114 research outputs found
An Efficient Algorithm for Automatic Structure Optimization in X-ray Standing-Wave Experiments
X-ray standing-wave photoemission experiments involving multilayered samples
are emerging as unique probes of the buried interfaces that are ubiquitous in
current device and materials research. Such data require for their analysis a
structure optimization process comparing experiment to theory that is not
straightforward. In this work, we present a new computer program for optimizing
the analysis of standing-wave data, called SWOPT, that automates this
trial-and-error optimization process. The program includes an algorithm that
has been developed for computationally expensive problems: so-called black-box
simulation optimizations. It also includes a more efficient version of the Yang
X-ray Optics Program (YXRO) [Yang, S.-H., Gray, A.X., Kaiser, A.M., Mun, B.S.,
Sell, B.C., Kortright, J.B., Fadley, C.S., J. Appl. Phys. 113, 1 (2013)] which
is about an order of magnitude faster than the original version. Human
interaction is not required during optimization. We tested our optimization
algorithm on real and hypothetical problems and show that it finds better
solutions significantly faster than a random search approach. The total
optimization time ranges, depending on the sample structure, from minutes to a
few hours on a modern laptop computer, and can be up to 100x faster than a
corresponding manual optimization. These speeds make the SWOPT program a
valuable tool for realtime analyses of data during synchrotron experiments
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Understanding methanol dissociative adsorption and oxidation on amorphous oxide films
Interactions between a transition metal (oxide) catalyst and a support can tailor the number and nature of active sites, for instance in the methanol oxidation reaction. We here use ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify and compare the surface adsorbates that form on amorphous metal oxide films that maximize such interactions. Considering Al(1-x)MxOy (M = Fe or Mn) films at a range of methanol : oxygen gas ratios and temperatures, we find that the redox-active transition metal site (characterized by methoxy formation) dominates dissociative methanol adsorption, while basic oxygen sites (characterized by carbonate formation) play a lesser role. Product detection, however, indicates complete oxidation to carbon dioxide and water with partial oxidation products (dimethyl ether) comprising a minor species. Comparing the intensity of methoxy and hydroxyl features at a fixed XPS chemical shift suggests methanol deprotonation during adsorption in oxygen rich conditions for high transition metal content. However, increasing methanol partial pressure and lower metal site density may promote oxygen vacancy formation and the dehydroxylation pathway, supported by a nominal reduction in the oxidation state of iron sites. These findings illustrate that AP-XPS and mass spectrometry together are powerful tools in understanding metal-support interactions, quantifying and probing the nature of catalytic active sites, and considering the link between electronic structure of materials and their catalytic activity
Hard X-ray standing-wave photoemission insights into the structure of an epitaxial Fe/MgO multilayer magnetic tunnel junction
The Fe/MgO magnetic tunnel junction is a classic spintronic system, with current importance technologically and interest for future innovation. The key magnetic properties are linked directly to the structure of hard-to-access buried interfaces, and the Fe and MgO components near the surface are unstable when exposed to air, making a deeper probing, nondestructive, in-situ measurement ideal for this system. We have thus applied hard X-ray photoemission spectroscopy (HXPS) and standing-wave (SW) HXPS in the few kilo-electron-volt energy range to probe the structure of an epitaxially grown MgO/Fe superlattice. The superlattice consists of 9 repeats of MgO grown on Fe by magnetron sputtering on an MgO(001) substrate, with a protective Al2O3 capping layer. We determine through SW-HXPS that 8 of the 9 repeats are similar and ordered, with a period of 33 ± 4 Å, with the minor presence of FeO at the interfaces and a significantly distorted top bilayer with ca. 3 times the oxidation of the lower layers at the top MgO/Fe interface. There is evidence of asymmetrical oxidation on the top and bottom of the Fe layers. We find agreement with dark-field scanning transmission electron microscope (STEM) and X-ray reflectivity measurements. Through the STEM measurements, we confirm an overall epitaxial stack with dislocations and warping at the interfaces of ca. 5 Å. We also note a distinct difference in the top bilayer, especially MgO, with possible Fe inclusions. We thus demonstrate that SW-HXPS can be used to probe deep buried interfaces of novel magnetic devices with few-angstrom precision
Depth-Resolved Composition and Electronic Structure of Buried Layers and Interfaces in a LaNiO/SrTiO Superlattice from Soft- and Hard- X-ray Standing-Wave Angle-Resolved Photoemission
LaNiO (LNO) is an intriguing member of the rare-earth nickelates in
exhibiting a metal-insulator transition for a critical film thickness of about
4 unit cells [Son et al., Appl. Phys. Lett. 96, 062114 (2010)]; however, such
thin films also show a transition to a metallic state in superlattices with
SrTiO (STO) [Son et al., Appl. Phys. Lett. 97, 202109 (2010)]. In order to
better understand this transition, we have studied a strained LNO/STO
superlattice with 10 repeats of [4 unit-cell LNO/3 unit-cell STO] grown on an
(LaAlO)(SrAlTaO) substrate using soft x-ray
standing-wave-excited angle-resolved photoemission (SWARPES), together with
soft- and hard- x-ray photoemission measurements of core levels and
densities-of-states valence spectra. The experimental results are compared with
state-of-the-art density functional theory (DFT) calculations of band
structures and densities of states. Using core-level rocking curves and x-ray
optical modeling to assess the position of the standing wave, SWARPES
measurements are carried out for various incidence angles and used to determine
interface-specific changes in momentum-resolved electronic structure. We
further show that the momentum-resolved behavior of the Ni 3d eg and t2g states
near the Fermi level, as well as those at the bottom of the valence bands, is
very similar to recently published SWARPES results for a related
LaSrMnO/SrTiO superlattice that was studied using the
same technique (Gray et al., Europhysics Letters 104, 17004 (2013)), which
further validates this experimental approach and our conclusions. Our
conclusions are also supported in several ways by comparison to DFT
calculations for the parent materials and the superlattice, including
layer-resolved density-of-states results
Direct observation of the band gap transition in atomically thin ReS
ReS is considered as a promising candidate for novel electronic and
sensor applications. The low crystal symmetry of the van der Waals compound
ReS leads to a highly anisotropic optical, vibrational, and transport
behavior. However, the details of the electronic band structure of this
fascinating material are still largely unexplored. We present a
momentum-resolved study of the electronic structure of monolayer, bilayer, and
bulk ReS using k-space photoemission microscopy in combination with
first-principles calculations. We demonstrate that the valence electrons in
bulk ReS are - contrary to assumptions in recent literature - significantly
delocalized across the van der Waals gap. Furthermore, we directly observe the
evolution of the valence band dispersion as a function of the number of layers,
revealing a significantly increased effective electron mass in single-layer
crystals. We also find that only bilayer ReS has a direct band gap. Our
results establish bilayer ReS as a advantageous building block for
two-dimensional devices and van der Waals heterostructures
Origin of the surface-orientation dependence of the reduction kinetics of ultrathin ceria
Performance of catalytic redox reactions depends crucially on the oxygen storage and release capability of the catalyst and with that the catalyst’s defect chemistry. Here, we show that the surface defect chemistry of cerium oxide, a prototypical reducible oxide, differs markedly between two surface terminations. The results are in good agreement with density functional theory calculations and provide important guiding factors for rational design of industrially relevant catalysts. The study is conducted by preparing (100) and (111) terminated nanoislands of cerium oxide next to each other on Cu(111). Leveraging the benefits of full-field imaging capability of photoemission electron microscopy (PEEM), we follow the structural and chemical properties of the nanoislands under reducing hydrogen atmosphere simultaneously and in situ. The results, summarized in Figure 1, directly reveal different overall reducibility that can be traced to equilibrium oxygen vacancy concentrations via a kinetic model. The density functional theory calculations provide further details regarding the equilibrium co-ordination of oxygen vacancies for both surface planes. Conjoining the two, the unique simultaneous nature of the PEEM-facilitated structure–activity relationship study allows us to separate the thermodynamics of reduction from the kinetics of oxygen exchange, revealing the fact that the difference in reducibility of the two surfaces of ceria is not determined by the kinetic rate constants of the reduction reaction, but rather by the equilibrium concentration of oxygen vacancies, an information that has not been provided by the isolated model system approach to date. Surprisingly, the reason for the different reducibilities is a purely geometric one: the creation of nearest neighbor oxygen vacancies.
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Simultaneous ambient pressure X-ray photoelectron spectroscopy and grazing incidence X-ray scattering in gas environments
We have developed an experimental system to simultaneously observe surface
structure, morphology, composition, chemical state, and chemical activity for
samples in gas phase environments. This is accomplished by simultaneously
measuring X-ray photoelectron spectroscopy (XPS) and grazing incidence X-ray
scattering (GIXS) in gas pressures as high as the multi-Torr regime, while also
recording mass spectrometry. Scattering patterns reflect near-surface sample
structures from the nano- to the meso-scale. The grazing incidence geometry
provides tunable depth sensitivity while scattered X-rays are detected across a
broad range of angles using a newly designed pivoting-UHV-manipulator for
detector positioning. At the same time, XPS and mass spectrometry can be
measured, all from the same sample spot and in ambient conditions. To
demonstrate the capabilities of this system, we measured the chemical state,
composition, and structure of Ag-behenate on a Si(001) wafer in vacuum and in
O atmosphere at various temperatures. These simultaneous structural,
chemical, and gas phase product probes enable detailed insights into the
interplay between structure and chemical state for samples in gas phase
environments. The compact size of our pivoting-UHV-manipulator makes it
possible to retrofit this technique into existing spectroscopic instruments
installed at synchrotron beamlines. Because many synchrotron facilities are
planning or undergoing upgrades to diffraction limited storage rings with
transversely coherent beams, a newly emerging set of coherent X-ray scattering
experiments can greatly benefit from the concepts we present here.Comment: 21 pages, 4 figure
Correlating Surface Crystal Orientation and Gas Kinetics in Perovskite Oxide Electrodes
Solid–gas interactions at electrode surfaces determine the efficiency of solid-oxide fuel cells and electrolyzers. Here, the correlation between surface–gas kinetics and the crystal orientation of perovskite electrodes is studied in the model system LaSrCoFeO. The gas-exchange kinetics are characterized by synthesizing epitaxial half-cell geometries where three single-variant surfaces are produced [i.e., LaSrCoFeO/LaSrGaMgO/SrRuO/SrTiO (001), (110), and (111)]. Electrochemical impedance spectroscopy and electrical conductivity relaxation measurements reveal a strong surface-orientation dependency of the gas-exchange kinetics, wherein (111)-oriented surfaces exhibit an activity >3-times higher as compared to (001)-oriented surfaces. Oxygen partial pressure ((Formula presented.))-dependent electrochemical impedance spectroscopy studies reveal that while the three surfaces have different gas-exchange kinetics, the reaction mechanisms and rate-limiting steps are the same (i.e., charge-transfer to the diatomic oxygen species). First-principles calculations suggest that the formation energy of vacancies and adsorption at the various surfaces is different and influenced by the surface polarity. Finally, synchrotron-based, ambient-pressure X-ray spectroscopies reveal distinct electronic changes and surface chemistry among the different surface orientations. Taken together, thin-film epitaxy provides an efficient approach to control and understand the electrode reactivity ultimately demonstrating that the (111)-surface exhibits a high density of active surface sites which leads to higher activity.R.G. and A.F. contributed equally to this work. R.G., A.F., A.L., T.C., E.E., and L.W.M. acknowledge the support of the National Science Foundation under Grant OISE-1545907. D.P. acknowledges funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 797123. G.V. acknowledges the support of the National Science Foundation under Grant DMR-1708615. V.T. and T.I. acknowledge financial support from a Grant-in-Aid for Specially Promoted Research No. 16H06293) from MEXT, Japan and through the Japan Society for the Promotion of Science and the Solid Oxide Interfaces for Faster Ion Transport JSPS Core-to-Core Program (Advanced Research Networks). J.K. acknowledge the support by World Premier International Research Center Initiative (WPI), Ministry of Education, Culture, Sports, Science, and Technology of Japan (MEXT), Japan, Solid Oxide Interfaces for Faster Ion Transport (SOIFIT) JSPS/EPSRC (EP/P026478/1) Core-to-Core Program (Advanced Research Networks). This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231
Bulk Electronic Structure of Lanthanum Hexaboride (LaB6) by Hard X-ray Angle-Resolved Photoelectron Spectroscopy
In the last decade rare-earth hexaborides have been investigated for their
fundamental importance in condensed matter physics, and for their applications
in advanced technological fields. Among these compounds, LaB has a special
place, being a traditional d-band metal without additional f- bands. In this
paper we investigate the bulk electronic structure of LaB using hard x-ray
photoemission spectroscopy, measuring both core-level and angle-resolved
valence-band spectra. By comparing La 3d core level spectra to cluster model
calculations, we identify well-screened peak residing at a lower binding energy
compared to the main poorly-screened peak; the relative intensity between these
peaks depends on how strong the hybridization is between La and B atoms. We
show that the recoil effect, negligible in the soft x-ray regime, becomes
prominent at higher kinetic energies for lighter elements, such as boron, but
is still negligible for heavy elements, such as lanthanum. In addition, we
report the bulk-like band structure of LaB determined by hard x-ray
angle-resolved photoemission spectroscopy (HARPES). We interpret HARPES
experimental results by the free-electron final-state calculations and by the
more precise one-step photoemission theory including matrix element and phonon
excitation effects. In addition, we consider the nature and the magnitude of
phonon excitations in HARPES experimental data measured at different
temperatures and excitation energies. We demonstrate that one step theory of
photoemission and HARPES experiments provide, at present, the only approach
capable of probing true bulk-like electronic band structure of rare-earth
hexaborides and strongly correlated materials.Comment: Total 26 pages, Total 11 figure
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Interface properties and built-in potential profile of a LaCr O3/SrTi O3 superlattice determined by standing-wave excited photoemission spectroscopy
LaCrO3(LCO)/SrTiO3(STO) heterojunctions are intriguing due to a polar discontinuity along [001], exhibiting two distinct and controllable charged interface structures [(LaO)+/(TiO2)0 and (SrO)0/(CrO2)-] with induced polarization, and a resulting depth-dependent potential. In this study, we have used soft- and hard-x-ray standing-wave excited photoemission spectroscopy (SW-XPS) to quantitatively determine the elemental depth profile, interface properties, and depth distribution of the polarization-induced built-in potentials. We observe an alternating charged interface configuration: a positively charged (LaO)+/(TiO2)0 intermediate layer at the LCOtop/STObottom interface and a negatively charged (SrO)0/(CrO2)- intermediate layer at the STOtop/LCObottom interface. Using core-level SW data, we have determined the depth distribution of species, including through the interfaces, and these results are in excellent agreement with scanning transmission electron microscopy and electron energy-loss spectroscopy mapping of local structure and composition. SW-XPS also enabled deconvolution of the LCO and STO contributions to the valence-band (VB) spectra. Using a two-step analytical approach involving first SW-induced core-level binding-energy shifts and then VB modeling, the variation in potential across the complete superlattice is determined in detail. This potential is in excellent agreement with density functional theory models, confirming this method as a generally useful tool for interface studies
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