Synthesis and characterization of smooth ultrananocrystalline diamond films via low pressure bias-enhanced nucleation and growth

This letter describes the fundamental process underlying the synthesis of ultrananocrystalline diamond (UNCD) films, using a new low-pressure, heat-assisted bias-enhanced nucleation (BEN)/bias enhanced growth (BEG) technique, involving H2/CH4 gas chemistry. This growth process yields UNCD films similar to those produced by the Ar-rich/CH4 chemistries, with pure diamond nanograins (3–5 nm), but smoother surfaces (~6 nm rms) and higher growth rate (~1 µm/h). Synchrotron-based x-Ray absorption spectroscopy, atomic force microscopy, and transmission electron microscopy studies on the BEN-BEG UNCD films provided information critical to understanding the nucleation and growth mechanisms, and growth condition-nanostructure-property relationships

Are diamonds a MEMS\u27 best friend?

Next-generation military and civilian communication systems will require technologies capable of handling data/ audio, and video simultaneously while supporting multiple RF systems operating in several different frequency bands from the MHz to the GHz range [1]. RF microelectromechanical/nanoelectromechanical (MEMS/NEMS) devices, such as resonators and switches, are attractive to industry as they offer a means by which performance can be greatly improved for wireless applications while at the same time potentially reducing overall size and weight as well as manufacturing costs

Dynamic Processes in Biology, Chemistry, and Materials Science: Opportunities for UltraFast Transmission Electron Microscopy - Workshop Summary Report

This report summarizes a 2011 workshop that addressed the potential role of rapid, time-resolved electron microscopy measurements in accelerating the solution of important scientific and technical problems. A series of U.S. Department of Energy (DOE) and National Academy of Science workshops have highlighted the critical role advanced research tools play in addressing scientific challenges relevant to biology, sustainable energy, and technologies that will fuel economic development without degrading our environment. Among the specific capability needs for advancing science and technology are tools that extract more detailed information in realistic environments (in situ or operando) at extreme conditions (pressure and temperature) and as a function of time (dynamic and time-dependent). One of the DOE workshops, Future Science Needs and Opportunities for Electron Scattering: Next Generation Instrumentation and Beyond, specifically addressed the importance of electron-based characterization methods for a wide range of energy-relevant Grand Scientific Challenges. Boosted by the electron optical advancement in the last decade, a diversity of in situ capabilities already is available in many laboratories. The obvious remaining major capability gap in electron microscopy is in the ability to make these direct in situ observations over a broad spectrum of fast (µs) to ultrafast (picosecond [ps] and faster) temporal regimes. In an effort to address current capability gaps, EMSL, the Environmental Molecular Sciences Laboratory, organized an Ultrafast Electron Microscopy Workshop, held June 14-15, 2011, with the primary goal to identify the scientific needs that could be met by creating a facility capable of a strongly improved time resolution with integrated in situ capabilities. The workshop brought together more than 40 leading scientists involved in applying and/or advancing electron microscopy to address important scientific problems of relevance to DOE’s research mission. This workshop built on previous workshops and included three breakout sessions identifying scientific challenges in biology, biogeochemistry, catalysis, and materials science frontier areas of fundamental science that underpin energy and environmental science that would significantly benefit from ultrafast transmission electron microscopy (UTEM). In addition, the current status of time-resolved electron microscopy was examined, and the technologies that will enable future advances in spatio-temporal resolution were identified in a fourth breakout session

Tailoring silica–alumina-supported Pt–Pd as poison-tolerant catalyst for aromatics hydrogenation

The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt–Pd catalysts supported on amorphous silica–alumina was studied. Electron-energy-loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt–Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high-resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, which was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt–Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt–Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also, high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt–Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts toward sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal–sulfur bond on the electron-deficient Pt atoms. Thus, increasing the fraction of electron-deficient Pt on the surface of the bimetallic clusters increases the efficiency of the catalyst in the presence of sulfur-containing compounds

In Situ Spectroscopic Characterization of Ni_1–<i>x</i>Zn_<i>x</i>/ZnO Catalysts and Their Selectivity for Acetylene Semihydrogenation in Excess Ethylene

The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. Ni_0.85Zn_0.15O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni_1–<i>x</i>Zn_<i>x</i>, at ∼400 °C with <i>x</i> increasing with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β₁-NiZn formation at ∼550 °C. In comparison to a Ni/SiO₂ catalyst, Ni/ZnO necessitates a higher temperature for the reduction of Ni^II to Ni⁰, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO₂. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H–D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO₂. These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene

Continuously Tuning Epitaxial Strains by Thermal Mismatch

Strain engineering of thin films is a conventionally employed approach to enhance material properties and to energetically prefer ground states that would otherwise not be attainable. Controlling strain states in perovskite oxide thin films is usually accomplished through coherent epitaxy by using lattice-mismatched substrates with similar crystal structures. However, the limited choice of suitable oxide substrates makes certain strain states experimentally inaccessible and a continuous tuning impossible. Here, we report a strategy to continuously tune epitaxial strains in perovskite films grown on Si(001) by utilizing the large difference of thermal expansion coefficients between the film and the substrate. By establishing an adsorption-controlled growth window for SrTiO₃ thin films on Si using hybrid molecular beam epitaxy, the magnitude of strain can be solely attributed to thermal expansion mismatch, which only depends on the difference between growth and room temperature. Second-harmonic generation measurements revealed that structure properties of SrTiO₃ films could be tuned by this method using films with different strain states. Our work provides a strategy to generate continuous strain states in oxide/semiconductor pseudomorphic buffer structures that could help achieve desired material functionalities

Current status and future directions for in situ transmission electron microscopy

This review article discusses the current and future possibilities for the application of in situ transmission electron microscopy to reveal synthesis pathways and functional mechanisms in complex and nanoscale materials. The findings of a group of scientists, representing academia, government labs and private sector entities (predominantly commercial vendors) during a workshop, held at the Center for Nanoscale Science and Technology-National Institute of Science and Technology (CNST-NIST), are discussed. We provide a comprehensive review of the scientific needs and future instrument and technique developments required to meet them. Published by Elsevier B.V