is widely used to observe graphene on metal substrates. However, the origin of the SEM image contrast of graphene is not well understood. In this work, we performed in situ SEM imaging of layer-number-controlled graphene on a Ni substrate using a high-pass energy filter for secondary electrons. We found that the graphene layer contrast was maximized at 15-20 eV, corresponding to the π-σ* interband transition in graphene. Our results indicate that the SEM image of graphene is produced by attenuation of the electrons emitted from the metal substrate by the monoatomic layers of graphene.

Conjugates between photosystem I and a carbon nanotube for a photoresponse device.

Photosystem I (PS I) is a large pigment-protein complex embedded in the thylakoid membranes that performs light-driven electron transfer across the thylakoid membrane. Carbon nanotubes exhibit excellent electrical conductivities and excellent strength and stiffness. In this study, we generated PSI-carbon nanotube conjugates dispersed in a solution aimed at application in artificial photosynthesis. PS I complexes in which a carbon nanotube binding peptide was introduced into the middle of the PsaE subunit were conjugated on a single-walled carbon nanotube, orienting the electron acceptor side to the nanotube. Spectral and photoluminescence analysis showed that the PS I is bound to a single-walled carbon nanotube, which was confirmed by transmission electron microscopy. Photocurrent observation proved that the photoexcited electron originated from PSI and transferred to the carbon nanotube with light irradiation, which also confirmed its orientated conjugation. The PS I-carbon nanotube conjugate will be a useful nano-optoelectronic device for the development of artificial systems.

Biomolecular recognition ability of RecA proteins for DNA on single-walled carbon nanotubes.

We examined the biomolecular recognition ability of RecA proteins using single-walled carbon nanotubes (SWNTs) wrapped with a single-stranded DNA (ssDNA) molecule as a mimic for the usual ssDNA molecules. The ssDNA-SWNT hybrids showed larger diameters compared to those of the usual ssDNA molecules. As a result, RecA molecules bound to the ssDNA-SWNTs, as observed using atomic force microscopy and agarose gel electrophoresis. On the other hand, when carboxymethylcellulose (CMC) was used rather than ssDNA, the RecA molecules did not bind to the CMC-SWNT hybrids. Our results indicate that RecA molecules recognize ssDNA on SWNT surfaces as DNA molecules through their biomolecular recognition ability.

Water Encapsulation Control in Individual Single-Walled Carbon Nanotubes by Laser Irradiation.

Owing to one-dimensionality, nanoscale curvature, and high chemical stability, single-walled carbon nanotubes (SWNTs) have unique surfaces for gas molecules: outer surface as adsorption (exohedral) site and inner surface that provides encapsulation (endohedral) space. Because as-grown SWNTs have different structure (chirality and diameter) and they are normally bundled, it is extremely difficult to investigate the intrinsic properties of SWNTs as adsorbent. Here we demonstrate controlling adsorption and encapsulation states of water in individual suspended SWNTs using laser irradiation with monitoring of their behavior by photoluminescence measurement and perform molecular dynamics simulation. The laser heating and the pressure control make water molecules encapsulated or ejected for SWNTs, which are individually oxidized and opened with laser heating. The precise control of oxidization makes it possible to observe the cluster formation of water molecules during the encapsulation process and to confine water molecules inside SWNTs even in vacuum.

Photoluminescence measurements and molecular dynamics simulations of water adsorption on the hydrophobic surface of a carbon nanotube in water vapor.

Hydrophilicity or hydrophobicity is a macroscopic property of the surface, and its atomic scale understanding has not been established. We have studied adsorption of water molecules on the "hydrophobic" carbon nanotube surface at room temperature in water vapor. Based on optical measurements of individual single-walled carbon nanotubes suspended between micropillars in water vapor together with molecular dynamics simulations, we found that water molecules form a stable adsorption layer of 1-2 ML thickness on the nanotube surface and they show rapid adsorption and desorption transition at a critical pressure. This adsorption layer is created by lateral hydrogen bonding of water molecules confined in the weak van der Waals potential of the surface. In spite of hydrophobic hydration, carbon nanotubes exhibit hydrophobicity macroscopically.

Investigation of catalytic properties of Al2O3 particles in the growth of single-walled carbon nanotubes.

We systematically investigate the catalytic properties of Al2O3 particles in the growth of carbon nanotubes (CNTs) in chemical vapor deposition (CVD). Compared with the conventional metal catalysts, the particle size of Al2O3 catalyst has no influence on the number of nanotube walls because only single-walled carbon nanotubes (SWCNTs) are produced. Interestingly, one large Al2O3 particle can usually nucleate several SWCNTs. However, statistical analysis reveals that the average growth rate of SWCNTs from Al2O3 catalyst is about 200 nm/min, which is much lower than that of CNTs grown from Fe catalyst under the same conditions. Additionally, a low gas pressure is found to be important for the growth of SWCNTs from Al2O3 catalyst. These results reflect that Al2O3 catalyst has different catalytic properties from the conventional metal catalysts, which will be helpful for the elucidation of the nanotube growth mechanism.

Transfer and alignment of random single-walled carbon nanotube films by contact printing.

We present a simple method to transfer large-area random single-walled carbon nanotube (SWCNT) films grown on SiO(2) substrates onto another surface through a simple contact printing process. The transferred random SWCNT films can be assembled into highly ordered, dense regular arrays with high uniformity and reproducibility by sliding the growth substrate during the transfer process. The position of the transferred SWCNT film can be controlled by predefined patterns on the receiver substrates. The process is compatible with a variety of substrates, and even metal meshes for transmission electron microscopy (TEM) can be used as receiver substrates. Thus, suspended web-like SWCNT networks and aligned SWCNT arrays can be formed over the grids of TEM meshes, so that the structures of the transferred SWCNTs can be directly observed by TEM. This simple technique can be used to controllably transfer SWCNTs for property studies, for the fabrication of devices, or even as support films for TEM meshes.

Brightening of triplet dark excitons by atomic hydrogen adsorption in single-walled carbon nanotubes observed by photoluminescence spectroscopy.

Adsorption and desorption of atomic hydrogen on single-walled carbon nanotubes were observed by photoluminescence spectroscopy. A satellite peak appeared at the lower energy side of the E11 photoluminescence emission peak after exposure to atomic hydrogen and then disappeared after annealing at 300 °C in vacuum. The energy difference between the satellite peak and E11 peak was 40-80 meV, depending on the tube diameter. The satellite peak was attributed to the triplet dark exciton that became optically active because of the effectively enhanced spin-orbit interaction induced by adsorbed hydrogen atoms.

Atomic-scale analysis on the role of molybdenum in iron-catalyzed carbon nanotube growth.

We have elucidated the synergetic role played by molybdenum in iron-catalyzed chemical vapor deposition growth of carbon nanotubes (CNTs) by in situ environmental transmission electron microscopy. Molybdenum can be well accommodated by Fe-based carbide nanoparticle catalysts of M(23)C(6)-type structure (M = Fe and Mo). We have also shown that molybdenum suppresses the nucleation of iron compounds that are known to exhibit no catalytic activity for the growth of CNTs.

The controlled growth of horizontally aligned single-walled carbon nanotube arrays by a gas flow process.

High-density horizontally aligned single-walled carbon nanotubes (SWCNTs) have been grown by annealing Fe catalyst in air and optimizing catalyst thickness in the gas flow process. The aligned SWCNT density reaches >60 nanotubes per 100 microm and the length can be a few millimeters. Interestingly, the growth of aligned SWCNT arrays can be extended from the catalyst substrate to a downstream substrate across the gap between them by gas flow when the two substrates are put close to each other, and thus an aligned SWCNT array has been achieved on an isolated clean substrate.

Carbon nanotube growth from diamond.

We demonstrate that nanosize diamond particles in a stable solid phase can act as nuclei for carbon nanotube (CNT) growth by chemical vapor deposition. This growth process is explained by a new growth mechanism, where the surface diffusion of carbon adatoms on the solid surface of nanoparticles plays an important role, contrary to the bulk diffusion in conventional metal catalysts. The use of diamond nanoparticles overcomes the issues of deactivation due to fusion with each other or reaction with substrate materials in the CNT growth using conventional metal catalysts and promotes high-density CNT growth from highly dense nanoparticles on any substrate.

Engineering low-aspect ratio carbon nanostructures: nanocups, nanorings, and nanocontainers.

The synthesis of carbon nanostructures, with interesting morphologies, has created a revolution in nanotechnology; carbon nanotube is a case in point, but other nanoscale morphologies of graphitic carbon could provide compelling uses. In particular short structures, including very short nanotubes, have proven impossible to be grown by existing techniques due to the difficulty in controlling and terminating growth during initial stages. Here we present architectures engineered from graphitic carbon, having up to 10(5) times smaller length/diameter (L/D) ratios compared to conventional nanotubes, revealing unique morphologies of nanocups, nanorings, and large area connected nanocup arrays. Such highly engineered hollow nanostructures were fabricated using precisely controlled short nanopores inside anodic aluminum oxide templates. The nanocups were effectively used to hold and contain other nanomaterials, for example, metal nanoparticles, leading to the formation of multicomponent hybrid nanostructures with unusual morphologies. The results reported here open up possibilities to integrate new morphologies of graphitic carbon in nanotechnology applications.