Operando tribochemical formation of onion-like-carbon leads to macroscale superlubricity.

Stress-induced reactions at the sliding interface during relative movement are known to cause structural or chemical modifications in contacting materials. The nature of these modifications at the atomic level and formation of byproducts in an oil-free environment, however, remain poorly understood and pose uncertainties in predicting the tribological performance of the complete tribosystem. Here, we demonstrate that tribochemical reactions occur even in dry conditions when hydrogenated diamond-like carbon (H-DLC) surface is slid against two-dimensional (2D) molybdenum disulfide along with nanodiamonds in dry nitrogen atmosphere. Detailed experimental studies coupled with reactive molecular dynamics simulations reveal that at high contact pressures, diffusion of sulfur from the dissociated molybdenum disulfide led to amorphization of nanodiamond and subsequent transformation to onion-like carbon structures (OLCs). The in situ formation of OLCs at the sliding interface provide reduced contact area as well as incommensurate contact with respect to the H-DLC surface, thus enabling successful demonstration of superlubricity.

Metal-induced rapid transformation of diamond into single and multilayer graphene on wafer scale.

The degradation of intrinsic properties of graphene during the transfer process constitutes a major challenge in graphene device fabrication, stimulating the need for direct growth of graphene on dielectric substrates. Previous attempts of metal-induced transformation of diamond and silicon carbide into graphene suffers from metal contamination and inability to scale graphene growth over large area. Here, we introduce a direct approach to transform polycrystalline diamond into high-quality graphene layers on wafer scale (4 inch in diameter) using a rapid thermal annealing process facilitated by a nickel, Ni thin film catalyst on top. We show that the process can be tuned to grow single or multilayer graphene with good electronic properties. Molecular dynamics simulations elucidate the mechanism of graphene growth on polycrystalline diamond. In addition, we demonstrate the lateral growth of free-standing graphene over micron-sized pre-fabricated holes, opening exciting opportunities for future graphene/diamond-based electronics.

Direct Observation of Photoinduced Charge Separation in Ruthenium Complex/Ni(OH)2 Nanoparticle Hybrid.

Ni(OH)2 have emerged as important functional materials for solar fuel conversion because of their potential as cost-effective bifunctional catalysts for both hydrogen and oxygen evolution reactions. However, their roles as photocatalysts in the photoinduced charge separation (CS) reactions remain unexplored. In this paper, we investigate the CS dynamics of a newly designed hybrid catalyst by integrating a Ru complex with Ni(OH)2 nanoparticles (NPs). Using time resolved X-ray absorption spectroscopy (XTA), we directly observed the formation of the reduced Ni metal site (~60 ps), unambiguously demonstrating CS process in the hybrid through ultrafast electron transfer from Ru complex to Ni(OH)2 NPs. Compared to the ultrafast CS process, the charge recombination in the hybrid is ultraslow (≫50 ns). These results not only suggest the possibility of developing Ni(OH)2 as solar fuel catalysts, but also represent the first time direct observation of efficient CS in a hybrid catalyst using XTA.

Characterization of surface modifications by white light interferometry: applications in ion sputtering, laser ablation, and tribology experiments.

In materials science and engineering it is often necessary to obtain quantitative measurements of surface topography with micrometer lateral resolution. From the measured surface, 3D topographic maps can be subsequently analyzed using a variety of software packages to extract the information that is needed. In this article we describe how white light interferometry, and optical profilometry (OP) in general, combined with generic surface analysis software, can be used for materials science and engineering tasks. In this article, a number of applications of white light interferometry for investigation of surface modifications in mass spectrometry, and wear phenomena in tribology and lubrication are demonstrated. We characterize the products of the interaction of semiconductors and metals with energetic ions (sputtering), and laser irradiation (ablation), as well as ex situ measurements of wear of tribological test specimens. Specifically, we will discuss: i. Aspects of traditional ion sputtering-based mass spectrometry such as sputtering rates/yields measurements on Si and Cu and subsequent time-to-depth conversion. ii. Results of quantitative characterization of the interaction of femtosecond laser irradiation with a semiconductor surface. These results are important for applications such as ablation mass spectrometry, where the quantities of evaporated material can be studied and controlled via pulse duration and energy per pulse. Thus, by determining the crater geometry one can define depth and lateral resolution versus experimental setup conditions. iii. Measurements of surface roughness parameters in two dimensions, and quantitative measurements of the surface wear that occur as a result of friction and wear tests. Some inherent drawbacks, possible artifacts, and uncertainty assessments of the white light interferometry approach will be discussed and explained.

High-resolution secondary ion mass spectrometry depth profiling of nanolayers.

RATIONALE: Although the fundamental physical limits for depth resolution of secondary ion mass spectrometry are well understood in theory, the experimental work to achieve and demonstrate them is still ongoing. We report results of high-resolution TOF SIMS (time-of-flight secondary ion mass spectrometry) depth profiling experiments on a nanolayered structure, a stack of 16 alternating MgO and ZnO ~5.5 nm layers grown on a Si substrate by atomic layer deposition. METHODS: The measurements were performed using a newly developed approach implementing a low-energy direct current normally incident Ar(+) ion beam for ion milling (250 eV and 500 eV energy), in combination with a pulsed 5 keV Ar(+) ion beam at 60° incidence for TOF SIMS analysis. By this optimized arrangement, a noticeably improved version of the dual-beam (DB) approach to TOF SIMS depth profiling is introduced, which can be dubbed gentleDB. RESULTS: The mixing-roughness-information model was applied to detailed analysis of experimental results. It revealed that the gentleDB approach allows ultimate depth resolution by confining the ion beam mixing length to about two monolayers. This corresponds to the escape depth of secondary ions, the fundamental depth resolution limitation in SIMS. Other parameters deduced from the measured depth profiles indicated that a single layer thickness is equal to 6 nm so that the 'flat' layer thickness d is 3 nm and the interfacial roughness σ is 1.5 nm, thus yielding d + 2σ = 6 nm. CONCLUSIONS: We have demonstrated that gentleDB TOF SIMS depth profiling with noble gas ion beams is capable of revealing the structural features of a stack of nanolayers, resolving its original surface and estimating the roughness of interlayer interfaces, information which is difficult to obtain by traditional approaches.

Ion microscopy with resonant ionization mass spectrometry: time-of-flight depth profiling with improved isotopic precision.

There are four generally mutually exclusive requirements that plague many mass spectrometric measurements of trace constituents: (1) the small size (limited by the depth probed) of many interesting materials requires high useful yields to simply detect some trace elements, (2) the low concentrations of interesting elements require efficient discrimination from isobaric interferences, (3) it is often necessary to measure the depth distribution of elements with high surface and low bulk contributions, and (4) many applications require precise isotopic analysis. Resonant ionization mass spectrometry has made dramatic progress in addressing these difficulties over the past five years.

Laser-driven acoustic desorption of organic molecules from back-irradiated solid foils.

Laser-induced acoustic desorption (LIAD) from thin metal foils is a promising technique for gentle and efficient volatilization of intact organic molecules from surfaces of solid substrates. Using the single-photon ionization method combined with time-of-flight mass spectrometry, we have examined the neutral component of the desorbed flux in LIAD and compared it to that from direct laser desorption. These basic studies of LIAD, conducted for molecules of various organic dyes (rhodamine B, fluorescein, anthracene, coumarin, BBQ), have demonstrated detection of intact parent molecules of the analyte even at its surface concentrations corresponding to a submonolayer coating. In some cases (rhodamine B, fluorescein, BBQ), the parent molecular ion peak was accompanied by a few fragmentation peaks of comparable intensity, whereas for others, only peaks corresponding to intact parent molecules were detected. At all measured desorbing laser intensities (from 100 to 500 MW/cm2), the total amount of desorbed parent molecules depended exponentially on the laser intensity. Translational velocities of the desorbed intact molecules, determined for the first time in this work, were of the order of hundreds of meters per second, less than what has been observed in our experiments for direct laser desorption, but substantially greater than the possible perpendicular velocity of the substrate foil surface due to laser-generated acoustic waves. Moreover, these velocities did not depend on the desorbing laser intensity, which implies the presence of a more sophisticated mechanism of energy transfer than direct mechanical or thermal coupling between the laser pulse and the adsorbed molecules. Also, the total flux of desorbed intact molecules as a function of the total number of desorbing laser pulses, striking the same point on the target, decayed following a power law rather than an exponential function, as would have been predicted by the shake-off model. To summarize, the results of our experiments indicate that the LIAD phenomenon cannot be described in terms of simple mechanical shake-off or direct laser desorption. Rather, they suggest that multistep energy-transfer processes are involved. Two possible (and not mutually exclusive) qualitative mechanisms of LIAD that are based on formation of nonequilibrium energy states in the adsorbate-substrate system are proposed and discussed.