Extended X-ray Absorption Fine Structure (EXAFS) Measurements on Alkali Metal Superatoms of Ta-Atom-Encapsulated Si16 Cage.

The silicon cage nanoclusters encapsulating a tantalum atom, termed Ta@Si16, exhibit characteristics of alkali metal "superatoms (SAs)". Despite this conceptual framework, the precise structures of Ta@Si16 and Ta@Si16+ remain unclear in quantum calculations due to three energetically close structural isomers: C3v, Td, and D4d structures. To identify the geometrical structure of Ta@Si16 SAs, structural analysis was conducted using extended X-ray absorption fine structure (EXAFS) with a high-intensity monochromatic X-ray source, keeping anaerobic conditions. Focusing on "superordered" films, which constitute amorphous thin films composed solely of Ta@Si16 SAs, this analysis preserved locally ordered structures. Spectral comparisons between experimental and simulated Ta L3-edge EXAFS unveil that Ta@Si16 SAs on a substrate adopt a C3v-derived structure, while Si K-edge EXAFS introduces spectral ambiguity in structural identifications, attributed to both intracluster and intercluster scatterings. These findings underscore the significance of locally ordered structure analyses in understanding and characterizing novel nanoscale materials.

Soft X-ray ARPES for three-dimensional crystals in the micrometre region.

An endstation dedicated to angle-resolved photoemission spectroscopy (ARPES) using a soft X-ray microbeam has been developed at the beamline BL25SU of SPring-8. To obtain a high photoemission intensity, this endstation is optimized for measurements under the condition of grazing beam incidence to a sample surface, where the glancing angle is 5° or smaller. A Wolter mirror is used for focusing the soft X-rays. Even at the glancing angle of 5°, the smallest beam spot still having a sufficient photon flux for ARPES is almost round on the sample surface and the FWHM diameter is ∼5 µm. There is no need to change the sample orientation for performing kx - ky mapping by virtue of the electron lens with a deflector of the photoelectron analyzer, which makes it possible to keep the irradiation area unchanged. A partially cleaved surface area as small as ∼20 µm was made on an Si(111) wafer and ARPES measurements were performed. The results are presented.

Enhancement of photovoltage by electronic structure evolution in multiferroic Mn-doped BiFeO3 thin films.

The bulk photovoltaic effect (BPVE) is a mechanism of recent focus for novel solar cells that exceed the power conversion efficiency of p-n junction solar cells because of the quantum mechanical effect to generate photocurrent known as shift current. Ferroelectrics are receiving attention again because of their high voltage generation by the BPVE and converse piezoelectric effect to realize high performance optical actuators. We have investigated the BPVE in ferroelectric BiFeO3 (BFO) single crystal thin films, whereby the photovoltage was enhanced by Mn doping, and 852 V generation was demonstrated at 80 K. The enhancement mechanism was also investigated using soft and hard X-ray photoelectron spectroscopy (SXPES, HAXPES), and soft X-ray absorption spectroscopy with synchrotron radiation. This report reveals a way to new voltage source applications employing the BPVE for high impedance devices with ferroelectrics. Important aspects for designing ferroelectric materials by impurity doping are also discussed.

Individual Atomic Imaging of Multiple Dopant Sites in As-Doped Si Using Spectro-Photoelectron Holography.

The atomic scale characterization of dopant atoms in semiconductor devices to establish correlations with the electrical activation of these atoms is essential to the advancement of contemporary semiconductor process technology. Spectro-photoelectron holography combined with first-principles simulations can determine the local three-dimensional atomic structures of dopant elements, which in turn affect their electronic states. In the work reported herein, this technique was used to examine arsenic (As) atoms doped into a silicon (Si) crystal. As 3d core level photoelectron spectroscopy demonstrated the presence of three types of As atoms at a total concentration of approximately 1020 cm-3, denoted as BEH, BEM, and BEL. On the basis of Hall effect measurements, the BEH atoms corresponded to electrically active As occupying substitutional sites and exhibiting larger thermal fluctuations than the Si atoms, while the BEM atoms corresponded to electrically inactive As embedded in the AsnV (n = 2-4) type clusters. Finally, the BEL atoms were assigned to electrically inactive As in locally disordered structures.

Development of optical choppers for time-resolved measurements at soft X-ray synchrotron radiation beamlines.

Two types of optical choppers for time-resolved measurements at synchrotron radiation soft X-ray beamlines have been developed. One type uses an air-spindle-type rotation mechanism with a two-stage differential pumping system to maintain the ultra-high vacuum of the X-ray beamline, and the other uses a magnetic bearing. Both can be installed at the soft X-ray beamlines at SPring-8, greatly improving the accessibility of pump-and-probe spectroscopy. The combination of X-ray chopper and pump-and-probe photoemission electron microscope at SPring-8 provides drastic improvements in signal-to-noise ratio and resolution compared with techniques using high-voltage gating of channel plate detectors. The choppers have the capability to be used not only at synchrotron radiation facilities but also at other types of soft X-ray and VUV beamlines.

Microscopically-tuned band structure of epitaxial graphene through interface and stacking variations using Si substrate microfabrication.

Graphene exhibits unusual electronic properties, caused by a linear band structure near the Dirac point. This band structure is determined by the stacking sequence in graphene multilayers. Here we present a novel method of microscopically controlling the band structure. This is achieved by epitaxy of graphene on 3C-SiC(111) and 3C-SiC(100) thin films grown on a 3D microfabricated Si(100) substrate (3D-GOS (graphene on silicon)) by anisotropic etching, which produces Si(111) microfacets as well as major Si(100) microterraces. We show that tuning of the interface between the graphene and the 3C-SiC microfacets enables microscopic control of stacking and ultimately of the band structure of 3D-GOS, which is typified by the selective emergence of semiconducting and metallic behaviours on the (111) and (100) portions, respectively. The use of 3D-GOS is thus effective in microscopically unlocking various potentials of graphene depending on the application target, such as electronic or photonic devices.

Orbital-specific tunability of many-body effects in bilayer graphene by gate bias and metal contact.

Graphene, a 2D crystal bonded by π and σ orbitals, possesses excellent electronic properties that are promising for next-generation optoelectronic device applications. For these a precise understanding of quasiparticle behaviour near the Dirac point (DP) is indispensable because the vanishing density of states (DOS) near the DP enhances many-body effects, such as excitonic effects and the Anderson orthogonality catastrophe (AOC) which occur through the interactions of many conduction electrons with holes. These effects renormalize band dispersion and DOS, and therefore affect device performance. For this reason, we have studied the impact of the excitonic effects and the AOC on graphene device performance by using X-ray absorption spectromicroscopy on an actual graphene transistor in operation. Our work shows that the excitonic effect and the AOC are tunable by gate bias or metal contacts, both of which alter the Fermi energy, and are orbital-specific.

From isotope labeled CH3CN to N2 inside single-walled carbon nanotubes.

The observation of one-dimensional N2 inside single-walled carbon nanotubes raises the questions, how are the N2 molecules formed and how do they manage to make their way to this peculiar place? We have used N(15) and C(13) isotope labeled acetonitrile during the synthesis of single-walled carbon nanotubes to investigate this process. The isotope shifts of phonons and vibrons are observed by Raman spectroscopy and X-ray absorption. We identify the catalytic decomposition of acetonitrile as the initial step in the reaction pathway to single-walled carbon nanotubes containing encapsulated N2.

Capability of insulator study by photoemission electron microscopy at SPring-8.

The observation method of photoemission electron microscopy (PEEM) on insulating samples has been established in an extremely simple way. Surface conductivity is induced locally on an insulating surface by continuous radiation of soft X-rays, and Au films close to the area of interest allow the accumulated charges on the insulated area to be released to ground level. Magnetic domain observations of a NiZn ferrite, local X-ray absorption spectroscopy of sapphire, high-resolution imaging of a poorly conducting Li0.9CoO2 film surface, and Au pattern evaporation on a fine rock particle are demonstrated. Using this technique, all users' experiments on poorly conducting samples have been performed successfully at the PEEM experimental station of SPring-8.

Detection and in situ switching of unreversed interfacial antiferromagnetic spins in a perpendicular-exchange-biased system.

By using the perpendicular-exchange-biased Pt/Co/α-Cr(2)O(3) system, we provide experimental evidence that the unreversed uncompensated Cr spins exist at the Co/α-Cr(2)O(3) interface. The unreversed uncompensated Cr spin manifests itself in both the vertical shift of an element-specific magnetization curve and the relative peak intensity of soft-x-ray magnetic circular dichroism spectrum. We also demonstrate an in situ switching of the interfacial Cr spins and correspondingly a reversal of the exchange bias without interfacial atomic diffusion. Such switching shows the direct relationship between the interfacial antiferromagnetic spins and origin of the exchange bias. The demonstrated switching of exchange bias would likely offer a new design of advanced spintronics devices, using the perpendicular-exchange-biased system, with low power consumption and ultrafast operation.

Development of a soft X-ray angle-resolved photoemission system applicable to 100†µm crystals.

A system for angle-resolved photoemission spectroscopy (ARPES) of small single crystals with sizes down to 100 µm has been developed. Soft X-ray synchrotron radiation with a spot size of ∼40 µm × 65 µm at the sample position is used for the excitation. Using this system an ARPES measurement has been performed on a Si crystal of size 120 µm × 100 µm × 80 µm. The crystal was properly oriented on a sample stage by measuring the Laue spots. The crystal was cleaved in situ with a microcleaver at 100 K. The cleaved surface was adjusted to the beam spot using an optical microscope. Consequently, clear band dispersions along the Γ-X direction reflecting the bulk electronic states were observed with a photon energy of 879 eV.

Ultrahigh-vacuum cleaving system for sub-100-microm crystals.

An ultrahigh-vacuum cleaver has been developed for cleaving small crystals with sizes of less than 100 microm. The cleaver is fully driven by stepping motors in order to control its position on the micrometer scale. A pair of blades with sharp edges is used to nip and cleave crystals. To position the edges of the blades relative to a small crystal, they are observed using an optical microscope with a long working distance. A silicon crystal with a size of approximately 80 microm has been cleaved by using the developed system, and the cleanliness of the obtained surface has been verified by photoemission spectroscopy.

In situ positioning of a few hundred micrometer-sized cleaved surfaces for soft-x-ray angle-resolved photoemission spectroscopy by use of an optical microscope.

A method to position samples with small cleaved regions has been developed to be applied to the angle-resolved photoemission spectroscopy (ARPES) which uses soft-x-ray synchrotron radiation focused down to 160 x 180 microm(2). A long-working-distance optical microscope is used for the sample observation. A selected region on a sample can be optimally set at the position of measurements, which is realized by the spatial resolution of the photoelectron analyzer. Using this method, electronic band dispersions of bulk silicon have been measured by ARPES for a partially cleaved region with a size of approximately 200 x 500 microm(2).

A video camera system for coaxial observation of a sample with an incident soft X-ray beam.

A video camera system for observing a sample from the direction of an incident soft X-ray beam has been developed. The sample is seen via two reflecting mirrors. The first mirror, which has a hole to allow the soft X-ray beam to pass through, is set on the beam axis in a vacuum. The second mirror is used to cancel out the mirror inversion of the image. This camera system is used for efficient positioning of samples in a soft X-ray beam.

Nanoscale chemical imaging by scanning tunneling microscopy assisted by synchrotron radiation.

Nanoscale chemical imaging using scanning tunneling microscopy is demonstrated with a core-level excitation of the probed element by a synchrotron radiation light. Pronounced element-specific contrasts were observed in the spatial resolution of approximately 10 nm on checkerboard-patterned Ni and Fe samples in differential photoinduced current images taken with the scanning tunneling microscopy tip under the synchrotron radiation irradiation whose photon energies are above and below the Ni (Fe) L absorption edge. The local detection of the photoinduced secondary electrons through the surface barrier lowered by the proximate tip and/or via the tunneling process probably plays an important role in achieving the high-spatial resolution.

Construction and development of a time-resolved x-ray magnetic circular dichroism-photoelectron emission microscopy system using femtosecond laser pulses at BL25SU SPring-8.

A femtosecond pulsed laser system has been installed at the BL25SU soft x-ray beamline at SPring-8 for time-resolved pump-probe experiments with synchronization of the laser pulses to the circularly polarized x-ray pulses. There are four different apparatuses situated at the beamline; for photoemission spectroscopy, two-dimensional display photoelectron diffraction, x-ray magnetic circular dichroism (XMCD) with electromagnetic coils, and photoelectron emission microscopy (PEEM). All four can be used for time-resolved experiments, and preliminary investigations have been carried out using the PEEM apparatus to observe magnetization dynamics in combination with XMCD. In this article, we describe the details of the stroboscopic pump-probe XMCD-PEEM experiment, and present preliminary data. The repetition rate of the laser pulses is set using a pulse selector to match the single bunches of SPring-8's hybrid filling pattern, which consists of several single bunches and a continuous bunch train. Electrons ejected during the bunch train, which do not provide time-resolved signal, are eliminated by periodically reducing the channel plate voltage using a custom-built power supply. The pulsed laser is used to create 300 ps long magnetic field pulses, which cause magnetic excitations in micron-sized magnetic elements which contain magnetic vortex structures. The observed frequency of the motion is consistent with previously reported observations and simulations.

A new spin-polarized photoemission spectrometer with very high efficiency and energy resolution.

A new spin- and angle-resolved photoemission spectrometer was developed adopting the very-low-energy-electron-diffraction (VLEED)-type spin polarimeter. The Fe(001)p(1x1)-O film grown on MgO(001) crystal for the VLEED target yields significantly high spin-resolving power, the effective Sherman function of 0.40+/-0.02, with long lifetime and stability compared to the conventional Fe(001) target. Under the favor of high resolving power, approximately 100 times higher efficiency than that of conventional Mott-type spin polarimeter, the figure of merit of 1.9+/-0.2x10(-2) was achieved. Owing to this high efficiency, high-energy resolution can be realized with this new spin-polarized photoemission spectrometer. The simplified ways of target preparation and revitalization make the VLEED spin polarimeter much more convenient and feasible for the spin-polarized photoemission spectroscopy.