Gyula Eres

Role of hydrogen in chemical vapor deposition growth of large single-crystal graphene.

We show that graphene chemical vapor deposition growth on copper foil using methane as a carbon source is strongly affected by hydrogen, which appears to serve a dual role: an activator of the surface bound carbon that is necessary for monolayer growth and an etching reagent that controls the size and morphology of the graphene domains. The resulting growth rate for a fixed methane partial pressure has a maximum at hydrogen partial pressures 200-400 times that of methane. The morphology and size of the graphene domains, as well as the number of layers, change with hydrogen pressure from irregularly shaped incomplete bilayers to well-defined perfect single layer hexagons. Raman spectra suggest the zigzag termination in the hexagons as more stable than the armchair edges.

Patterned growth of individual and multiple vertically aligned carbon nanofibers

The results of studies of patterned growth of vertically aligned carbon nanofibers (VACNFs) prepared by plasma-enhanced chemical vapor deposition are reported. Nickel (Ni) dots of various diameters and Ni lines with variable widths and shapes were fabricated using electron beam lithography and evaporation, and served for catalytic growth of VACNFs whose structure was determined by high resolution transmission electron microscopy. It is found that upon plasma pre-etching and heating up to 600–700 °C, thin films of Ni break into droplets which initiate the growth of VACNFs. Above a critical dot size multiple droplets are formed, and consequently multiple VACNFs grow from a single evaporated dot. For dot sizes smaller than the critical size only one droplet is formed, resulting in a single VACNF. In the case of a patterned line, the growth mechanism is similar to that from a dot. VACNFs grow along the line, and above a critical linewidth multiple VACNFs are produced across the line. The mechanism of the form...

Free-standing optical gold bowtie nanoantenna with variable gap size for enhanced Raman spectroscopy.

We describe plasmonic interactions in suspended gold bowtie nanoantenna leading to strong electromagnetic field (E) enhancements. Surface-enhanced Raman scattering (SERS) was used to demonstrate the performance of the nanoantenna. In addition to the well-known gap size dependence, up to 2 orders of magnitude additional enhancement is observed with elevated bowties. The overall behavior is described by a SERS enhancement factor exceeding 10(11) along with an anomalously weak power law dependence of E on the gap size in a range from 8 to 50 nm that is attributed to a plasmonic nanocavity effect occurring when the plasmonic interactions enter a strongly coupled regime.

Effect of catalyst film thickness on carbon nanotube growth by selective area chemical vapor deposition

The correlation between prepatterned catalyst film thickness and carbon nanotube (CNT) growth by selective area chemical vapor deposition (CVD) was studied using Fe and Ni as catalyst. To eliminate sample-to-sample variations and create a growth environment in which the film thickness is the sole variable, samples with continuously changing catalyst film thickness from 0 to 60 nm were fabricated by electron-gun evaporation. Using thermal CVD CNTs preferentially grow as a dense mat on the thin regions of the catalyst film. Moreover, beyond a certain critical film thickness no tubes were observed. The critical film thickness for CNT growth was found to increase with substrate temperature. There appears to be no strong correlation between the film thickness and the diameter of the tubes. In contrast, using plasma enhanced CVD with Ni as catalyst, vertically oriented CNTs grow in the entire range of catalyst film thickness. The diameter of these CNTs shows a strong correlation with the catalyst film thickness...

Fast and highly anisotropic thermal transport through vertically aligned carbon nanotube arrays

This letter reports on fast and highly anisotropic thermal transport through millimeter-tall, vertically aligned carbon nanotube arrays (VANTAs) synthesized by chemical vapor deposition on Si substrates. Thermal diffusivity measurements were performed for both longitudinal and transverse to the nanotube alignment direction, with longitudinal values as large as 2.1±0.2cm2∕s and anisotropy ratios as large as 72. Longitudinal thermal conductivities of 15.3±1.8W∕(mK) for porous 8±1vol% VANTAs in air and 5.5±0.7W∕(mK) for epoxy-infiltrated VANTAs already exceed those of phase-changing thermal interface materials used in microelectronics. Data suggest that further improvements are possible through optimization of density and defects in the arrays.

Growth behavior of carbon nanotubes on multilayered metal catalyst film in chemical vapor deposition

Abstract The temperature and time dependences of carbon nanotube (CNT) growth by chemical vapor deposition are studied using a multilayered Al/Fe/Mo catalyst on silicon substrates. Within the 600–1100 °C temperature range of these studies, narrower temperature ranges were determined for the growth of distinct types of aligned multi-walled CNTs and single-walled CNTs by using high-resolution transmission electron microscopy and Raman spectroscopy. At 900 °C, in contrast to earlier work, double-walled CNTs are found more abundant than single-walled CNTs. Defects also are found to accumulate faster than the ordered graphitic structure if the growth of CNTs is extended to long durations.

Characterization of thin-film amorphous semiconductors using spectroscopic ellipsometry

Spectroscopic ellipsometry (SE) has been used to routinely characterize amorphous silicon nitride and diamond thin films. Since SE measurements do not yield quantities of interest directly, the SE data must first be fit to a model to obtain useful parameters such as film thickness and optical functions. Recently, we have developed the Tauc-Lorentz (TL) model for the optical functions of amorphous materials [Appl. Phys. Lett. 69, 371373, 2137 (1996).], which has been very useful in interpreting these SE results. A 4parameter model is usually sufficient to describe the optical functions of the thin film to the accuracy of the ellipsometer. One of these parameters, the band gap Eg, correlates with other mechanical and chemical properties of the film, such as the silicon-to-nitrogen ratio in silicon nitride films, and to the sp 3 -bonded carbon fraction and the hardness of

In situ control of the catalyst efficiency in chemical vapor deposition of vertically aligned carbon nanotubes on predeposited metal catalyst films

Premature termination of growth, presumably because of catalyst deactivation, is an undesirable side effect of chemical vapor deposition of vertically aligned carbon nanotubes on predeposited metal catalyst films. The addition of ferrocene, an effective precursor for in situ Fe formation, was found to enhance carbon nanotubegrowth rates and extend growth to 3.25 mm thick carbon nanotube films. Ferrocene was introduced into the gas stream by thermal evaporation concurrently with acetylene using a specially constructed source. The key factor facilitating the growth of thick carbon nanotube films was the independent and precise control of the ferrocene amount in the feedstock. The carbon nanotube films were characterized by scanning and transmission electron microscopy, and Raman spectroscopy. The temperature dependence of the carbon nanotubegrowth with ferrocene exhibits a steep drop at high substrate temperatures and a loss of vertical alignment at 900 ° C . The negative temperature coefficient of the growth rate suggests that the reaction mechanism of vertically aligned carbon nanotubegrowth is governed by a heterogeneous intermediate step.

In situ growth rate measurements and length control during chemical vapor deposition of vertically aligned multiwall carbon nanotubes

Time-resolved reflectivity is employed as an in situ diagnostic in thermal chemical vapor deposition of vertically aligned arrays of multiwall carbon nanotubes (VAA–MWNT). Fabry–Ṕerot interference fringes and attenuation of a reflected HeNe laser beam are used to measure the length of VAA–MWNT throughout the first 3–8 μm of growth yielding in situ measurements of growth rates and kinetics and the capability to observe the onset and termination of growth. VAA–MWNT growth is characterized between 565 and 750 °C on Si substrates with evaporated Al/Fe/Mo multilayer catalysts and acetylene feedstock. Nanotube lengths were controlled by rapid evacuation of the chamber at predetermined reflectivities, and it was demonstrated that growth can be restarted at later times. The extinction coefficients of the VAA–MWNT were studied and correlated with nanotube wall structure. Growth rates for VAA–MWNT are found to vary depending on the catalyst preparation, temperature, and time. Both the highest growth rates (0.3 μm/s...

Cooperative Island Growth of Large-Area Single-Crystal Graphene on Copper Using Chemical Vapor Deposition

In this work we explore the kinetics of single-crystal graphene growth as a function of nucleation density. In addition to the standard methods for suppressing nucleation of graphene by pretreatment of Cu foils using oxidation, annealing, and reduction of the Cu foils prior to growth, we introduce a new method that further reduces the graphene nucleation density by interacting directly with the growth process at the onset of nucleation. The successive application of these two methods results in roughly 3 orders of magnitude reduction in graphene nucleation density. We use a kinetic model to show that at vanishingly low nucleation densities carbon incorporation occurs by a cooperative island growth mechanism that favors the formation of substrate-size single-crystal graphene. The model reveals that the cooperative growth of millimeter-size single-crystal graphene grains occurs by roughly 3 orders of magnitude increase in the reactive sticking probability of methane compared to that in random island nucleation.