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At least 55 records · Page 3

Quasiperiodic potassium adlayer on decagonal Al–Ni–Co quasicrystal

Quasiperiodicity in free-electron-like metals is a subject of significant interest within the scientific community. In this work, utilizing scanning tunneling microscopy (STM), low energy electron diffraction (LEED), and density functional theory (DFT), we demonstrate the formation of a quasiperiodic potassium monolayer on the tenfold surface of decagonal Al–Ni–Co quasicrystal. A dispersed growth comprising of isolated K adatoms is observed at sub-monolayer coverage, which coalesce with increasing coverage and forms pentagonal and decagonal quasiperiodic motifs. LEED demonstrates distinct rings of spots displaying decagonal symmetry. Furthermore, our DFT calculation using the W-approximant surface that closely resembles d-Al–Ni–Co shows that sizable adsorbate-substrate interaction makes the potassium adatoms bind to the quasiperiodically dispersed favorable adsorption sites resulting in the formation of quasiperiodic potassium monolayer. Notably, the experimental motifs obtained from STM measurements align remarkably well with the DFT predictions, underscoring the intricate relationship between the electronic structure of the substrate that drives the quasiperiodic growth of the potassium adlayer.

alkali metal↗

Spatially Enhanced Electrostatic Doping in Graphene Realized via Heterointerfacial Precipitated Metals

Forming heavily-doped regions in 2D materials, like graphene, is a steppingstone to the design of emergent devices and heterostructures. Here, a selective-area approach is presented to tune the work-function and carrier density in monolayer graphene by spatially synthesizing sub-monolayer gallium beneath the 2D-solid. The localized metallic gallium is formed via precipitation from an underlying diamond-like carbon (DLC) film that is spatially implanted with gallium-ions. By controlling the interfacial precipitation process with annealing temperature, spatially precise ambipolar tuning of the graphene work-function is achieved, and the tunning effect preserved upon cooling to ambient conditions. Consequently, charge carrier densities from ≈1.8 × 10 10 cm -2 (hole-doped) to ≈7 × 10 13 cm -2 (electron-doped) are realized, confirmed by in situ and ex situ measurements. The theoretical studies corroborated the role of gallium at the heterointerface on charge transfer and electrostatic doping of the graphene overlayer. Specifically, sub-monolayer gallium facilitates heavy n-doping in graphene. Extending this doping strategy to other implantable elements in DLC provides a new means of exploring the physics and chemistry of highly-doped 2D materials.

36 MATERIALS SCIENCE↗

Overcoming Secondary Nucleation of Misoriented Domains during Wafer-Scale Epitaxy of Single-Crystal Graphene on Ge(110)

The wafer-scale synthesis of single-crystal graphene on technologically important substrates is a major challenge inhibiting the development of next-generation devices that harness the exceptional electronic, thermal, and mechanical properties of single-crystal graphene. Here, in this work, the factors controlling the domain orientation of graphene grown epitaxially on Ge(110) are elucidated, and this insight is utilized to produce graphene with minimal polycrystallinity. In the early stages of growth, most graphene islands have unidirectionally aligned lattices. However, we discover a secondary nucleation phenomenon in which misoriented graphene domains nucleate near/from the island edges, introducing defective grain boundaries and significantly increasing polycrystallinity throughout growth. We find that secondary nucleation occurs when islands grow over Ge steps, which form because of an interplay between the island growth and Ge surface topography evolution. Strategies for suppressing secondary nucleation are developed, enabling the synthesis of graphene in which the predominant crystal orientation has high coverage >99% and low rotational spread <0.6°. This work overcomes the irreproducibility of graphene epitaxy on Ge(110) reported in the literature, providing a route toward the large-area synthesis of single-crystal graphene on technologically useful semiconductors.

chemical vapor deposition↗

Quantum-Well Bound States in Graphene Heterostructure Interfaces

We present experimental evidence of electronic and optical interlayer resonances in graphene van der Waals heterostructure interfaces. Using the spectroscopic mode of a low-energy electron microscope (LEEM), we characterized these interlayer resonant states up to 10 eV above the vacuum level. Compared with nontwisted, AB-stacked bilayer graphene (AB BLG), an ≈ 0.2 Å increase was found in the interlayer spacing of 30° twisted bilayer graphene (30°-tBLG). In addition, we used Raman spectroscopy to probe the inelastic light-matter interactions. A unique type of Fano resonance was found around the D and G modes of the graphene lattice vibrations. This anomalous, robust Fano resonance is a direct result of quantum confinement and the interplay between discrete phonon states and the excitonic continuum.

36 MATERIALS SCIENCE↗

The metal to metal interface and its effect on adhesion and friction

The paper considers the interface between two bulk metals and the effect of this interface on adhesive bonding, resistance to tangential displacements, friction and the interfacial transport from one surface to another. Using Auger emission spectroscopy, field ion microscopy, and low energy electron diffraction techniques, the influence of surface orientation, lattice registry, crystal lattice structure and defects, metal surface chemistry and alloying on the characteristics of the interface was studied for noble, platinum, transition, and Group 4B metals. With dissimilar metals in contact, epitaxial transfer of the cohesively weaker to the cohesively stronger metal has been observed. Surface chemical activity of the noble and platinum metals is shown to affect interfacial behavior as does a valence bonding in the transition metals, and the degree of metallic nature in the Group 4B elements. Alloying elements, e.g., Si and Fe, can alter interfacial behavior by segregation to the surface of metals or by altering bulk properties such as crystal transformation kinetics.

Buckley, D. H.↗

The Surface Chemistry of Methanol on Cu 3 Pd(111): Effects of Metal Alloying and Reaction with Hydrogen

Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) was used to study the adsorption and surface chemistry of methanol on a Cu 3 Pd(111) model surface. The composition and morphological properties of the pristine Cu 3 Pd(111) substrate were analyzed using a combination of low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and low-energy ion scattering (LEIS). The results of ion scattering showed segregation of Pd toward the surface, with a Pd/Cu ratio close to 0.5, a larger value than the ratio of 0.33 expected for a Cu 3 Pd bimetallic structure. The surface of the alloy exhibited a good LEED pattern with three-fold long-range periodicities. In STM, clusters of palladium with hexagonal arrays and Pd- Pd distances of 2.7-2.8 Å were detected. Bonding to copper perturbed the electronic properties of the atoms in the Pd clusters, shifting their 4d states toward higher binding energy with respect to the Fermi level. Further, the valence band spectrum of Cu 3 Pd(111) exhibited a line shape that was very different from those displayed by Cu(111) or Pd(111). At low pressures, the adsorption of methanol on Cu 3 Pd(111) at 300 K mainly produced CH 3 O, CO and CH x species. AP-XPS showed that most Pd atoms in the surface of the Cu 3 Pd(111) alloy interacted with the decomposition products of methanol. No significant changes were observed in the core levels of copper upon the adsorption and dissociation of methanol, suggesting that the molecule mainly interacted with Pd sites of the alloy. Reaction with hydrogen led to fast removal of CH x , C and PdC x species from Cu 3 Pd(111) at moderate (< 450 K) temperatures and prevented a CH x → C transformation. If the stability of adsorbed CH 3 O is used as a descriptor for the hydrogenation of CO 2 to methanol, Cu 3 Pd should be a much better catalyst than monometallic palladium. This may be a consequence of electronic and ensemble effects in the alloy that moderate the reactivity of Pd sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Decagonal Sn clathrate on d-Al-Ni-Co

Decagonal quasiperiodic ordering of Sn thin films on d-Al-Ni-Co is shown based on scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory (DFT). Interestingly, the decagonal structural correlations are partially retained even up to a large film thickness of 10 nm grown at 165±10K. The nucleation centers called “Sn white flowers” identified by STM at submonolayer thickness are recognized as valid patches of the decagonal clathrate structure with low adsorption energies of these motifs. Due to the excellent lattice matching (to within 1%) between columns of Sn dodecahedra in the clathrate structure and pentagonal motifs at the d-Al-Ni-Co surface, the interfacial energy favors clathrate over the competing Sn crystalline forms. DFT study of the Sn/Al-Ni-Co composite model shows good mechanical stability, as shown by the work of separation of Sn from Al-Ni-Co slab that is comparable to the clathrate self-separation energy. Finally, the relaxed surface terminations of the R 2 T 4 clathrate approximant are in self-similarity correspondence with the motifs observed in the STM images from monolayer to the thickest Sn film.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of electron–electron interactions on the emission characteristics of ultracold, nanoscale photoemission-based electron sources

For nearly 60 years, cold field emitters have been the source of choice for electron microscopy due to their high brightness and relatively low energy spread. In this paper, we have examined an alternative: nanoscale electron sources based on near-threshold photoemission. While these sources have not yet been realized, they hold the potential to produce significantly brighter beams than cold field emitters. We model electron–electron Coulomb interactions in beams emitted from such sources to calculate the impact of these interactions on the brightness and the energy spread. Our results show that these sources can theoretically deliver more than an order of magnitude brighter electron beams compared to cold field emitters along with more than an order of magnitude smaller energy spread, before being limited by the Coulomb interactions. Electron sources with such high brightness and low energy spread would be transformational for electron microscopy, enabling electron energy loss-based vibrational spectroscopy at the sub-nanometer scale.

Gevorkyan, G S↗

Highly Active Hydrogen Evolution Reaction (HER) Catalysts Formed by Energetic Pt n Cluster Deposition: Deposition Dynamics and the HER Mechanism

Mass-selected Pt n + (n ≤ 7) were deposited at variable energies on highly oriented pyrolytic graphite (HOPG), creating highly active hydrogen evolution reaction (HER) electrocatalysts. HER mass activities were ~2 to >10 times higher than those for the surface atoms in bulk Pt and for Pt n deposited on several other supports. Thus, high activity reflects the Pt-C structures formed by energetic Pt n -HOPG impacts, in addition to high Pt surface availability. The Pt n /HOPG electrodes were probed by X-ray photoelectron spectroscopy, low energy ion scattering, and electron microscopy. Born-Oppenheimer molecular dynamics (BOMD) was used to simulate Pt n - HOPG impacts, revealing the types of structures formed at different energies, then DFT was used to probe their most important HER pathways. For low deposition energies, the Pt n deposit onto the HOPG surface with sub-unit sticking probability, aggregating at defects. With increasing deposition energy, the sticking probability initially decreases, then rises to unity as subplantation and defect creation allow formation of strongly bonded platinum-carbon structures. Barriers for HER on these structures were found to be low and weakly dependent on Pt n size, consistent with experiment. The activities were highest for small covalently-bonded Pt-C structures created at high deposition energies. The larger aggregated structures formed at low energies were less active, but still substantially better than the bulk Pt surface monolayer. The catalysts were stable in repeated potential cycling at reducing potentials, but electrodes containing subplanted Pt became more active when scanned to oxidizing potentials, due to emergence of subplanted Pt onto the surface.

08 HYDROGEN↗

Exotic Long-Range Surface Reconstruction on La 0.7 Sr 0.3 MnO 3 Thin Films

Due to an extremely diverse phase space, La 1–x Sr x MnO 3 , as with other manganites, offers a wide range of tunability and applications including colossal magnetoresistance and use as spin-polarized electrodes. Here, we study an unprecedented, exotic surface reconstruction (6 × 6) in La 1–x Sr x MnO 3 (x = 0.3) observed via low-energy electron diffraction (LEED). Scanning tunneling microscopy (STM) shows the surface is relatively flat, with unit-cell step heights, and X-ray photoelectron spectroscopy (XPS) reveals a strong degree of Sr segregation at the surface. By combining electron diffraction and first-principles computations, we propose that the long-range surface reconstruction consists of a Sr-segregated surface with La (6 × 6) ordering. This study expands our understanding of manganite systems and underscores their ability to form interesting surface reconstructions, driven largely by cation segregation that can potentially be controlled for tuning surface ordering.

36 MATERIALS SCIENCE↗

Targeted Dy intercalation under graphene/SiC for tuning its electronic band structure

Metal intercalation of graphene is a promising method to tune its electronic band structure and generate novel electronic and topological phases. The tuning depends critically on the ability to bond the intercalated atoms at predesigned, subsurface interlayer locations because the emerging band structure depends on metal location. In this work, we have studied Dy intercalation under single-layer graphene (SLG) on SiC using spot profile analysis–low-energy electron diffraction and scanning tunneling microscopy (STM). The experimental work is complemented with density-functional theory (DFT) analysis. Because different diffraction spots originate from different subsurface interlayer regions, it is possible to identify changes in the intercalation location by monitoring the spot intensity as a function of growth conditions. DFT calculations of the chemical potential as a function of intercalated Dy coverage support the variation of the stability of the intercalated phase at different intercalated locations. The preferred location is confirmed from STM studies showing the removal of the 6 × 6 moiré corrugation at the preferred location, observed at higher Dy coverage.

2-dimensional systems↗

Dipolar Aleppo lattice: Ground state ordering and ergodic dynamics in the absence of vertex frustration

We introduce the Aleppo spin ice geometry, another variation of decimated square ice patterns, which in contrast to similar systems previously studied, does not exhibit vertex frustration. Using synchrotron-based photoemission electron microscopy, we directly visualize low-energy states achieved after thermal annealing, in addition to temperature-dependent moment fluctuations. The results reveal the observation of ground state patterns and the absence of ergodicity-breaking dynamics. Our observations further confirm vertex frustration to be an important criterion for the emergence of ergodicity transitions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Epitaxial growth of monolayer PdTe 2 and patterned PtTe 2 by direct tellurization of Pd and Pt surfaces

Two-dimensional (2D) palladium ditelluride (PdTe 2 ) and platinum ditelluride (PtTe 2 ) are two Dirac semimetals, which have fascinating quantum properties such as superconductivity, magnetism and topological order and show the promising applications in future nanoelectronics and optoelectronics. However, the synthesis of PdTe 2 and PtTe 2 monolayers (MLs) is hindered by a strong interlayer coupling and orbital hybridization. Here, in this study, we demonstrate an efficient synthesis of PdTe 2 and PtTe 2 MLs Large-area and high quality MLs of PdTe 2 and patterned PtTe 2 were epitaxially grown on the Pd(111) and Pt(111) surfaces by direct telurization in ultra-high vacuum. This was confirmed by x-ray photoelectron spectroscopy, low energy electron diffraction and scanning tunnelling microscopy. PdTe 2 ML demonstrated high thermal stability showing no decomposition sign after annealing at 470 °C. A well-ordered (2 × 2) PtTe 2 structure with Kagome lattice was observed on Te/Pt(111) surface following annealing at 200 °C in UHV, where the (2 × 2) pattern was formed by Te atom vacancies. PtTe 2 multilayer film was prepared as well, and it demonstrated the excitation of the Dirac plasmons as measured by high-resolution electron energy loss spectroscopy. The direct tellurization offers the simple and reliable protocol for the preparation of the ML of PdTe 2 and patterned PtTe 2 , and this opens new opportunities for quantum phenomena research and for practical optoelectronics applications.

2D materials↗

Identification and characterization of extraterrestrial non-chondritic interplanetary dust

Interplanetary dust particles (IDPs) are among the most pristine and primitive extraterrestrial materials available for direct study. Most of the stratospheric particles selected for study from the JSC Curatorial Collection were chondritic in composition (major element abundances within a factor of two of chondritic meteorites) because this composition virtually ensures that the particle is from an extraterrestrial source. It is likely that some of the most interesting classes of IDP's have not been recognized simply because they are not chondritic or do not fit established criteria for extraterrestrial origin. Indeed, mass spectroscopy data from the Giotto Flyby of comet Halley indicate that a substantial fraction of the dust is in the submicron size range and that a majority of these particles contain C, H, O, and/or N as major elements. The preponderance of CHON particles in the coma of Halley implies that similar particles may exist in the JSC stratospheric dust collection. However, the JSC collection also contains a variety of stratospheric contaminants from terrestrial sources which have these same characteristics. Because established criteria for extraterrestrial origin may not apply to such particles in individual cases, and integrated approach is required in which a variety of analysis techniques are applied to the same particle. Non-chondritic IDP's, like their chondritic counterparts, can be used to elucidate pre- and early solar system processes and conditions. The study of non-chondritic IDP's may additionally yield unique information which bears on the nature of cometary bodies and the processing of carbonaceous and other low atomic number materials. A suite of complementary techniques, including Low Voltage Scanning Electron Microscopy (LVSEM), Energy-Dispersive X-ray Microanalysis (EDX), Secondary Ion Mass Spectrometry (SIMS) isotope-ratio imaging and Analytical Electron Microscopy (AEM), were utilized to accomplish the following two objectives: (1) to develop criteria for the unequivocal identification of extraterrestrial non-chondritic IDP's; and (2) to infer IDP parent body, solar nebula, and pre-solar conditions through the study of phases, textures, and components contained within non-chondritic IDP's. The general approach taken is designed to maximize the total information obtained from each particle. Techniques will be applied in order from least destructive to most destructive.

Blake, D. F.↗

Low Repetition-Rate, High-Resolution Femtosecond Transmission Electron Microscopy

Spatial and energy resolutions of state-of-the-art transmission electron microscopes (TEMs) have surpassed 50 pm and 5 meV. However, with respect to the time domain, even the fastest detectors combined with the brightest sources may only be able to reach the microsecond timescale. Thus, conventional methods are incapable of resolving myriad fundamental ultrafast (i.e., attosecond to picosecond) atomic-scale dynamics. The successful demonstration of femtosecond (fs) laser-based (LB) ultrafast transmission electron microscopy (UEM) nearly 20 years ago provided a means to span this nearly 10-order-of-magnitude temporal gap. While nanometer-picosecond UEM studies of dynamics are now well established, ultrafast Å-scale imaging has gone largely unrealized. Further, while instrument development has rightly been an emphasis, and while new modalities and uses of pulsed-beam TEM continue to emerge, the overall chemical and materials application space has been only modestly explored to date. In this Perspectives article, we argue that these apparent shortfalls can be attributed to a simple lack of data and detail. We speculate that present work and continued growth of the field will ultimately lead to the realization that Å-scale fs dynamics can indeed be imaged with minimally modified UEM instrumentation and with repetition rates (f rep ) below - and perhaps even well below - 1 MHz. We further argue that use of low f rep , whether for LB UEM or for chopped/bunched beams, significantly expands the accessible application space. Furthermore, this calls for systematically establishing modality-specific limits so that especially promising technologies can be pursued, thus ultimately facilitating broader adoption as individual instrument capabilities expand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Helium bubble formation in aged plutonium metal at ambient conditions

A model of helium bubble formation is developed that assumes the initial nascent bubbles are generated when two diffusing helium atoms come within a distance of about the interatomic spacing of the plutonium atoms. These nascent bubbles are assumed to be locked in place and grow as additional helium atoms diffuse across their surfaces. Calculations of the helium-bubble number density and sizes as a function of age are compared to experiment. This leads to an inferred helium diffusion coefficient of-the-order of 10 -20 m 2 /s, supports the idea that most of the helium from alpha-decay end up in bubbles, and that previous transmission electron microscopy size estimates are biased low. The energy that helium can transfer to 40-year-old plutonium, upon expansion, is determined to be <0.1 Joules per gram of metal. The model predicts differences between the bubble properties in naturally and accelerated aged plutonium.

36 MATERIALS SCIENCE↗

Imaging analysis of LDEF craters

Two small craters in Al from the Long Duration Exposure Facility (LDEF) experiment tray A11E00F (no. 74, 119 micron diameter and no. 31, 158 micron diameter) were analyzed using Auger electron spectroscopy (AES), time-of-flight secondary ion mass spectroscopy (TOF-SIMS), low voltage scanning electron microscopy (LVSEM), and SEM energy dispersive spectroscopy (EDS). High resolution images and sensitive elemental and molecular analysis were obtained with this combined approach. The result of these analyses are presented.

Radicatidibrozolo, F.↗