Controllable chemical vapor deposition of large area uniform nanocrystalline graphene directly on silicon dioxide

Metal-catalyst-free chemical vapor deposition (CVD) of large area uniform nanocrystalline graphene on oxidized silicon substrates is demonstrated. The material grows slowly, allowing for thickness control down to monolayer graphene. The as-grown thin films are continuous with no observable pinholes, and are smooth and uniform across whole wafers, as inspected by optical-, scanning electron-, and atomic force microscopy. The sp 2 hybridized carbon structure is confirmed by Raman spectroscopy. Room temperature electrical measurements show ohmic behavior (sheet resistance similar to exfoliated graphene) and up to 13 of electric-field effect. The Hall mobility is ∼40 cm 2/Vs, which is an order of magnitude higher than previously reported values for nanocrystalline graphene. Transmission electron microscopy, Raman spectroscopy, and transport measurements indicate a graphene crystalline domain size ∼10 nm. The absence of transfer to another substrate allows avoidance of wrinkles, holes, and etching residues which are usually detrimental to device performance. This work provides a broader perspective of graphene CVD and shows a viable route toward applications involving transparent electrodes. © 2012 American Institute of Physics.

The parameter space of graphene chemical vapor deposition on polycrystalline Cu

A systematic study of the parameter space of graphene chemical vapor deposition (CVD) on polycrystalline Cu foils is presented, aiming at a more fundamental process rationale in particular regarding the choice of carbon precursor and mitigation of Cu sublimation. CH 4 as precursor requires H 2 dilution and temperatures ≥1000 °C to keep the Cu surface reduced and yield a high-quality, complete monolayer graphene coverage. The H 2 atmosphere etches as-grown graphene; hence, maintaining a balanced CH 4/H 2 ratio is critical. Such balance is more easily achieved at low-pressure conditions, at which however Cu sublimation reaches deleterious levels. In contrast, C 6H 6 as precursor requires no reactive diluent and consistently gives similar graphene quality at 100-150 °C lower temperatures. The lower process temperature and more robust processing conditions allow the problem of Cu sublimation to be effectively addressed. Graphene formation is not inherently self-limited to a monolayer for any of the precursors. Rather, the higher the supplied carbon chemical potential, the higher the likelihood of film inhomogeneity and primary and secondary multilayer graphene nucleation. For the latter, domain boundaries of the inherently polycrystalline CVD graphene offer pathways for a continued carbon supply to the catalyst. Graphene formation is significantly affected by the Cu crystallography; i.e., the evolution of microstructure and texture of the catalyst template form an integral part of the CVD process. © 2012 American Chemical Society.

Diameter and wall number control of carbon nanotubes by chemical vapor deposition

We analyze the relationship between the average wall number (N) and the diameter (d) for carbon nanotubes (CNTs) grown by chemical vapour deposition. It is found that N depends linearly on d for diameters in the range of 2.5-10 nm, while single wall nanotubes predominate for diameters under about 2.1 nm. The linear relationship is found to depend somewhat on the growth conditions. It is also verified that the mean diameter depends on the diameter of the originating catalyst nanoparticle, and thus on the initial catalyst thickness where a thin film catalyst is used. This simplifies the characterisation of CNTs by electron microscopy. We also find a linear relationship between nanotube diameter and initial catalyst film thickness. © 2013 AIP Publishing LLC.

Hafnia nanoparticles - a model system for graphene growth on a dielectric

We study graphene growth on hafnia (HfO2) nanoparticles by chemical vapour deposition using optical microscopy, high resolution transmission electron microscopy and Raman spectroscopy. We find that monoclinic HfO2 nanoparticles neither reduce to a metal nor form a carbide while nucleating nanometer domain-sized few layer graphene. Hence we regard this as an interesting non-metallic catalyst model system with the potential to explore graphene growth directly on a (high-k) dielectric. HfO2 nanoparticles coated with few layer graphene by atmospheric pressure CVD with methane and hydrogen at 950 °C. (© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) Graphene growth on hafnia (HfO2) nanoparticles by chemical vapour deposition (CVD) is studied. It is found that monoclinic HfO2 nanoparticles neither reduce to a metal nor form a carbide while nucleating nanometer domain-sized few layer graphene. Hence the authors of this Letter regard this as an interesting non-metallic catalyst model system with the potential to explore graphene growth directly on a (high-k) dielectric. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environment induced variation in the photoconductivity of graphene observed by terahertz spectroscopy

Chemical vapour deposition (CVD) grown graphene sheets were investigated using optical-pump terahertz-probe spectroscopy, revealing a dramatic variation in the photoinduced terahertz conductivity of graphene in different atmospheres. © 2012 IEEE.

In-Situ grown carbon nanotubes for enhanced CO2 detection in non-dispersive-infra-red system

Non-dispersive-infra-red (NDIR) sensors are believed to be one of the most selective and robust solutions for CO2 detection, though cost prohibits their broader integration. In this paper we propose a commercially viable silicon-on-insulator (SOI) complementary metal-oxide (CMOS) micro-electro-mechanical (MEMS) technology for an IR thermal emitter. For the first time, vertically aligned multi walled carbon nanotubes (VA-MWCNTs) are suggested as a possible coating for the enhancement of the emission intensity of the optical source of a NDIR system. VA-MWCNTs have been grown in situ by chemical vapour deposition (CVD) exclusively on the heater area. Optical microscopy, scanning electron microscopy and Raman spectroscopy have been used to verify the quality of the VA-MWCNTs growth. The CNT-coated emitter demonstrated an increased response to CO2 of approx. 60%. Furthermore, we show that the VA-MWCNTs are stable up to temperatures of 500°C for up to 100 hours. © 2013 IEEE.

Effect of hydrogen dilution on the deposition of carbon-rich a-SiC:H films by the electron cyclotron resonance method

The deposition of hydrogenated amorphous silicon carbide (a-SiC:H) films from a mixture of silane, acetylene and hydrogen gas using the electron cyclotron resonance chemical vapour deposition (ECR-CVD) process is reported. The variation in the deposition and film characteristics such as the deposition rate, optical band gap and IR absorption as a function of the hydrogen dilution is investigated. The deposition rate increases to a maximum value of about 250 Å min-1 at a hydrogen dilution ratio of about 20 (hydrogen flow (sccm)/acetylene + silane flow (sccm)) and decreases in response to a further increase in the hydrogen dilution. There is no strong dependence of the optical band gap on the hydrogen dilution within the dilution range investigated (10-60) and the optical band gap calculated from the E04 method varied marginally from about 2.85 to 3.17 eV. The room temperature photoluminescence (PL) peak energy and intensity showed a prominent shift to a maximum value of about 2.17 eV corresponding to maximum PL intensity at a moderate hydrogen dilution of about 30. The PL intensity showed a strong dependence on the hydrogen dilution variation.

SiO2 coating of silver nanoparticles by photoinduced chemical vapor deposition.

Gas-phase silver nanoparticles were coated with silicon dioxide (SiO2) by photoinduced chemical vapor deposition (photo-CVD). Silver nanoparticles, produced by inert gas condensation, and a SiO2 precursor, tetraethylorthosilicate (TEOS), were exposed to vacuum ultraviolet (VUV) radiation at atmospheric pressure and varying temperatures. The VUV photons dissociate the TEOS precursor, initiating a chemical reaction that forms SiO2 coatings on the particle surfaces. Coating thicknesses were measured for a variety of operation parameters using tandem differential mobility analysis and transmission electron microscopy. The chemical composition of the particle coatings was analyzed using energy dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The highest purity films were produced at 300-400 degrees C with low flow rates of additional oxygen. The photo-CVD coating technique was shown to effectively coat nanoparticles and limit core particle agglomeration at concentrations up to 10(7) particles cm(-3).

Microwave power effects on the properties of phosphorus-doped SiC:H films prepared using ECR-CVD

There has been a growing interest in hydrogenated silicon carbide films (SiC:H) prepared using the electron cyclotron resonance-chemical vapour deposition (ECR-CVD) technique. Using the ECR-CVD technique, SiC:H films have been prepared from a mixture of methane, silane and hydrogen, with phosphine as the doping gas. The effects of changes in the microwave power (from 150 to 900 W) on the film properties were investigated in a series of phosphorus-doped SiC:H films. In particular, the changes in the deposition rate, optical bandgap, activation energy and conductivity were investigated in conjunction with results from Raman scattering and Fourier transform infra-red (FTIR) analysis. It was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the amorphous matrix of the SiC:H films. This occurs in correspondence to a rapid increase in the conductivity and a reduction in the activation energy, both of which exhibit small variations in samples deposited at microwave powers exceeding 500 W. Analysis of IR absorption results suggests that hydrogen is bonded to silicon in the Si-H stretching mode and to carbon in the sp3 CHn rocking/wagging and bending mode in films deposited at higher microwave powers.

Gas-phase production of multifunctional composite nanoparticles by photoinduced chemical vapor deposition

As these results indicate, photo-CVD coating is a robust process that allows for the creation of core-shell nanoparticles. In the present work we demonstrated that photo-CVD can effectively coat Fe2O3 particles with silica for purposes of biological applications. TDMA results combined with TEM images indicate that all particles are effectively coated and that particle coating thicknesses can be tuned to desired thickness depending on the application. In addition, the ability to vary coating properties and to coat high concentrations of particles makes this technique of interest for industrial production where uniform properties are needed for large quantities of particles [2]. Copyright © 2010 by ASME.

Transient terahertz spectroscopy of mono- and tri-layer CVD-grown MoS 2

Molybdenum disulpide, a novel two-dimensional semiconductor, was studied using optical-pump terahertz-probe spectroscopy. Mono and trilayer samples grown by chemical vapour deposition were compared to reveal their dynamic electrical response. © 2013 IEEE.

Low-temperature growth of carbon nanotubes by plasma-enhanced chemical vapor deposition

Vertically aligned carbon nanotubes were grown at temperatures as low as 120degreesC by plasma-enhanced chemical vapor deposition. A systematic study of the temperature dependence of the growth rate and the structure of the as-grown nanotubes is presented using a C2H2/NH3 system and nickel as the catalyst. The activation energy for the growth rate was found to be 0.23 eV, much less than for thermal chemical vapor deposition (1.2-1.5 eV). This suggests growth occurs by surface diffusion of carbon on nickel. The result could allow direct growth of nanotubes onto low-temperature substrates like plastics, and facilitate the integration in sensitive nanoelectronic devices. (C) 2003 American Institute of Physics.

Effects of pre-treatment and plasma enhancement on chemical vapor deposition of carbon nanotubes from ultra-thin catalyst films

We report a detailed study of surface-bound chemical vapor deposition of carbon nanotubes and nanofibers from evaporated transition metal catalysts exposed to ammonia diluted acetylene. We show that a reduction of the Fe/Co catalyst film thickness below 3 nm results into a transition from large diameter (> 40 nm), bamboo-like nanofibers to small diameter (similar to 5 nm) multi-walled carbon nanotubes. The nanostructuring of ultrathin catalyst films critically depends on the gas atmosphere, with the resulting island distribution initiating the carbon nucleation. Compared to purely thermal chemical vapor deposition, we find that, for small diameter nanotube growth, DC plasma assistance is detrimental to graphitization and sample homogeneity and cannot prevent an early catalyst poisoning. (c) 2006 Elsevier B.V. All rights reserved.