Growth of Continuous Monolayer Graphene with Millimeter-sized Domains Using Industrially Safe Conditions.

We demonstrate the growth of continuous monolayer graphene films with millimeter-sized domains on Cu foils under intrinsically safe, atmospheric pressure growth conditions, suitable for application in roll-to-roll reactors. Previous attempts to grow large domains in graphene have been limited to isolated graphene single crystals rather than as part of an industrially useable continuous film. With both appropriate pre-treatment of the Cu and optimization of the CH4 supply, we show that it is possible to grow continuous films of monolayer graphene with millimeter scale domains within 80 min by chemical vapour deposition. The films are grown under industrially safe conditions, i.e., the flammable gases (H2 and CH4) are diluted to well below their lower explosive limit. The high quality, spatial uniformity, and low density of domain boundaries are demonstrated by charge carrier mobility measurements, scanning electron microscope, electron diffraction study, and Raman mapping. The hole mobility reaches as high as ~5,7002 m(2) V(-1) s(-1) in ambient conditions. The growth process of such high-quality graphene with a low H2 concentration and short growth times widens the possibility of industrial mass production

Growth of high quality, high density single-walled carbon nanotube forests on copper foils

We demonstrate the growth of high quality single-walled carbon nanotube (SWCNT) forests on commercial Cu foils by cold-wall chemical vapor deposition. Time-of-flight secondary ion mass spectrometry was employed to study the effect of annealing on the catalyst evolution with or without an AlOₓ barrier layer. X-ray photoelectron spectroscopy was used to investigate the chemical states of the catalyst and the barrier layer. SWCNT forests can be reproducibly grown on Cu foils sputter-coated with Al and Fe layers as thin as 6 nm and 0.4 nm, respectively. Al transforms into AlOₓ on exposure to air and during annealing. Most importantly, such a thin AlOₓ barrier layer ensures not only the growth of SWCNTs but also an Ohmic contact between the as grown SWCNTs and the Cu base as measured by a two-point probe station. The as-grown SWCNTs exhibit a bimodal distribution of diameters ranging from 0.6 to 4.5 nm, with two peaks centered at 0.8 nn and 2.6 nm, respectively.This work supported by Honda Research Institute USA Inc. Sugime H. acknowledges a research fellowship from the Japanese Society for the Promotion of Science (JSPS).This is the author accepted manuscript. The final version is available from Elsevier via http://dx.doi.org/10.1016/j.carbon.2015.11.04

Low temperature growth of fully covered single-layer graphene using a CoCu catalyst.

A bimetallic CoCu alloy thin-film catalyst is developed that enables the growth of uniform, high-quality graphene at 750 °C in 3 min by chemical vapour deposition. The growth outcome is found to vary significantly as the Cu concentration is varied, with ∼1 at% Cu added to Co yielding complete coverage single-layer graphene growth for the conditions used. The suppression of multilayer formation is attributable to Cu decoration of high reactivity sites on the Co surface which otherwise serve as preferential nucleation sites for multilayer graphene. X-ray photoemission spectroscopy shows that Co and Cu form an alloy at high temperatures, which has a drastically lower carbon solubility, as determined by using the calculated Co-Cu-C ternary phase diagram. Raman spectroscopy confirms the high quality (ID/IG < 0.05) and spatial uniformity of the single-layer graphene. The rational design of a bimetallic catalyst highlights the potential of catalyst alloying for producing two-dimensional materials with tailored properties

Growth of high-density carbon nanotube forests on conductive TiSiN supports

This is the accepted manuscript. The final version is available at http://scitation.aip.org/content/aip/journal/apl/106/8/10.1063/1.4913762.We grow vertically aligned carbon nanotube forests on refractory conductive films of TiSiN and achieve area densities of (5.1 ± 0.1) × 1012 tubes cm−2 and mass densities of about 0.3 g cm−3. The TiSiN films act as diffusion barriers limiting catalyst diffusion into the bulk of the support, and their low surface energy favours catalyst de-wetting, inducing forests to grow by the root growth mechanism. The nanotube area density is maximised by an additional discontinuous AlOx layer, which inhibits catalyst nanoparticle sintering by lateral surface diffusion. The forests and the TiSiN support show ohmic conduction. These results suggest that TiSiN is the favoured substrate for nanotube forest growth on conductors and liable of finding real applications in microelectronics.The authors acknowledge funding from European project Grafol. J.Y. thanks Sarah Fearn and David McPhail from Imperial College London for use of the SIMS instrument. A.W.R. is supported by EPSRC (Platform Grant Nos. EP/F048009/1 and EP/K032518/1) and Korean Institute for Energy Research. H.S. acknowledges a research fellowship from the Japanese Society for the Promotion of Science

Low-Temperature Growth of Carbon Nanotube Forests Consisting of Tubes with Narrow Inner Spacing Using Co/Al/Mo Catalyst on Conductive Supports.

We grow dense carbon nanotube forests at 450 °C on Cu support using Co/Al/Mo multilayer catalyst. As a partial barrier layer for the diffusion of Co into Mo, we apply very thin Al layer with the nominal thickness of 0.50 nm between Co and Mo. This Al layer plays an important role in the growth of dense CNT forests, partially preventing the Co-Mo interaction. The forests have an average height of ∼300 nm and a mass density of 1.2 g cm(-3) with tubes exhibiting extremely narrow inner spacing. An ohmic behavior is confirmed between the forest and Cu support with the lowest resistance of ∼8 kΩ. The forest shows a high thermal effusivity of 1840 J s(-0.5) m(-2) K(-1), and a thermal conductivity of 4.0 J s(-1) m(-1) K(-1), suggesting that these forests are useful for heat dissipation devices.This work has been funded by the European projects Technotubes and Grafol. H.S. acknowledges a research fellowship from the Japanese Society for the Promotion of Science (JSPS).This is the accepted manuscript. The final version is available at http://pubs.acs.org/doi/abs/10.1021/acsami.5b04846

Carbon nanotube forests as top electrode in electroacoustic resonators

We grow carbon nanotube forests on piezoelectric AlN films and fabricate and characterize nanotube-based solidly mounted bulk acoustic wave resonators employing the forests as the top electrode material. The devices show values for quality factor at anti-resonance of ∼430, and at resonance of ∼100. The effective coupling coefficient is of ∼6%, and the resonant frequencies are up to ∼800 MHz above those observed with metallic top electrodes. AlN promotes a strong catalyst-support interaction, which reduces Fe catalyst mobility, and thus enforces the growth of forests by the base growth mechanism.This work was partially supported by the European Commission through the project GRAFOL and the COST action IC1208 and by the Ministerio de Economía y Competitividad del Gobierno de España through project MAT2013-45957.This is the accepted manuscript. The final version is available at http://scitation.aip.org/content/aip/journal/apl/107/13/10.1063/1.4932197

Cold-gas chemical vapor deposition to identify the key precursor for rapidly growing vertically-aligned single-wall and few-wall carbon nanotubes from pyrolyzed ethanol

Vertically-aligned carbon nanotubes (VA-CNTs) were rapidly grown from ethanol and their chemistry has been studied using a "cold-gas" chemical vapor deposition (CVD) method. Ethanol vapor was preheated in a furnace, cooled down and then flowed over cobalt catalysts upon ribbon-shaped substrates at 800 °C, while keeping the gas unheated. CNTs were obtained from ethanol on a sub-micrometer scale without preheating, but on a millimeter scale with preheating at 1000 °C. Acetylene was predicted to be the direct precursor by gas chromatography and gas-phase kinetic simulation, and actually led to millimeter-tall VA-CNTs without preheating when fed with hydrogen and water. There was, however a difference in CNT structure, i.e. mainly few-wall tubes from pyrolyzed ethanol and mainly single-wall tubes for unheated acetylene, and the by-products from ethanol pyrolysis possibly caused this difference. The "cold-gas" CVD, in which the gas-phase and catalytic reactions are separately controlled, allowed us to further understand CNT growth. © 2012 Elsevier Ltd. All rights reserved