Transfer of Graphene with Protective Oxide Layers

Transfer of graphene, grown by Chemical Vapor Deposition (CVD), to a substrate of choice, typically involves deposition of a polymeric layer (typically, poly(methyl methacrylate, PMMA or polydimethylsiloxane, PDMS). These polymers are quite hard to remove without leaving some residues behind. Here we study a transfer of graphene with a protective thin oxide layer. The thin oxide layer is grown by Atomic Deposition Layer (ALD) on the graphene right after the growth stage on Cu foils. One can further aid the oxide-graphene transfer by depositing a very thin polymer layer on top of the composite (much thinner than the usual thickness) following by a more aggressive polymeric removal methods, thus leaving the graphene intact. We report on the nucleation growth process of alumina and hafnia films on the graphene, their resulting strain and on their optical transmission. We suggest that hafnia is a better oxide to coat the graphene than alumina in terms of uniformity and defects.Comment: 13 pgs, 13 figure

Achieving Superlubricity with 2D Transition Metal Carbides (MXenes) and MXene/Graphene Coatings

Two-dimensional (2D) materials have demonstrated unique friction and antiwear properties unmatched by their bulk (3D) counterparts. A relatively new, large and quickly growing family of two-dimensional early transition metal carbides and nitrides (MXenes) present a great potential in different applications. There is a growing interest in understanding the mechanical and tribological properties of MXenes, however, no report of MXene superlubricity in a solid lubrication process at the macroscale has been presented. Here we investigate the tribological properties of two-dimensional titanium carbide (Ti3C2) MXene deposited on SiO2-coated silicon (Si) substrates subjected to wear by sliding against a diamond-like carbon (DLC)-coated steel ball counterbody using a ball-on-disc tribometer. We have observed that a reduction of the friction coefficient to the superlubric regime (0.0067 ± 0.0017) can be achieved with Ti3C2 MXene in dry nitrogen environment. Moreover, the addition of graphene to Ti3C2 further reduced the friction by 37.3% and wear by the factor of 2 as compared to Ti3C2 alone, while the superlubricity behavior of the MXene remains unchanged. These results open up new possibilities for exploring the family of MXenes in various tribological applications

Small Amplitude Reciprocating Wear Performance of Diamond-like Carbon Films: Dependence of Film Composition and Counterface Material

Small amplitude (50 μm) reciprocating wear of hydrogen-containing diamond-like carbon (DLC) films of different compositions has been examined against silicon nitride and polymethyl-methacrylate (PMMA) counter-surfaces, and compared with the performance of an uncoated steel substrate. Three films were studied: a DLC film of conventional composition, a fluorine-containing DLC film (F-DLC), and silicon-containing DLC film. The films were deposited on steel substrates from plasmas of organic precursor gases using the Plasma Immersion Ion Implantation and Deposition (PIIID) process, which allows for the non-line-of-sight deposition of films with tailored compositions. The amplitude of the resistive frictional force during the reciprocating wear experiments was monitored in situ, and the magnitude of film damage due to wear was evaluated using optical microscopy, optical profilometry, and atomic force microscopy. Wear debris was analyzed using scanning electron microscopy and energy dispersive spectroscopy. In terms of friction, the DLC and silicon-containing DLC films performed exceptionally well, showing friction coefficients less than 0.1 for both PMMA and silicon nitride counter-surfaces. DLC and silicon-containing DLC films also showed significant reductions in transfer of PMMA compared with the uncoated steel. The softer F-DLC film performed similarly well against PMMA, but against silicon nitride, friction displayed nearly periodic variations indicative of cyclic adhesion and release of worn film material during the wear process. The results demonstrate that the PIIID films achieve the well-known advantageous performance of other DLC films, and furthermore that the film performance can be significantly affected by the addition of dopants. In addition to the well-established reduction of friction and wear that DLC films generally provide, we show here that another property, low adhesiveness with PMMA, is another significant benefit in the use of DLC films

Thermal Stability and Rehybridization of Carbon Bonding in Tetrahedral Amorphous Carbon

We preform a quantitative investigation of the energetics of thermally induced sp3 → sp2 conversion of carbon-carbon bonds in tetrahedral amorphous carbon (ta-C) films by using near edge x-ray absorption fine structure (NEXAFS) and Raman spectroscopy. We investigate the evolution of the bonding configuration in ta-C thin films subjected to high temperature annealing in flowing Argon gas using a rapid thermal annealing furnace over the range of 200-1000 ºC. We observe no substantial change in bonding structure below 600 ºC, and by 1000 ºC a significant increase in the sp2 bonding in the film is observed. No oxygen bonding is detected in the NEXAFS spectra, but we do observe an isosbestic point, demonstrating that the thermally driven sp3 → sp2 conversion reaction occurs without passing through an intermediate transition state. This allows us to use NEAFS spectra of thermally annealed ta-C films to quantitatively determine that the activation energy for directly converting the sp3-bonded carbon to the s

Temperature dependence of mechanical stiffness and dissipation in ultrananocrystalline diamond

Ultrananocrystalline diamond (UNCD) films are promising for radio frequency micro electro mechanical systems (RF-MEMS) resonators due to the extraordinary physical properties of diamond, such as high Young’s modulus, quality factor, and stable surface chemistry. UNCD films used for this study are grown on 150 mm silicon wafers using hot filament chemical vapor deposition (HFCVD) at 680°C. UNCD fixed free (cantilever) resonator structures designed for the resonant frequencies in the kHz range have been fabricated using conventional microfabrication techniques and are wet released. Resonant excitation and ring down measurements in the temperature range of 138 K to 300 K were conducted under ultra high vacuum (UHV) conditions in a custom built UHV AFM stage to determine the temperature dependence of Young’s Modulus and dissipation (quality factor) in these UNCD cantilever structures. We measured a temperature coefficient of frequency (TCF) of 121 and 133 ppm/K for the cantilevers of 350 ìm and 400 ìm length respectively. Young’s modulus of the cantilevers increased by about 3.1% as the temperature was reduced from 300 K to 138 K. This is the first such measurement for UNCD and suggests that the nanostructure plays a significant role in modifying the thermo-mechanical response of the material. The quality factor of these resonators showed a moderate increase as the cantilevers were cooled from 300 K to 138 K. The results suggest that surface and bulk defects significantly contribute to the observed dissipation in UNCD resonators

Mechanical stiffness and dissipation in ultrananocrystalline diamond microresonators

We have characterized mechanical properties of ultrananocrystalline diamond UNCD thin films grown using the hot filament chemical vapor deposition HFCVD technique at 680 °C, significantly lower than the conventional growth temperature of 800 °C. The films have 4.3% sp2 content in the near-surface region as revealed by near edge x-ray absorption fine structure spectroscopy. The films, 1 m thick, exhibit a net residual compressive stress of 3701 MPa averaged over the entire 150 mm wafer. UNCD microcantilever resonator structures and overhanging ledges were fabricated using lithography, dry etching, and wet release techniques. Overhanging ledges of the films released from the substrate exhibited periodic undulations due to stress relaxation. This was used to determine a biaxial modulus of 8382 GPa. Resonant excitation and ring-down measurements in the kHz frequency range of the microcantilevers were conducted under ultrahigh vacuum UHV conditions in a customized UHV atomic force microscope system to determine Young’s modulus as well as mechanical dissipation of cantilever structures at room temperature. Young’s modulus is found to be 79030 GPa. Based on these measurements, Poisson’s ratio is estimated to be 0.0570.038. The quality factors Q of these resonators ranged from 5000 to 16000. These Q values are lower than theoretically expected from the intrinsic properties of diamond. The results indicate that surface and bulk defects are the main contributors to the observed dissipation in UNCD resonators

Origin of Ultralow Friction andWear in Ultrananocrystalline Diamond

The impressively low friction and wear of diamond in humid environments is debated to originate from either the stability of the passivated diamond surface or sliding-induced graphitization/rehybridization of carbon. We find ultralow friction and wear for ultrananocrystalline diamond surfaces even in dry environments, and observe negligible rehybridization except for a modest, submonolayer amount under the most severe conditions (high load, low humidity). This supports the passivation hypothesis, and establishes a new regime of exceptionally low friction and wear for diamond