Adsorptive graphene doping: Effect of a polymer contaminant

© 2017 Author(s). Transfer-induced contamination of graphene and the limited stability of adsorptive dopants are two of the main issues faced in the practical realization of graphene-based electronics. Herein, we assess the stability of HNO3, MoO3, and AuCl3 dopants upon transferred graphene with different extents of polymer contamination. Sheet resistivity measurements prove that polymer residues induce a significantly degenerative effect in terms of doping stability for HNO3 and MoO3 and a highly stabilizing effect for AuCl3. Further characterization by Raman spectroscopy and atomic force microscopy (AFM) provides insight into the stability mechanism. Together, these findings demonstrate the relevance of contamination in the field of adsorptive doping for the realization of graphene-based functional devices

Effect of catalyst pretreatment on chirality-selective growth of single-walled carbon nanotubes

We show that catalyst pre-treatment conditions can have a profound effect on the chiral distribution in single-walled carbon nanotubes chemical vapor deposition. Using a SiO2-supported Cobalt model catalyst and pre-treatment in NH3, we obtain a comparably narrowed chiral distribution with a downshifted tube diameter range, independent of the hydrocarbon source. Our findings demonstrate that the state of the catalyst at the point of nanotube nucleation is of fundamental importance for chiral control, thus identifying the pre-treatment atmosphere as a key parameter for control of diameter and chirality distributions.B.C.B acknowledges a Research Fellowship at Hughes Hall, Cambridge. J.R. thanks the Alexander von Humboldt Foundation for support.This is the original submitted version, prior to peer-review. The final version's available from ACS at http://pubs.acs.org/doi/abs/10.1021/jp4085348

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

Stability of graphene doping with MoO<inf>3</inf>and I<inf>2</inf>

We dope graphene by evaporation of MoO_3 or by solution-deposition of I_2 and assess the doping stability for its use as transparent electrodes. Electrical measurements show that both dopants increase the graphene sheet conductivity and find that MoO_3-doped graphene is significantly more stable during thermal cycling. Raman spectroscopy finds that neither dopant creates defects in the graphene lattice. In-situ photoemission determines the minimum necessary thickness of MoO_3 for full graphene doping.This is the author's accepted manuscript. Copyright (2014) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Applied Physics Letters (volume 105) and may be found at http://scitation.aip.org/content/aip/journal/apl/105/10/10.1063/1.489502

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

Stable, efficient p-type doping of graphene by nitric acid

We systematically dope monolayer graphene with different concentrations of nitric acid over a range of temperatures, and analyze the variation of sheet resistance under vacuum annealing up to 300 °C.</p

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 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

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

Identifying the catalyst chemical state and adsorbed species during methanol conversion on copper using ambient pressure X-ray spectroscopies

Methanol is a promising chemical for the safe and efficient storage of hydrogen, where methanol conversion reactions can generate a hydrogen-containing gas mixture. Understanding the chemical state of the catalyst over which these reactions occur and the interplay with the adsorbed species present is key to the design of improved catalysts and process conditions. Here we study polycrystalline Cu foils using ambient pressure X-ray spectroscopies to reveal the Cu oxidation state and identify the adsorbed species during partial oxidation (CH3OH + O2), steam reforming (CH3OH + H2O), and autothermal reforming (CH3OH + O2 + H2O) of methanol at 200 °C surface temperature and in the mbar pressure range. We find that the Cu surface remains highly metallic throughout partial oxidation and steam reforming reactions, even for oxygen-rich conditions. However, for autothermal reforming the Cu surface shows significant oxidation towards Cu2O. We rationalise this behaviour on the basis of the shift in equilibrium of the CH3OH* + O* ⇌ CH3O* + OH* caused by the addition of H2O