Beamline simulations using monochromators with high d-spacing crystals.

Monochromators for synchrotron radiation beamlines typically use perfect crystals for the hard X-ray regime and gratings for soft X-rays. There is an intermediate range, typically 1-3 keV (tender X-rays), which common perfect crystals have difficulties covering and gratings have low efficiency, although some less common crystals with high d-spacing could be suitable. To evaluate the suitability of these crystals for a particular beamline, it is useful to evaluate the crystals' performance using tools such as ray-tracing. However, simulations for double-crystal monochromators are only available for the most used crystals such as Si, Ge or diamond. Here, an upgrade of the SHADOW ray-tracing code and complementary tools in the OASYS suite are presented to simulate high d-spacing crystals with arbitrary, and sometimes complex, structures such as beryl, YB66, muscovite, etc. Isotropic and anisotropic temperature factors are also considered. The YB66 crystal with 1936 atomic sites in the unit cell is simulated, and its applicability for tender X-ray monochromators is discussed in the context of new low-emittance storage rings.

Oxygen Electromigration and Energy Band Reconstruction Induced by Electrolyte Field Effect at Oxide Interfaces.

Electrolyte gating is a powerful means for tuning the carrier density and exploring the resultant modulation of novel properties on solid surfaces. However, the mechanism, especially its effect on the oxygen migration and electrostatic charging at the oxide heterostructures, is still unclear. Here we explore the electrolyte gating on oxygen-deficient interfaces between SrTiO_{3} (STO) crystals and LaAlO_{3} (LAO) overlayer through the measurements of electrical transport, x-ray absorption spectroscopy, and photoluminescence spectra. We found that oxygen vacancies (O_{vac}) were filled selectively and irreversibly after gating due to oxygen electromigration at the amorphous LAO/STO interface, resulting in a reconstruction of its interfacial band structure. Because of the filling of O_{vac}, the amorphous interface also showed an enhanced electron mobility and quantum oscillation of the conductance. Further, the filling effect could be controlled by the degree of the crystallinity of the LAO overlayer by varying the growth temperatures. Our results reveal the different effects induced by electrolyte gating, providing further clues to understand the mechanism of electrolyte gating on buried interfaces and also opening a new avenue for constructing high-mobility oxide interfaces.

The surface electronic structure of silicon terminated (100) diamond.

A combination of synchrotron-based x-ray spectroscopy and contact potential difference measurements have been used to examine the electronic structure of the (3 × 1) silicon terminated (100) diamond surface under ultra high vacuum conditions. An occupied surface state which sits 1.75 eV below the valence band maximum has been identified, and indications of mid-gap unoccupied surface states have been found. Additionally, the pristine silicon terminated surface is shown to possess a negative electron affinity of -0.86 ± 0.1 eV.

Observation of perfect diamagnetism and interfacial effect on the electronic structures in infinite layer Nd0.8Sr0.2NiO2 superconductors.

Nickel-based complex oxides have served as a playground for decades in the quest for a copper-oxide analog of the high-temperature superconductivity. They may provide clues towards understanding the mechanism and an alternative route for high-temperature superconductors. The recent discovery of superconductivity in the infinite-layer nickelate thin films has fulfilled this pursuit. However, material synthesis remains challenging, direct demonstration of perfect diamagnetism is still missing, and understanding of the role of the interface and bulk to the superconducting properties is still lacking. Here, we show high-quality Nd0.8Sr0.2NiO2 thin films with different thicknesses and demonstrate the interface and strain effects on the electrical, magnetic and optical properties. Perfect diamagnetism is achieved, confirming the occurrence of superconductivity in the films. Unlike the thick films in which the normal-state Hall-coefficient changes signs as the temperature decreases, the Hall-coefficient of films thinner than 5.5 nm remains negative, suggesting a thickness-driven band structure modification. Moreover, X-ray absorption spectroscopy reveals the Ni-O hybridization nature in doped infinite-layer nickelates, and the hybridization is enhanced as the thickness decreases. Consistent with band structure calculations on the nickelate/SrTiO3 heterostructure, the interface and strain effect induce a dominating electron-like band in the ultrathin film, thus causing the sign-change of the Hall-coefficient.

Unravelling strong electronic interlayer and intralayer correlations in a transition metal dichalcogenide.

Electronic correlations play important roles in driving exotic phenomena in condensed matter physics. They determine low-energy properties through high-energy bands well-beyond optics. Great effort has been made to understand low-energy excitations such as low-energy excitons in transition metal dichalcogenides (TMDCs), however their high-energy bands and interlayer correlation remain mysteries. Herewith, by measuring temperature- and polarization-dependent complex dielectric and loss functions of bulk molybdenum disulphide from near-infrared to soft X-ray, supported with theoretical calculations, we discover unconventional soft X-ray correlated-plasmons with low-loss, and electronic transitions that reduce dimensionality and increase correlations, accompanied with significantly modified low-energy excitons. At room temperature, interlayer electronic correlations, together with the intralayer correlations in the c-axis, are surprisingly strong, yielding a three-dimensional-like system. Upon cooling, wide-range spectral-weight transfer occurs across a few tens of eV and in-plane p-d hybridizations become enhanced, revealing strong Coulomb correlations and electronic anisotropy, yielding a two-dimensional-like system. Our result shows the importance of strong electronic, interlayer and intralayer correlations in determining electronic structure and opens up applications of utilizing TMDCs on plasmonic nanolithrography.

Experimental observation of the crystallization of a paired holon state.

An excitation at 201 meV is observed in the doped-hole ladder cuprate Sr14Cu24O41, using ultraviolet resonance Raman scattering with incident light at 3.7 eV polarized along the rungs. The excitation is of charge nature, with a temperature independent excitation energy, and can be understood via an intraladder pair-breaking process. The intensity tracks closely the order parameter of the charge density wave in the ladder CDW(L), but persists above its transition temperature T(CDW(L)), indicating a strong local pairing above the T(CDW(L)). The 201 meV excitation vanishes in La6Ca8Cu24O(41+δ), and La5Ca9Cu24O41 which are samples with no holes in the ladders. Our results suggest that the doped holes in the ladder are composite bosons consisting of paired holons that order below T(CDW).

Ferromagnetism in dilute magnetic semiconductors through defect engineering: Li-doped ZnO.

We demonstrate, both theoretically and experimentally, that cation vacancy can be the origin of ferromagnetism in intrinsic dilute magnetic semiconductors. The vacancies can be controlled to tune the ferromagnetism. Using Li-doped ZnO as an example, we found that while Li itself is nonmagnetic, it generates holes in ZnO, and its presence reduces the formation energy of Zn vacancy, and thereby stabilizes the zinc vacancy. Room temperature ferromagnetism with p type conduction was observed in pulsed laser deposited ZnO:Li films with certain doping concentration and oxygen partial pressure.

Temperature dependence of solvation forces as measured in atomic force microscopy.

An atomic force microscope (AFM) has been used to study the effect of temperature on solvation forces in the liquids octamethylcyclotetrasiloxane, n-hexadecane, and n-dodecanol confined between the AFM tip and a graphite surface. Discrete solvation layers can be observed for all three liquids at all the temperatures measured (298-348K). However, with increasing temperature there is a significant decrease in the magnitude of the measured solvation forces and a reduction in the number of solvation oscillations which can be observed. Solvation forces per se are only weakly temperature dependent and the most plausible explanation is that we are measuring how the layers are squeezed from the tip-sample gap. The squeeze out process is a thermally activated phenomenon and gives rise to the large change in the magnitude of the force oscillations with temperature. A simple analysis is provided based on transition rate theory. The large change in solvation force with temperature has implications for the measurement of localized forces using AFM, particularly in interpreting biological interactions and single asperity friction.

Shape-controlled growth of indium and aluminum nanostructures on MoS2(0001).

The growth of indium and aluminum nanostructures on molybdenum disulphide (MoS2)(0001) substrate has been studied using scanning tunneling microscopy in ultra-high vacuum. At low coverage and room temperature (RT), mostly ultra-thin (approximately 1.2-2 nm) triangular In islands were observed on MoS2. With increasing coverage or high flux, large coalesced irregular islands along with triangular and round-shaped ones of increased average height were found. Triangular and round-shaped islands were obtained after annealing the RT-deposited In on MoS2 sample at 450 K. At approximately 375 K, exclusively triangular In islands were observed. Al nanoparticles with diameter in 4-16 nm range were obtained after a low-flux deposited whereas ramified islands were observed in a high flux at RT. Ultra-thin (approximately 1.20-2 nm) Al islands and films were obtained on MoS2 after deposition at 500 K. These results demonstrate that the shape of In and Al nanostructures grown on MoS2 can be controlled in self-assembly by adjusting substrate temperature, deposition flux and amount.

Synthesis of "cactus" top-decorated aligned carbon nanotubes and their third-order nonlinear optical properties.

We report a new morphology of "cactus" top-decorated aligned carbon nanotubes grown by the PECVD method using pure C2H2 gas. Unlike most previous reports, no additional carrier gas is used for pretreatment. Carbon nanotubes can still grow and maintain the tubular structure underneath the "cactus" tops. It is proposed that the H atoms produced by the dissociation of C2H2 activate the catalyst nanoparticles. Scanning electron microscopy (SEM) shows that the top "cactus" morphology is composed of a large quantity of small nanosheets. Transmission electron microscopy (TEM) reveals the amorphous carbon nature of these "cactus" structures. The formation of these "cactus" structures is possibly due to covalent absorption and reconstruction of carbon atoms on the broken graphite layers of nanotubes produced by the strong ion bombardment under plasma. The third-order optical nonlinearities and nonlinear dynamics are also investigated. The third-order nonlinear susceptibility magnitude /chi(3)/ is found to be 2.2 x 10(-11) esu, and the relaxation process takes place in about 1.8 ps.

Fabrication of size-tunable gold nanoparticles array with nanosphere lithography, reactive ion etching, and thermal annealing.

Two-dimensional ordered arrays of gold (Au) nanoparticles were fabricated using two different variants of the nanosphere lithography technique. First, ordered arrays of polystyrene nanospheres on Si substrate were used as deposition masks through which gold films were deposited by electron beam evaporation. After the removal of the nanospheres, an array of triangular Au nanodisks was left on the Si substrate. After thermal annealing at increasing temperature, systematic shape transition of the nanostructures from original triangular Au nanodisks to rounded nanoparticles was observed. This approach allows us to systematically vary the size and morphology of the particles. In the second and novel technique, we made use of reactive ion etching to simultaneously reduce the dimension of the masking nanospheres and create arrays of nanopores on the substrate prior to the deposition of the Au films. These samples were subsequently annealed, which resulted in size-tunable and ordered Au nanoparticle arrays with the nanoparticles nested in the nanopores of the templated substrate. With the nanoparticles anchored in the nanopores, the substrate could be useful as a template for growth of other nanomaterials.

Anomalous spectral features of a neutral bilayer graphene.

Graphene and its bilayer are two-dimensional systems predicted to show exciting many-body effects near the neutrality point. The ideal tool to investigate spectrum reconstruction effects is angle-resolved photoemission spectroscopy (ARPES) as it probes directly the band structure with information about both energy and momentum. Here we reveal, by studying undoped exfoliated bilayer graphene with ARPES, two essential aspects of its many-body physics: the electron-phonon scattering rate has an anisotropic k-dependence and the type of electronic liquid is non-Fermi liquid. The latter behavior is evident from an observed electron-electron scattering rate that scales linearly with energy from 100 meV to 600 meV and that is associated with the proximity of bilayer graphene to a two-dimensional quantum critical point of competing orders.

Optimized growth of graphene on SiC: from the dynamic flip mechanism.

Thermal decomposition of single-crystal SiC is one of the popular methods for growing graphene. However, the mechanism of graphene formation on the SiC surface is poorly understood, and the application of this method is also hampered by its high growth temperature. In this study, based on the ab initio calculations, we propose a vacancy assisted Si-C bond flipping model for the dynamic process of graphene growth on SiC. The fact that the critical stages during growth take place at different energy costs allows us to propose an energetic-beam controlled growth method that not only significantly lowers the growth temperature but also makes it possible to grow high-quality graphene with the desired size and patterns directly on the SiC substrate.

Cationic-vacancy-induced room-temperature ferromagnetism in transparent, conducting anatase Ti1-xTaxO2 (x~0.05) thin films.

We report room-temperature ferromagnetism (FM) in highly conducting, transparent anatase Ti(1-x)Ta(x)O(2) (x∼0.05) thin films grown by pulsed laser deposition on LaAlO(3) substrates. Rutherford backscattering spectrometry (RBS), X-ray diffraction, proton-induced X-ray emission, X-ray absorption spectroscopy (XAS) and time-of-flight secondary-ion mass spectrometry indicated negligible magnetic contaminants in the films. The presence of FM with concomitant large carrier densities was determined by a combination of superconducting quantum interference device magnetometry, electrical transport measurements, soft X-ray magnetic circular dichroism (SXMCD), XAS and optical magnetic circular dichroism, and was supported by first-principles calculations. SXMCD and XAS measurements revealed a 90 per cent contribution to FM from the Ti ions, and a 10 per cent contribution from the O ions. RBS/channelling measurements show complete Ta substitution in the Ti sites, though carrier activation was only 50 per cent at 5 per cent Ta concentration, implying compensation by cationic defects. The role of the Ti vacancy (V(Ti)) and Ti(3+) was studied via XAS and X-ray photoemission spectroscopy, respectively. It was found that, in films with strong FM, the V(Ti) signal was strong while the Ti(3+) signal was absent. We propose (in the absence of any obvious exchange mechanisms) that the localized magnetic moments, V(Ti) sites, are ferromagnetically ordered by itinerant carriers. Cationic-defect-induced magnetism is an alternative route to FM in wide-band-gap semiconducting oxides without any magnetic elements.

Gas sensing properties of tin oxide nanostructures synthesized via a solid-state reaction method.

A high-yield synthesis of SnO(2) nanoparticles via a facile, economical and easily scalable solid-state molten salt synthesis method has been demonstrated. The inorganic additive, molar ratios of chemicals and annealing temperature were found to control the size and porosity of the SnO(2) nanoparticles. The synthesized SnO(2) nanostructures were uniform, well dispersed and exhibited high crystallinity. Hydrogen sensors made from the SnO(2) nanoparticles were found to possess high sensitivity and stability. Other than tailoring the material's structure in terms of size and porosity, another potential method of enhancing the gas sensitivity is functionalization with noble Pd metal.

Molecular anchor Cu-S formed on a thiophene mediated Si(111)-(7x7) surface.

Thiophene molecule selectively binds to the adjacent adatom-rest atom pair on the Si(111)-(7x7) surface through its alpha-carbon atoms, leading to the covalent attachment of a C-S-C linkage and remaining C=C (beta-carbon) bond onto the surface. Photoemission studies show that Cu atom readily adsorbs onto the S atom of the functional group to form the Cu-S molecular anchor in two forms: one points away from the thiophene C=C group; the other points toward the C=C group.

Water-Bridge-Assisted Ionic Conduction in Probe-Induced Conical Polymer Pattern Formation.

Formation of conical polymer structures by atomic force microscopy (AFM) nanolithography and the electrical-conduction mechanism involved in the AFM- probe-induced patterning process are reported. The current is dominated by water-bridge-assisted ionic conduction. Polymer phase transition and mass redistribution occur without modification or degradation of the poly(methyl methacrylate) (PMMA) material.

Rule for structures of open metal surfaces.

We present a clear and simple rule for determining the relaxation sequences on open (stepped, vicinal, or high-Miller-index) metal surfaces. At the bulk-truncated configuration of a surface, a surface slab is defined where the coordination of atoms is reduced from the bulk. The rule predicts that the interlayer spacings within this slab contract, while the interlayer spacing between this slab and the substrate expands. By first-principles calculations, we show that this rule is obeyed on all open Cu surfaces with interlayer spacings down to about 0.5 A. We also illustrate a direct relation of the relaxation sequences to the charge redistribution on these surfaces, which is demonstrated to be driving the multilayer relaxations. The applicability of the rule can be extended to other fcc and bcc metals, including unreconstructed and missing-row surfaces.