Christopher Muratore

Carbon Nanotube−MoS2 Composites as Solid Lubricants

Solid lubricants (SLs) characterized by low coefficients of friction (mu) and wear rates (w) drastically improve the life span of instruments that undergo extreme frictional wear. However, the performance of SLs such as sputtered or nanoparticulate molybdenum disulfide (MoS(2)), tungsten disulfide (WS(2)), or graphite deteriorates heavily under extreme operational conditions such as elevated temperatures and high humidity. Here, we present our preliminary results, which demonstrate that composites of carbon nanotubes (CNTs) and MoS(2) produced by electrodeposition of MoS(2) on vertically aligned CNT films have low mu ( approximately 0.03) and w (approximately 10(-13) mm(3)/N.mm) even at 300 degrees C, which are about 2 orders of magnitude better than those of nanoparticulate MoS(2)-based coatings. The high load-bearing capacity of CNTs provides a strong enduring support to MoS(2) nanoclusters and is responsible for their ultralow w. The incorporation of these composites in liquid lubricants reduces the friction coefficient of the liquid lubricants by approximately 15%. The technique described here to produce SL coatings with extremely appealing frictional properties will provide valuable solutions for a variety of tribological applications where the coatings encounter high temperature, reduced pressure, and/or low- and high-humidity conditions.

Continuous ultra-thin MoS2 films grown by low-temperature physical vapor deposition

Uniform growth of pristine two dimensional (2D) materials over large areas at lower temperatures without sacrifice of their unique physical properties is a critical pre-requisite for seamless integration of next-generation van der Waals heterostructures into functional devices. This Letter describes a vapor phase growth technique for precisely controlled synthesis of continuous, uniform molecular layers of MoS2 on silicon dioxide and highly oriented pyrolitic graphite substrates of over several square centimeters at 350u2009°C. Synthesis of few-layer MoS2 in this ultra-high vacuum physical vapor deposition process yields materials with key optical and electronic properties identical to exfoliated layers. The films are composed of nano-scale domains with strong chemical binding between domain boundaries, allowing lift-off from the substrate and electronic transport measurements from contacts with separation on the order of centimeters.

Cross-plane thermal properties of transition metal dichalcogenides

In this work, we explore the thermal properties of hexagonal transition metal dichalcogenide compounds with different average atomic masses but equivalent microstructures. Thermal conductivity values of sputtered thin films were compared to bulk crystals. The comparison revealed a >10 fold reduction in thin film thermal conductivity. Structural analysis of the films revealed a turbostratic structure with domain sizes on the order of 5–10u2009nm. Estimates of phonon scattering lengths at domain boundaries based on computationally derived group velocities were consistent with the observed film microstructure, and accounted for the reduction in thermal conductivity compared to values for bulk crystals.

Infrared Optical Properties of Amorphous and Nanocrystalline Ta2O5 Thin Films

The optical constants of tantalum pentoxide (Ta2O5) are determined in a broad spectral region from the visible to the far infrared. Ta2O5 films of various thicknesses from approximately 170 to 1600u2009nm are deposited using reactive magnetron sputtering on Si substrates. X-ray diffraction shows that the as-deposited films are amorphous, and annealing in air at 800u2009°C results in the formation of nanocrystalline Ta2O5. Ellipsometry is used to obtain the dispersion in the visible and near-infrared. Two Fourier-transform infrared spectrometers are used to measure the transmittance and reflectance at wavelengths from 1 to 1000u2009μm. The surface topography and microstructure of the samples are examined using atomic force microscopy, confocal microscopy, and scanning electron microscopy. Classical Lorentz oscillators are employed to model the absorption bands due to phonons and impurities. A simple model is introduced to account for light scattering in the annealed films, which contain micro-cracks. For the unanneale...

Nitrogen and hydrogen plasma treatments of multiwalled carbon nanotubes

This article investigates plasma treatment of vertically aligned multiwall carbon nanotube (CNT) films in different plasma environments for modification of surface chemistry and morphology. The surfaces of the CNTs were functionalized with a pulsed dc plasma treatment, where the power was directly applied to the nanotube film in low pressure argon/nitrogen and argon/hydrogen backgrounds. Optical emission spectroscopy was used to detect atomic and molecular excitations in the gas mixtures as well as in pure gases in the vicinity of the CNT films. In situ x-ray photoelectron spectroscopy was performed on the treated samples to examine CNT surface chemistry after treatment. The analysis of CNT films after nitrogen and hydrogen treatment indicated formation of both Cue5f8N and Cue5f8H bonds, respectively. Correlations of the plasma characteristics to the surface chemistry and morphology of the CNT surfaces are discussed.

Limited thermal conductance of metal-carbon interfaces

The thermal conductance for a series of metal-graphite interfaces has been experimentally measured with time-domain thermoreflectance (TDTR). For metals with Debye temperatures up to ∼400u2009K, a linear relationship exists with the thermal conductance values. For metals with Debye temperatures in excess of ∼400u2009K, the measured metal-graphite thermal conductance values remain constant near 60u2009MW m−2 K−1. Titanium showed slightly higher conductance than aluminum, despite the closeness of atomic mass and Debye temperature for the two metals. Surface analysis was used to identify the presence of titanium carbide at the interface in contrast to the aluminum and gold-carbon interfaces (with no detectable carbide phases). It was also observed that air-cleaved graphite surfaces in contact with metals yielded slightly higher thermal conductance than graphite surfaces cleaved in vacuo. Examination of samples with scanning electron microscopy revealed that the lack of absorbed molecules on the graphite surface resulted...

Effect of plasma flux composition on the nitriding rate of stainless steel

The total ion flux and nitriding rate for stainless steel specimens exposed to a modulated electron beam generated argon-nitrogen plasma were measured as a function of distance from the electron beam axis. The total ion flux decreased linearly with distance, but the nitriding rate increased under certain conditions, contrary to other ion flux/nitriding rate comparisons published in the literature. Variation in ion flux composition with distance was explored with a mass spectrometer and energy analyzer as a possible explanation for the anomalous nitriding rate response to ion flux magnitude. A transition in ion flux composition from mostly N2+ to predominantly N+ ions with increasing distance was observed. Significant differences in molecular and atomic nitrogen ion energy distributions at a negatively biased electrode were also measured. An explanation for nitriding rate dependence based on flux composition and magnitude is proposed.

Etching with electron beam generated plasmas

A modulated electron beam generated plasma has been used to dry etch standard photoresist materials and silicon. Oxygen–argon mixtures were used to etch organic resist material and sulfur hexafluoride mixed with argon or oxygen was used for the silicon etching. Etch rates and anisotropy were determined with respect to gas compositions, incident ion energy (from an applied rf bias) and plasma duty factor. For 1818 negative resist and i-line resists the removal rate increased nearly linearly with ion energy (up to 220nm∕min at 100eV), with reasonable anisotropic pattern transfer above 50eV. Little change in etch rate was seen as gas composition went from pure oxygen to 70% argon, implying the resist removal mechanism in this system required the additional energy supplied by the ions. With silicon substrates at room temperature, mixtures of argon and sulfur hexafluoride etched approximately seven times faster (1375nm∕min) than mixtures of oxygen and sulfur hexafluoride (∼200nm∕min) with 200eV ions, the diffe...

Temporally and spatially resolved plasma spectroscopy in pulsed laser deposition of ultra-thin boron nitride films

Physical vapor deposition (PVD) has recently been investigated as a viable, alternative growth technique for two-dimensional materials with multiple benefits over other vapor deposition synthesis methods. The high kinetic energies and chemical reactivities of the condensing species formed from PVD processes can facilitate growth over large areas and at reduced substrate temperatures. In this study, chemistry, kinetic energies, time of flight data, and spatial distributions within a PVD plasma plume ablated from a boron nitride (BN) target by a KrF laser at different pressures of nitrogen gas were investigated. Time resolved spectroscopy and wavelength specific imaging were used to identify and track atomic neutral and ionized species including B+, B*, N+, N*, and molecular species including N2*, N2+, and BN. Formation and decay of these species formed both from ablation of the target and from interactions with the background gas were investigated and provided insights into fundamental growth mechanisms of...

Control of plasma flux composition incident on TiN films during reactive magnetron sputtering and the effect on film microstructure

A hybrid plasma enhanced physical vapor deposition (PEPVD) system consisting of an unbalanced dc magnetron and a pulsed electron beam-produced plasma was used to deposit reactively sputtered titanium nitride thin films. The system allowed for control of the magnitudes of the ion and neutral flux, in addition to the type of nitrogen ions (atomic or molecular) that comprised the flux. For all deposition experiments, the magnitude of the ion flux incident on the substrate was held constant, but the composition of the total flux was varied. X-ray diffraction and atomic force microscopy showed that crystallographic texture and surface morphology of the films were affected by the plasma flux composition during growth.