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At least 73 records · Page 4

Epitaxial c-axis oriented BaTiO{sub 3} thin films on SrTiO{sub 3}-buffered Si(001) by atomic layer deposition

Atomic layer deposition (ALD) of epitaxial c-axis oriented BaTiO{sub 3} (BTO) on Si(001) using a thin (1.6 nm) buffer layer of SrTiO{sub 3} (STO) grown by molecular beam epitaxy is reported. The ALD growth of crystalline BTO films at 225 °C used barium bis(triisopropylcyclopentadienyl), titanium tetraisopropoxide, and water as co-reactants. X-ray diffraction (XRD) reveals a high degree of crystallinity and c-axis orientation of as-deposited BTO films. Crystallinity is improved after vacuum annealing at 600 °C. Two-dimensional XRD confirms the tetragonal structure and orientation of 7–20-nm thick films. The effect of the annealing process on the BTO structure is discussed. A clean STO/Si interface is found using in-situ X-ray photoelectron spectroscopy and confirmed by cross-sectional scanning transmission electron microscopy. The capacitance-voltage characteristics of 7–20 nm-thick BTO films are examined and show an effective dielectric constant of ∼660 for the heterostructure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Anharmonicity and atomic distribution of SnTe and PbTe thermoelectrics

The structure and lattice dynamics of rock-salt thermoelectric materials SnTe and PbTe are investigated with single crystal and powder neutron diffraction, inelastic neutron scattering (INS), and first-principles simulations. Our first-principles calculations of the radial distribution function (RDF) in both SnTe and PbTe show a clear asymmetry in the first nearest-neighbor (1NN) peak, which increases with temperature, in agreement with experimental reports (Ref. 1,2). We show that this peak asymmetry for the 1NN Sn–Te or Pb–Te bond results from large-amplitude anharmonic vibrations (phonons). No atomic off-centering is found in our simulations. In addition, the atomic mean square displacements derived from our diffraction data reveal stiffer bonding at the anion site, in good agreement with the partial phonon densities of states from INS, and first-principles calculations. In conclusion, these results provide clear evidence for large-amplitude anharmonic phonons associated with the resonant bonding leading to the ferroelectric instability.

36 MATERIALS SCIENCE↗

Evolution of atomic structure during nanoparticle formation

Understanding the mechanism of nanoparticle formation during synthesis is a key prerequisite for the rational design and engineering of desirable materials properties, yet remains elusive due to the difficulty of studying structures at the nanoscale under real conditions. Here, the first comprehensive structural description of the formation of a nanoparticle, yttria-stabilized zirconia (YSZ), all the way from its ionic constituents in solution to the final crystal, is presented. The transformation is a complicated multi-step sequence of atomic reorganizations as the material follows the reaction pathway towards the equilibrium product. Prior to nanoparticle nucleation, reagents reorganize into polymeric species whose structure is incompatible with the final product. Instead of direct nucleation of clusters into the final product lattice, a highly disordered intermediate precipitate forms with a local bonding environment similar to the product yet lacking the correct topology. During maturation, bond reforming occurs by nucleation and growth of distinct domains within the amorphous intermediary. The present study moves beyond kinetic modeling by providing detailed real-time structural insight, and it is demonstrated that YSZ nanoparticle formation and growth is a more complex chemical process than accounted for in conventional models. This level of mechanistic understanding of the nanoparticle formation is the first step towards more rational control over nanoparticle synthesis through control of both solution precursors and reaction intermediaries.

solar (photovoltaic), electrodes - solar, charge t↗

Ion-Atom Cold Collisions and Atomic Clocks

Collisions between ultracold neutral atoms have for some time been the subject of investigation, initially with hydrogen and more recently with laser cooled alkali atoms. Advances in laser cooling and trapping of neutral atoms in a Magneto-Optic Trap (MOT) have made cold atoms available as the starting point for many laser cooled atomic physics investigations. The most spectacularly successful of these, the observation of Bose-Einstein Condensation (BEC) in a dilute ultra-cold spin polarized atomic vapor, has accelerated the study of cold collisions. Experimental and theoretical studies of BEC and the long range interaction between cold alkali atoms is at the boundary of atomic and low temperature physics. Such studies have been difficult and would not have been possible without the development and advancement of laser cooling and trapping of neutral atoms. By contrast, ion-atom interactions at low temperature, also very difficult to study prior to modern day laser cooling, have remained largely unexplored. But now, many laboratories worldwide have almost routine access to cold neutral atoms. The combined technologies of ion trapping, together with laser cooling of neutrals has made these studies experimentally feasible and several very important, novel applications might come out of such investigations . This paper is an investigation of ion-atom interactions in the cold and ultra-cold temperature regime. Some of the collisional ion-atom interactions present at room temperature are very much reduced in the low temperature regime. Reaction rates for charge transfer between unlike atoms, A + B(+) approaches A(+) + B, are expected to fall rapidly with temperature, approximately as T(sup 5/2). Thus, cold mixtures of atoms and ions are expected to coexist for very long times, unlike room temperature mixtures of the same ion-atom combination. Thus, it seems feasible to cool ions via collisions with laser cooled atoms. Many of the conventional collisional interactions, exploited as a useful tool at room temperature and higher, are greatly enhanced at low energy. For example, collisional spin transfer from one species of polarized atoms to another has long been a useful method for polarizing a sample of atoms where no other means was available. Because optical pumping cannot be used to polarize the nuclear spin of Xe-129 or He-3 (for use in nmr imaging of the lungs), the nuclear spins are polarized via collisions with an optically pumped Rb vapor in a cell containing both gases. In another case, a spin polarized thermal Cs beam was used to polarize the hyperfine states of trapped He(+)-3 ions in order to measure their hyperfine clock transition frequency. The absence of an x-ray light source to optically pump the ground state of the He(+)-3 ion necessitated this alternative state preparation. Similarly, Cd(+) and Sr(+) ions were spin-oriented via collisions in a cell with optically pumped Rb vapor. Resonant RF spin changing transitions in the ground state of the ions were detected by changes in the Rb resonance light absorption. Because cold collision spin exchange rates scale with temperature as T(sup -1/2) this technique is expected to be a far more powerful tool than the room temperature counterpart. This factor of 100 or more enhancement in spin exchange reaction rates at low temperatures is the basis for a novel trapped ion clock where laser cooled neutrals will cool, state select and monitor the ion clock transition. The advantage over conventional direct laser cooling of trapped ions is that the very expensive and cumbersome UV laser light sources, required to excite the ionic cooling transition, are effectively replaced by simple diode lasers.

Prestage, John D.↗

A Versatile Approach for Quantification of Surface Site Fractions using Reaction Kinetics: The Case of CO Oxidation on Supported Ir Single Atoms and Nanoparticles

Supported metal single atom catalysts have shown unique activity and selectivity for several reactions. Investigating the reaction mechanism on single atom catalysts and unambiguous assignment of the activity and selectivity requires catalysts with exclusively single atoms. However, it is challenging to prepare pure single atom catalysts with conventional impregnation methods, which typically result in a mixture of single atoms and nanoparticles. Here, we show that owing to different reaction mechanisms on single atoms and nanoparticles, reaction kinetics can serve as a surface sensitive characterization technique for quantifying their surface site fractions. As a case study, we use CO oxidation kinetics on Ir/MgAl2O4 to quantify the surface site fractions of single atoms and nanoparticles and the results are consistent with aberration-corrected scanning transmission electron microscopy, X-ray absorption fine structure and infrared spectroscopies. Additionally, by carefully choosing the reaction conditions, the activity of single atoms (or nanoparticles) can be made dominant, enabling detection of a small fraction, or allowing a study of their reaction mechanism on a catalyst containing a mixture of single atoms and nanoparticles. These results are general and could be applied to other systems where two types of sites have different reaction mechanisms.

Single atom catalyst, Kinetics, CO oxidation, x-ra↗

Atom Skimmers and Atom Lasers Utilizing Them

Atom skimmers are devices that act as low-pass velocity filters for atoms in thermal atomic beams. An atom skimmer operating in conjunction with a suitable thermal atomic-beam source (e.g., an oven in which cesium is heated) can serve as a source of slow atoms for a magneto-optical trap or other apparatus in an atomic-physics experiment. Phenomena that are studied in such apparatuses include Bose-Einstein condensation of atomic gases, spectra of trapped atoms, and collisions of slowly moving atoms. An atom skimmer includes a curved, low-thermal-conduction tube that leads from the outlet of a thermal atomic-beam source to the inlet of a magneto-optical trap or other device in which the selected low-velocity atoms are to be used. Permanent rare-earth magnets are placed around the tube in a yoke of high-magnetic-permeability material to establish a quadrupole or octupole magnetic field leading from the source to the trap. The atoms are attracted to the locus of minimum magnetic-field intensity in the middle of the tube, and the gradient of the magnetic field provides centripetal force that guides the atoms around the curve along the axis of the tube. The threshold velocity for guiding is dictated by the gradient of the magnetic field and the radius of curvature of the tube. Atoms moving at lesser velocities are successfully guided; faster atoms strike the tube wall and are lost from the beam.

Hulet, Randall↗

Iridium Atoms Bonded to Crystalline Powder MgO: Characterization by Imaging and Spectroscopy

Samples with low loadings of metals on well-defined supports provide some of the best opportunities to determine the metal–support structure and bonding. We illustrate methods for characterizing atomically dispersed heavy metals on metal oxide supports by aberration-corrected scanning transmission electron microscopy (STEM) complemented by fluorescence detection extended X-ray absorption fine structure and infrared spectroscopies. STEM images of Ir atoms derived from Ir(C 2 H 4 ) 2 (acac) (acac = acetylacetonato) on high-surface-area MgO powder were obtained with minimized electron beam damage by quickly recording images near where the focus had been established. The images show that iridium at a loading of 1.0 wt % on MgO calcined at 1073 K was atomically dispersed, populating much of the surface of the MgO particles, which had irregular shapes—consequently the Ir atoms were bonded at various sites to two or three surface O atoms. In contrast, MgO calcined at 1273 K consisted of almost perfectly cubic crystals, and Ir atoms at a loading of only 0.01 wt % on this nearly ideal support were anchored preferentially at edges and corners of the (100) faces and bonded to three surface O atoms. The latter results indicate a path forward for the determination of precise structures of atomically dispersed metals on crystalline metal oxide supports.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetics of the Hydrogen Atom Abstraction Reactions from 1-Butanol by Hydroxyl Radical: Theory Matches Experiment and More

In the present work, we study the H atom abstraction reactions by hydroxyl radical at all five sites of 1-butanol. Multistructural variational transition state theory (MS-VTST) was employed to estimate the five thermal rate constants. MS-VTST utilizes a multifaceted dividing surface that accounts for the multiple conformational structures of the transition state, and we also include all the structures of the reactant molecule. The vibrational frequencies and minimum energy paths (MEPs) were computed using the M08-HX/MG3S electronic structure method. The required potential energy surfaces were obtained implicitly by direct dynamics employing interpolated variational transition state theory with mapping (IVTST-M) using a variational reaction path algorithm. The M08-HX/MG3S electronic model chemistry was then used to calculate multistructural torsional anharmonicity factors to complete the MS-VTST rate constant calculations. The results indicate that torsional anharmonicity is very important at higher temperatures, and neglecting it would lead to errors of 26 and 32 at 1000 and 1500 K, respectively. Our results for the sums of the site-specific rate constants agree very well with the experimental values of Hanson and co-workers at 896–1269 K and with the experimental results of Campbell et al. at 292 K, but slightly less well with the experiments of Wallington et al., Nelson et al., and Yujing and Mellouki at 253–372 K; nevertheless, the calculated rates are within a factor of 1.61 of all experimental values at all temperatures. Finally, this gives us confidence in the site-specific values, which are currently inaccessible to experiment.

Environmental Molecular Sciences Laboratory↗

Auger electron spectroscopy study of surface segregation in the binary alloys copper-1 atomic percent indium, copper-2 atomic percent tin, and iron-6.55 atomic percent silicon

Auger electron spectroscopy was used to examine surface segregation in the binary alloys copper-1 at. % indium, copper-2 at. % tin and iron-6.55 at. % silicon. The copper-tin and copper-indium alloys were single crystals oriented with the /111/ direction normal to the surface. An iron-6.5 at. % silicon alloy was studied (a single crystal oriented in the /100/ direction for study of a (100) surface). It was found that surface segregation occurred following sputtering in all cases. Only the iron-silicon single crystal alloy exhibited equilibrium segregation (i.e., reversibility of surface concentration with temperature) for which at present we have no explanation. McLean's analysis for equilibrium segregation at grain boundaries did not apply to the present results, despite the successful application to dilute copper-aluminum alloys. The relation of solute atomic size and solubility to surface segregation is discussed. Estimates of the depth of segregation in the copper-tin alloy indicate that it is of the order of a monolayer surface film.

Ferrante, J.↗

Accelerated Cu2O Reduction by Single Pt Atoms at the Metal-Oxide Interface§

The reducibility of metal oxides, when serving as the catalyst support or the active sites themselves, plays an important role in heterogeneous catalytic reactions. Here we present an integrated experimental and theoretical study that reveals how the addition of small amounts of atomically dispersed Pt at the metal/oxide interface dramatically enhances the reducibility of a Cu2O thin film by H2. X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) results reveal that upon oxidation, a PtCu single-atom alloy (SAA) surface is covered by a thin Cu2O film and is therefore unable to dissociate H2. Despite this, in situ studies using ambient pressure (AP) XPS reveal that the presence of a small amount of Pt under the oxide layer can, at the single-atom limit, promote the reduction of Cu2O by H2 at room temperature. We build two density functional theory based surface models to better understand these experimental findings: A Cu2O/Cu(111)-like surface oxide layer, known as the ‘29’ oxide, in which Pt is alloyed into the Cu(111) surface as well as a PtCu SAA. Our calculations suggest that the increased activity is due to the presence of atomically dispersed Pt under the surface oxide layer, which weakens the Cu-O bonds in its immediate vicinity, thus making the interface between subsurface Pt and the surface oxide a nucleation site for the formation of metallic Cu. This initial step in the reduction process results in the presence of surface Pt atoms surrounded by metallic Cu patches, and the Pt atoms become active in H2 dissociation, which consequently accelerates the reduction of the oxide layer. This work demonstrates how isolated Pt atoms at the metal/oxide interface of a Cu-based catalyst accelerate the reduction of the oxide and, therefore, helps maintain the active, reduced state of the catalyst under reaction conditions, as is required for the synthesis of methanol from CO2 hydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic-Structural Synergy for Catalytic CO Oxidation over Palladium-Nickel Nanoalloys

Alloying palladium (Pd) with other transition metals at the nanoscale has become an important pathway for preparation of low-cost, highly-active and stable catalysts. However the lack of understanding of how the alloying phase state, chemical composition and atomic-scale structure of the alloys at the nanoscale influence their catalytic activity impedes the rational design of Pd-nanoalloy catalysts. This work addresses this challenge by a novel approach to investigating the catalytic oxidation of carbon monoxide (CO) over palladium-nickel (PdNi) nanoalloys with well-defined bimetallic composition, which reveals a remarkable a maximal catalytic activity at Pd:Ni ratio of ~50:50. Key to understanding the structural-catalytic synergy is the use of high-energy synchrotron X-ray diffraction coupled to atomic pair distribution function (HE-XRD/PDF) analysis to probe the atomic structure of PdNi nanoalloys under controlled thermochemical treatments and CO reaction conditions. Three-dimensional (3D) models of the atomic structure of the nanoalloy particles were generated by reverse Monte Carlo simulations (RMC) guided by the experimental HE-XRD/PDF data. Structural details of the PdNi nanoalloys were extracted from the respective 3D models and compared with the measured catalytic properties. The comparison revealed a strong correlation between the phase state, chemical composition and atomic-scale structure of PdNi nanoalloys and their catalytic activity for CO oxidation. This correlation is further substantiated by analyzing the first atomic neighbor distances and coordination numbers inside the nanoalloy particles and at their surfaces. These findings have provided new insights into the structural synergy of nanoalloy catalysts by controlling the phase state, composition and atomic structure, complementing findings of traditional density functional theory studies.

Environmental Molecular Sciences Laboratory↗