Reversible Diameter Modulation of Single-Walled Carbon Nanotubes by Acetonitrile-Containing Feedstock

Changing the carbon feedstock from pure ethanol to a 5 vol % mixture of acetonitrile in ethanol during the growth of vertically aligned single-walled carbon nanotubes (SWNTs) reduces the mean diameter of the emerging SWNTs from approximately 2 to 1 nm. We show this feedstock-dependent change is reversible and repeatable, as demonstrated by multilayered vertically aligned SWNT structures. The reversibility of this process and lack of necessity for catalyst modification provides insight into the role of nitrogen in reducing the SWNT diameter

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

Effect of Gas Pressure on the Density of Horizontally Aligned Single-Walled Carbon Nanotubes Grown on Quartz Substrates

We investigate the influence of gas pressure on the growth of horizontally aligned single-walled carbon nanotubes (SWCNTs) on R-cut and r-cut crystal quartz substrates by alcohol catalytic chemical vapor deposition (CVD). The density of horizontally aligned SWCNTs was found to depend highly on gas pressure. A study of the SWCNT growth as a function of CVD time revealed that the density of horizontally aligned SWCNTs continued to increase for 10 min at reduced pressure, whereas the density saturated rapidly at higher pressure even though catalysts were not deactivated. We argue that variation of incubation time for low-pressure CVD is key for independent growth of horizontally aligned SWCNTs and hence higher density growth

On-Chip Sorting of Long Semiconducting Carbon Nanotubes for Multiple Transistors along an Identical Array

Ballistic transport and sub-10 nm channel lengths have been achieved in transistors containing one single-walled carbon nanotube (SWNT). To fill the gap between single-tube transistors and high-performance logic circuits for the replacement of silicon, large-area, high-density, and purely semiconducting (s-) SWNT arrays are highly desired. Here we demonstrate the fabrication of multiple transistors along a purely semiconducting SWNT array <i>via</i> an on-chip purification method. Water- and polymer-assisted burning from site-controlled nanogaps is developed for the reliable full-length removal of metallic SWNTs with the damage to s-SWNTs minimized even in high-density arrays. All the transistors with various channel lengths show large on-state current and excellent switching behavior in the off-state. Since our method potentially provides pure s-SWNT arrays over a large area with negligible damage, numerous transistors with arbitrary dimensions could be fabricated using a conventional semiconductor process, leading to SWNT-based logic, high-speed communication, and other next-generation electronic devices

Highly Stable and Tunable n‑Type Graphene Field-Effect Transistors with Poly(vinyl alcohol) Films

The intrinsic p-type behavior of graphene field-effect transistors (FETs) under ambient conditions poses a fundamental challenge for the assembly of complex electronic devices, such as integrated circuits. In this work, we present a protocol for tunable n-type doping of graphene FETs via poly­(vinyl alcohol) (PVA) coating. Using graphene grown by alcohol catalytic chemical vapor deposition, functionalization of the surface by this hydroxyl anion-rich polymer results in an evolution of the FETs from p-type to ambipolar or n-type even under ambient air conditions. The doping level of graphene is strongly related to the PVA film coating parameters, such as solution concentration, hardening temperature, and hardening time. This PVA coating proves to be a simple and stable approach to tuning the Dirac point and doping level of graphene, which is highly desirable and of great significance for the future of graphene-based electronic devices

Growth Analysis of Single-Walled Carbon Nanotubes Based on Interatomic Potentials by Molecular Dynamics Simulation

Molecular dynamics simulation was performed to understand the growth mechanism of single-walled carbon nanotubes (SWNTs) by using the Brenner–Tersoff potential as the interaction among carbon atoms (C–C) and the Tersoff-type potential as the interaction between carbon and metal (C–M) and between metal and metal atoms (M–M). The potential functions for C–M and M–M bonds were established from the results of ab initio calculations. The growth of high-quality SWNTs was simulated at a suitable temperature and supply ratio of carbon atoms. The potential energy of carbon atoms was strongly dependent on the number of C–C and C–M bonds. The dependence explains the growth process, including cap formation, its lift-off, and the continuous SWNT growth

Diameter Modulation of Vertically Aligned Single-Walled Carbon Nanotubes

We demonstrate wide-range diameter modulation of vertically aligned single-walled carbon nanotubes (SWNTs) using a wet chemistry prepared catalyst. In order to ensure compatibility to electronic applications, the current minimum mean diameter of 2 nm for vertically aligned SWNTs is challenged. The mean diameter is decreased to about 1.4 nm by reducing Co catalyst concentrations to 1/100 or by increasing Mo catalyst concentrations by five times. We also propose a novel spectral analysis method that allows one to distinguish absorbance contributions from the upper, middle, and lower parts of a nanotube array. We use this method to quantitatively characterize the slight diameter change observed along the array height. On the basis of further investigation of the array and catalyst particles, we conclude that catalyst aggregationrather than Ostwald ripeningdominates the growth of metal particles

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 (<i>n</i>, <i>m</i>), 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

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. <i>Ex situ</i> 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

Self-Limiting Chemical Vapor Deposition Growth of Monolayer Graphene from Ethanol

Using low-pressure chemical vapor deposition (LPCVD), we, for the first time, realize the self-limiting growth behavior of monolayer graphene on commercially available electroplated copper foils from a carbon precursor other than methane, and systematically investigate the growth of graphene from ethanol and compare its self-limiting behavior over copper facets with different identities. Results show that the growth of graphene from ethanol in the LPCVD process is a substrate-mediated process, in which the domains of graphene are determined by the lattice axes on the copper facets. Moreover, during the evolution of the domains, low-index copper facets of Cu(111) and Cu(100) play a critical role in the following self-limiting process of a continuous graphene sheet, whereas the Cu(110) and high-index facets favor nucleation and formation of secondary layers. In addition, a high degree of similarity exists between graphene grown from ethanol and methane, showing that, when the carbon flux is sufficiently low, the self-limiting growth of graphene on copper surfaces using LPCVD is independent of the precursor structure of ethanol and methane