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An efficient and chemoselective methodology deploying gold- N -heterocyclic carbene (NHC) complexes as catalysts in the hydrofluorination of terminal alkynes using aqueous HF has been developed. Mechanistic studies shed light on an in situ generated catalyst, formed by the reaction of Bronsted basic gold pre-catalysts with HF in water, which exhibits the highest reactivity and chemoselectivity. The catalytic system has a wide alkyl substituted-substrate scope, and stoichiometric as well as catalytic reactions with tailor-designed gold pre-catalysts enable the identification of various gold species involved along the catalytic cycle. Computational studies aid in understanding the chemoselectivity observed through examination of key mechanistic steps for phosphine- and NHC-coordinated gold species bearing the triflate counterion and the elusive key complex bearing a bifluoride counterion.

The thermal atomic layer etching (ALE) of germanium-rich SiGe was demonstrated using an oxidation and "conversion-etch" mechanism with oxygen (O-2) or ozone (O-3), hydrofluoric acid (HF), and trimethylaluminum [TMA, Al(CH3)(3)] as the reactants. The crystalline germanium-rich SiGe film was prepared using physical vapor deposition and had a composition of Si0.15Ge0.85. In situ spectroscopic ellipsometry was employed to monitor the thickness of both the SiGe film and the surface oxide layer on the SiGe film during thermal ALE. Using a reactant sequence of O-2-HF-TMA, the etch rate of the SiGe film increased progressively with temperatures from 225 to 290 degrees C. At 290 degrees C, the SiGe film thickness decreased linearly at a rate of 0.57 angstrom /cycle with a surface oxide thickness of 18-19 angstrom. This etch rate was obtained using reactant pressures of 25, 0.2, and 0.4Torr and doses of 1.5, 1.0, and 1.0s for O-2, HF, and TMA, respectively. The TMA and HF reactions were self-limiting and the O-2 reaction was reasonably self-limiting at 290 degrees C. Using an O-3-HF-TMA reaction sequence, the SiGe ALE etch rate was 0.42 angstrom /cycle at 290 degrees C. This etch rate was obtained using reactant pressures of 15, 0.2, and 0.4Torr and dose times of 0.5, 1.0, and 1.0s for O-3, HF, and TMA, respectively. The O-3, TMA, and HF reactions were all self-limiting at 290 degrees C. Atomic force microscopy images revealed that thermal ALE with the O-2-HF-TMA or O-3-HF-TMA reaction sequences did not roughen the surface of the SiGe film. The SiGe film was etched selectively compared with Si or Si3N4 at 290 degrees C using an O-2-HF-TMA reaction sequence. The etch rate for the SiGe film was >10 times faster than Si(100) or Si3N4 that was prepared using low-pressure chemical vapor deposition. This selectivity for the SiGe film will be useful to fabricate Si nanowires and nanosheets using SiGe as the sacrificial layer.

This paper contains a summary of the results from the first years of observations with the HIFI instrument onboard ESA's Herschel space observatory. The paper starts by outlining the goals and possibilities of far-infrared and submillimeter astronomy, the limitations of the Earth's atmosphere, and the scientific scope of the Herschel-HIFI mission. The presentation of science results from the mission follows the life cycle of gas in galaxies as grouped into five themes: Structure of the interstellar medium, First steps in interstellar chemistry, Formation of stars and planets, Solar system results and Evolved stellar envelopes. The HIFI observations paint a picture where the interstellar medium in galaxies has a mixed, rather than a layered structure; the same conclusion may hold for protoplanetary disks. In addition, the HIFI data show that exchange of matter between comets and asteroids with planets and moons plays a large role. The paper concludes with an outlook to future instrumentation in the far-infrared and submillimeter wavelength ranges., Invited review paper to appear in Advances of Space Research; 32 pages, 9 figures. See http://www.sron.rug.nl/~vdtak/adspres.pdf for a 14-page journal-style version

We present Herschel/HIFI observations of 30 transitions of water isotopologues toward the high-mass star forming region NGC 6334 I. The line profiles of H_2^{16}O, H_2^{17}O, H_2^{18}O, and HDO show a complex pattern of emission and absorption components associated with the embedded hot cores, a lower-density envelope, two outflow components, and several foreground clouds, some associated with the NGC 6334 complex, others seen in projection against the strong continuum background of the source. Our analysis reveals an H2O ortho/para ratio of 3 +/- 0.5 in the foreground clouds, as well as the outflow. The water abundance varies from ~10^{-8} in the foreground clouds and the outer envelope to ~10^{-6} in the hot core. The hot core abundance is two orders of magnitude below the chemical model predictions for dense, warm gas, but within the range of values found in other Herschel/HIFI studies of hot cores and hot corinos. This may be related to the relatively low gas and dust temperature (~100 K), or time dependent effects, resulting in a significant fraction of water molecules still locked up in dust grain mantles. The HDO/H_2O ratio in NGC 6334 I, ~2 10^{-4}, is also relatively low, but within the range found in other high-mass star forming regions., Comment: To appear in the Astrophysical Journal; 15 pages, 10 figures, 7 tables

A three step route to single diastereoisomers of the vicinal trifluoromethyl motif is described. The route starts from either syn- or anti-α,β-epoxy alcohols and takes a direct approach in that each of the three steps introduces a fluorine atom in a regio- and stereo-specific manner. Starting from either the syn- or the anti-α,β-epoxy alcohol, stereospecific reactions generate two separate diastereoisomeric series of this motif. The route is a significant improvement on an earlier six step strategy.

International audience; HF acid attack of SiO2 and Si3N4 substrates is analyzed to improve the sensitivity of a sensor based on inicrocantilever. Ex situ analysis of the etching using XPS, SIMS and AFM show significant changes in the anisotropy and the rate of the etching of the oxides on SiO2 and Si3N4 surface. Those differences influence the kinetic evolution of the plastic bending deflection of the cantilever coated with SiO2 and Si3N4 layer, respectively. The linear dependence between the HF concentration and the Si3N4 cantilever bending corresponds to a deep attack of the layer whereas the nonlinear behavior observed for SiO2 layer can be explained by a combination of deep and lateral etchina. The cantilever bending is discussed in terms of free surface energy, layer thickness and grain size. (c) 2006 Elsevier B.V All rights reserved.

The clumpy density structure of photon-dominated regions is well established, but the physical properties of the clumps and of the surrounding interclump medium are only approximately known. The aim of this paper is to constrain the physical and chemical conditions in the Orion Bar, a prototypical nearby photon-dominated region. We present observations of the HF J=1-0 line, which appears in emission toward the Orion Bar, and compare the brightness of the line to non-LTE radiative transfer calculations. The large width of the HF line suggests an origin of the emission in the interclump gas, but collisional excitation by H2 in the interclump gas underpredicts the observed line intensity by factors of 3-5. In contrast, an origin of the line in the dense clumps requires a density of ~10^9 cm^-3, 10-100 times higher than previous estimates, which is unlikely. However, electron impact excitation reproduces our observations for T = 100 K and n(e) = 10 cm^-3, as expected for the interclump gas. We conclude that HF emission is a signpost of molecular gas with a high electron density. Similar conditions may apply to active galactic nuclei where HF also appears in emission., Comment: Accepted for publication in A&A; 4 pages, 1 figure