RESUMO
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 â¼1 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.
RESUMO
We investigate the interfacial chemistry between Fe catalyst foils and monolayer hexagonal boron nitride (h-BN) following chemical vapor deposition and during subsequent atmospheric exposure, using scanning electron microscopy, X-ray photoemission spectroscopy, and scanning photoelectron microscopy. We show that regions of the Fe surface covered by h-BN remain in a metallic state during exposure to moist air for â¼40 h at room temperature. This protection is attributed to the strong interfacial interaction between h-BN and Fe, which prevents the rapid intercalation of oxidizing species. Local Fe oxidation is observed on bare Fe regions and close to defects in the h-BN film (e.g., domain boundaries, wrinkles, and edges), which over the longer-term provide pathways for slow bulk oxidation of Fe. We further confirm that the interface between h-BN and metallic Fe can be recovered by vacuum annealing at â¼600 °C, although this is accompanied by the creation of defects within the h-BN film. We discuss the importance of these findings in the context of integrated manufacturing and transfer-free device integration of h-BN, particularly for technologically important applications where h-BN has potential as a tunnel barrier such as magnetic tunnel junctions.
RESUMO
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.
RESUMO
We dope nanotube forests using evaporated MoO3 and observe the forest resistivity to decrease by 2 orders of magnitude, reaching values as low as â¼5 × 10(-5) Ωcm, thus approaching that of copper. Using in situ photoemission spectroscopy, we determine the minimum necessary MoO3 thickness to dope a forest and study the underlying doping mechanism. Homogenous coating and tube compaction emerge as key factors for decreasing the forest resistivity. When all nanotubes are fully coated with MoO3 and packed, conduction channels are created both inside the nanotubes and on the outside oxide layer. This is supported by density functional theory calculations, which show a shift of the Fermi energy of the nanotubes and the conversion of the oxide into a layer of metallic character. MoO3 doping removes the need for chirality control during nanotube growth and represents a step forward toward the use of forests in next-generation electronics and in power cables or conductive polymers.
RESUMO
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 â¼300 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 â¼8 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.
RESUMO
We have systematically studied the macroscopic adhesive properties of vertically aligned nanotube arrays with various packing density and roughness. Using a tensile setup in shear and normal adhesion, we find that there exists a maximum packing density for nanotube arrays to have adhesive properties. Too highly packed tubes do not offer intertube space for tube bending and side-wall contact to surfaces, thus exhibiting no adhesive properties. Likewise, we also show that the surface roughness of the arrays strongly influences the adhesion properties and the reusability of the tubes. Increasing the surface roughness of the array strengthens the adhesion in the normal direction, but weakens it in the shear direction. Altogether, these results allow progress toward mimicking the gecko's vertical mobility.
Assuntos
Adesivos/química , Materiais Biomiméticos/química , Nanotubos de Carbono/química , Adesividade , Animais , Biomimética , LagartosRESUMO
We evaluate the growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests. They are synthesized by chemical vapor deposition at 450 °C using a conductive Ti/Cu support and Co-Mo catalyst system. We find that Mo stabilizes Co particles preventing lift off during the initial growth stage, thus promoting the growth of ultrahigh mass density nanotube forests by the base growth mechanism. The morphology of the forest gradually changes with growth time, mostly because of a structural change of the catalyst particles. After 100 min growth, toward the bottom of the forest, the area density decreases from â¼ 3-6 × 10(11) cm(-2) to â¼ 5 × 10(10) cm(-2) and the mass density decreases from 1.6 to 0.38 g cm(-3). We also observe part of catalyst particles detached and embedded within nanotubes. The progressive detachment of catalyst particles results in the depletion of the catalyst metals on the substrate surfaces. This is one of the crucial reasons for growth termination and may apply to other catalyst systems where the same features are observed. Using the packed forest morphology, we demonstrate patterned forest growth with a pitch of â¼ 300 nm and a line width of â¼ 150 nm. This is one of the smallest patterning of the carbon nanotube forests to date.
RESUMO
We report the fabrication and characterization of hybrids of vertically-aligned carbon nanotube forests and gold nanoparticles for improved manipulation of their plasmonic properties. Raman spectroscopy of nanotube forests performed at the separation area of nanotube-nanoparticles shows a scattering enhancement factor of the order of 1 × 10(6). The enhancement is related to the plasmonic coupling of the nanoparticles and is potentially applicable in high-resolution scanning near-field optical microscopy, plasmonics, and photovoltaics.
RESUMO
We present a general catalyst design to synthesize ultrahigh density, aligned forests of carbon nanotubes by cyclic deposition and annealing of catalyst thin films. This leads to nanotube forests with an area density of at least 10(13) cm(-2), over 1 order of magnitude higher than existing values, and close to the limit of a fully dense forest. The technique consists of cycles of ultrathin metal film deposition, annealing, and immobilization. These ultradense forests are needed to use carbon nanotubes as vias and interconnects in integrated circuits and thermal interface materials. Further density increase to 10(14) cm(-2) by reducing nanotube diameter is possible, and it is also applicable to nanowires.
RESUMO
We report a straightforward method of patterning large ordered arrays of metallic nanoparticles using existing semiconductor processing technology. The topographies of contact holes created on full 200 mm wafers serve as templates to pattern Ni or Co nanoparticles. Over a large range of synthesis conditions, these patterned nanoparticles are demonstrated to successfully catalyse the growth of carbon nanotubes (CNTs) selectively in the patterned areas of the wafer. This approach to catalyst deposition is scalable and fully compatible with existing semiconductor processing technology. Thus, it can be exploited for a variety of applications where confinement of materials in nanometric domains is necessary. These results represent a further step towards the integration of CNTs into conventional Si-based technology.