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.

Anomalous Ferromagnetism of quasiparticle doped holes in cuprate heterostructures revealed using resonant soft X-ray magnetic scattering.

We report strong ferromagnetism of quasiparticle doped holes both within the ab-plane and along the c-axis of Cu-O planes in low-dimensional Au/d-La1.8Ba0.2CuO4/LaAlO3(001) heterostructures (d = 4, 8 and 12 unit-cells) using resonant soft X-ray and magnetic scattering together with X-ray magnetic circular dichroism. Interestingly, ferromagnetism is stronger at a hole doped peak and at an upper Hubbard band of O with spin-polarization degree as high as 40%, revealing strong ferromagnetism of Mottness. For in-ab-plane spin-polarizations, the spin of doped holes in O2p-Cu3d-O2p is a triplet state yielding strong ferromagnetism. For out-of-ab-plane spin-polarization, while the spins of doped holes in both O2p-O2p and Cu3d-Cu3d are triplet states, the spin of doped holes in Cu3d-O2p is a singlet state yielding ferrimagnetism. A ferromagnetic-(002) Bragg-peak of the doped holes is observed and enhanced as a function of d revealing strong ferromagnetism coupling between Cu-O layers along the c-axis.

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.

Nanoscale dielectric grating polarizers tuned to 4.43†eV for ultraviolet polarimetry.

Transmissive dielectric wire grid polarizers tuned to 4.43 eV (Mg II line, 280 nm), an important diagnostic line for solar physics, are presented in this communication. The polarizers are based on TiO2 gratings and designed with a period of ∼140 nm (7143 lines/mm), 40 nm line width (duty cycle of 0.286), and 100 nm line height. Several gratings are fabricated through electron beam lithography combined with reactive ion etching, whereby two parameters in the nanofabrication process are explored: e-beam dosage on the photoresist and TiO2 etching time. Polarization of samples is optically characterized using a spectroscopic ellipsometer in transmission mode, achieving the best result with an extinction ratio of ∼109 and a transmittance of 16.4% at the target energy of 4.43 eV. The shape of the gratings is characterized through atomic force microscopy (AFM) and scanning electron microscopy (SEM); the measured AFM profiles are distorted by the tip geometry, hence a simple deconvolution procedure is implemented to retrieve the real profile. By analysing the AFM and SEM profiles, we find that the real shapes of the different gratings are close to the design, but with a larger duty cycle than the intended value. With the real grating geometry, an improved model of the best sample was built with a finite-difference time-domain (FDTD) method that matches the result obtained through optical characterization.

A soft x-ray-ultraviolet (SUV) beamline and diffractometer for resonant elastic scattering and ultraviolet-vacuum ultraviolet reflectance at the Singapore synchrotron light source.

A new beamline and a six-circle UHV diffractometer have been constructed at the Singapore Synchrotron Light Source with a broad energy coverage from 3.5 to 1500 eV. The beamline is optimized for ultraviolet-vacuum-ultraviolet optical reflectivity and resonant soft X-ray scattering with medium energy resolution over a broad energy range, achieved by using a self-focusing monochromator consisting of a plane mirror and three variable line spacing gratings. The unique character of the diffractometer comprises 4-circles in the vertical plane and 2-circles in the horizontal plane. Thirteen motions are available inside the UHV chamber with a base pressure of 1 × 10-9 mbar. Two sample holders working independently over a temperature range of 37 K-400 K are controlled by a closed-cycle cryostat, while the bottom holder inside a high field compact pulsed magnet is available for measurements requiring a magnetic field.

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.

Electron transport and visible light absorption in a plasmonic photocatalyst based on strontium niobate.

Semiconductor compounds are widely used for photocatalytic hydrogen production applications, where photogenerated electron-hole pairs are exploited to induce catalysis. Recently, powders of a metallic oxide (Sr1-xNbO3, 0.03

Controlling Kondo-like Scattering at the SrTiO3-based Interfaces.

The observation of magnetic interaction at the interface between nonmagnetic oxides has attracted much attention in recent years. In this report, we show that the Kondo-like scattering at the SrTiO3-based conducting interface is enhanced by increasing the lattice mismatch and growth oxygen pressure PO2. For the 26-unit-cell LaAlO3/SrTiO3 (LAO/STO) interface with lattice mismatch being 3.0%, the Kondo-like scattering is observed when PO2 is beyond 1 mTorr. By contrast, when the lattice mismatch is reduced to 1.0% at the (La0.3Sr0.7)(Al0.65Ta0.35)O3/SrTiO3 (LSAT/STO) interface, the metallic state is always preserved up to PO2 of 100 mTorr. The data from Hall measurement and X-ray absorption near edge structure (XANES) spectroscopy reveal that the larger amount of localized Ti(3+) ions are formed at the LAO/STO interface compared to LSAT/STO. Those localized Ti(3+) ions with unpaired electrons can be spin-polarized to scatter mobile electrons, responsible for the Kondo-like scattering observed at the LAO/STO interface.

Electronic screening-enhanced hole pairing in two-leg spin ladders studied by high-resolution resonant inelastic x-ray scattering at Cu M edges.

We study the electronic screening mechanisms of the effective Coulomb on-site repulsion in hole-doped Sr(14)Cu(24)O(41) compared to undoped La(6)Ca(8)Cu(24)O(41) using polarization dependent high-resolution resonant inelastic x-ray scattering at Cu M edges. By measuring the energy of the effective Coulomb on-site repulsion and the spin excitations, we estimate superexchange and hopping matrix element energies along rungs and legs, respectively. Interestingly, hole doping locally screens the Coulomb on-site repulsion reducing it by as much as 25%. We suggest that the increased ratio of the electronic kinetic to the electronic correlation energy contributes to the local superexchange mediated pairing between holes.

Mechanisms of charge transfer and redistribution in LaAlO3/SrTiO3 revealed by high-energy optical conductivity.

In condensed matter physics the quasi two-dimensional electron gas at the interface of two different insulators, polar LaAlO3 on nonpolar SrTiO3 (LaAlO3/SrTiO3) is a spectacular and surprising observation. This phenomenon is LaAlO3 film thickness dependent and may be explained by the polarization catastrophe model, in which a charge transfer of 0.5e(-) from the LaAlO3 film into the LaAlO3/SrTiO3 interface is expected. Here we show that in conducting samples (≥ 4 unit cells of LaAlO3) there is indeed a ~0.5e(-) transfer from LaAlO3 into the LaAlO3/SrTiO3 interface by studying the optical conductivity in a broad energy range (0.5-35 eV). Surprisingly, in insulating samples (≤ 3 unit cells of LaAlO3) a redistribution of charges within the polar LaAlO3 sublayers (from AlO2 to LaO) as large as ~0.5e(-) is observed, with no charge transfer into the interface. Hence, our results reveal the different mechanisms for the polarization catastrophe compensation in insulating and conducting LaAlO3/SrTiO3 interfaces.

Self-consistent iteration procedure in analyzing reflectivity and spectroscopic ellipsometry data of multilayered materials and their interfaces.

For multilayered materials, reflectivity depends on the complex dielectric function of all the constituent layers, and a detailed analysis is required to separate them. Furthermore, for some cases, new quantum states can occur at the interface which may change the optical properties of the material. In this paper, we discuss various aspects of such analysis, and present a self-consistent iteration procedure, a versatile method to extract and separate the complex dielectric function of each individual layer of a multilayered system. As a case study, we apply this method to LaAlO3/SrTiO3 heterostructure in which we are able to separate the effects of the interface from the LaAlO3 film and the SrTiO3 substrate. Our method can be applied to other complex multilayered systems with various numbers of layers.

Terahertz conductivity of topological surface states in Bi1.5Sb0.5Te1.8Se1.2.

Topological insulators are electronic materials with an insulating bulk and conducting surface. However, due to free carriers in the bulk, the properties of the metallic surface are difficult to detect and characterize in most topological insulator materials. Recently, a new topological insulator Bi1.5Sb0.5Te1.7Se1.3 (BSTS) was found, showing high bulk resistivities of 1-10 Ω.cm and greater contrast between the bulk and surface resistivities compared to other Bi-based topological insulators. Using Terahertz Time-Domain Spectroscopy (THz-TDS), we present complex conductivity of BSTS single crystals, disentangling the surface and bulk contributions. We find that the Drude spectral weight is 1-2 orders of magnitude smaller than in other Bi-based topological insulators, and similar to that of Bi2Se3 thin films, suggesting a significant contribution of the topological surface states to the conductivity of the BSTS sample. Moreover, an impurity band is present about 30 meV below the Fermi level, and the surface and bulk carrier densities agree with those obtained from transport data. Furthermore, from the surface Drude contribution, we obtain a ~98% transmission through one surface layer--this is consistent with the transmission through single-layer or bilayer graphene, which shares a common Dirac-cone feature in the band structure.

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.

Electronic phase separation at the LaAlO3/SrTiO3 interface.

There are many electronic and magnetic properties exhibited by complex oxides. Electronic phase separation (EPS) is one of those, the presence of which can be linked to exotic behaviours, such as colossal magnetoresistance, metal-insulator transition and high-temperature superconductivity. A variety of new and unusual electronic phases at the interfaces between complex oxides, in particular between two non-magnetic insulators LaAlO(3) and SrTiO(3), have stimulated the oxide community. However, no EPS has been observed in this system despite a theoretical prediction. Here, we report an EPS state at the LaAlO(3)/SrTiO(3) interface, where the interface charges are separated into regions of a quasi-two-dimensional electron gas, a ferromagnetic phase, which persists above room temperature, and a (superconductor like) diamagnetic/paramagnetic phase below 60 K. The EPS is due to the selective occupancy (in the form of 2D-nanoscopic metallic droplets) of interface sub-bands of the nearly degenerate Ti orbital in the SrTiO(3). The observation of this EPS demonstrates the electronic and magnetic phenomena that can emerge at the interface between complex oxides mediated by the Ti orbital.

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).

Room-temperature ferromagnetism of Cu-doped ZnO films probed by soft X-ray magnetic circular dichroism.

We report direct evidence of room-temperature ferromagnetic ordering in O-deficient ZnO:Cu films by using soft x-ray magnetic circular dichroism and x-ray absorption. Our measurements have revealed unambiguously two distinct features of Cu atoms associated with (i) magnetically ordered Cu ions present only in the oxygen-deficient samples and (ii) magnetically disordered regular Cu2+ ions present in all the samples. We find that a sufficient amount of both oxygen vacancies (V(O)) and Cu impurities is essential to the observed ferromagnetism, and a non-negligible portion of Cu impurities is uninvolved in the magnetic order. Based on first-principles calculations, we propose a microscopic "indirect double-exchange" model, in which alignments of localized large moments of Cu in the vicinity of the V(O) are mediated by the large-sized vacancy orbitals.

Two-component dynamics of the order parameter of high temperature Bi2Sr2CaCu2O8+delta superconductors revealed by time-resolved Raman scattering.

We study the dynamics of the superconducting order parameter in the high-Tc cuprate Bi2Sr2CaCu2O8+delta by employing a novel time-resolved pump-probe Raman experiment. We find two different coupling mechanisms that contribute equally to the pair-breaking peak. One coupling sets in very fast at 2 ps and relaxes slowly, while the other one is delayed and sets in roughly at 5 ps and relaxes fast. A model that couples holes through phonons is able to reproduce one part of the condensate dynamics; thus, we argue that hole-spin interactions are of importance as well.

Strain amplification of the 4k_(F) chain instability in Sr14Cu24O41.

We used resonant soft x-ray scattering to study the chain ordering in Sr14Cu24O41 (SCO). We observed, for the first time, both the chain and ladder orders in SCO with the same probe. We found that the chain modulation in SCO is incommensurate with wave vector L_(c)=0.318, is strongly temperature (T) dependent, and is accompanied by a substantial hole modulation. By contrast, the chain modulation in a hole-depleted control sample La6Ca8Cu24O41 was commensurate (L_(c)=0.3), T independent, and purely structural. We conclude that the chain charge order in SCO is a 4k_(F) charge density wave stabilized by the misfit strain between the ladder and chain substructures.

Magnetizing oxides by substituting nitrogen for oxygen.

We describe a possible pathway to new magnetic materials with no conventional magnetic elements present. The substitution of nitrogen for oxygen in simple nonmagnetic oxides leads to holes in N 2p states which form local magnetic moments. Because of the very large Hund's rule coupling of Nitrogen and O 2p electrons and the rather extended spatial extent of the wave functions these materials are predicted to be ferromagnetic metals or small band gap insulators. Experimental studies support the theoretical calculations with regard to the basic electronic structure and the formation of local magnetic moments. It remains to be seen if these materials are magnetically ordered and, if so, below what temperature.