Beamline commissioning for microscopic measurements with ultraviolet and soft X-ray beam at the upgraded beamline BL-13B of the Photon Factory.

Beamline 13 of the Photon Factory has been in operation since 2010 as a vacuum ultraviolet and soft X-ray undulator beamline for X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and angle-resolved photoelectron spectroscopy (ARPES) experiments. The beamline and the end-station at branch B have been recently upgraded, enabling microscopic XPS, XAS, and ARPES measurements to be performed. In 2015, a planar undulator insertion device was replaced with an APPLE-II (advanced planar polarized light emitter II) undulator. This replacement allows use of linear, circular, and elliptical polarized light between 48 and 2000 eV with photon intensities of 109-1013 photons s-1. For microscopic measurements, a toroidal post-mirror was renewed to have more focused beam with profile sizes of 78 µm (horizontal) × 15 µm (vertical) and 84 µm × 11 µm at photon energies of 100 and 400 eV, respectively. A high-precision sample manipulator composed of an XYZ translator, a rotary feedthrough, and a newly developed goniometer, which is essential for microscopic measurements, has been used to control a sample specimen in six degrees of freedom, i.e. translation in the X, Y, and Z directions and rotation in the polar, azimuthal, and tilt directions. To demonstrate the performance of the focused beams, one- and two-dimensional XPS and XAS scan measurements of a copper grid have been performed. It was indicated from analysis of XPS and XAS intensity maps that the actual spatial resolution can be determined by the beam size.

A newly designed compact CEY-XAFS cell in the soft X-ray region and its application to surface XAFS measurements under ambient-pressure conditions without photoinduced side effects.

We report a newly designed compact cell to measure XAFS spectra with the conversion electron yield (CEY) method in the soft X-ray region under ambient-pressure gas conditions. Secondary electrons generated from the gas and sample by collision of X-ray-absorption-induced Auger electrons are collected by a positively biased collector electrode to obtain XAFS spectra. It was confirmed that this cell is applicable to soft X-ray surface XAFS measurements for different types of materials such as insulating organic materials and metal oxides under 1 bar gas conditions. During the measurements, photoinduced side effects were observed; i.e. photoinduced degradation of organic materials and photoinduced reduction/oxidation of metal oxides. We found that these photoinduced side effects can be sufficiently suppressed by controlling the measuring conditions. The presented measuring approach will enable surface XAFS spectra to be obtained in the soft X-ray region for various types of functional materials under ambient-pressure working conditions.

Development of a high-precision XYZ translator and estimation of beam profile of the vacuum ultraviolet and soft X-ray undulator beamline BL-13B at the Photon Factory.

A high-precision XYZ translator was developed for the microanalysis of electronic structures and chemical compositions on material surfaces by electron spectroscopy techniques, such as photoelectron spectroscopy and absorption spectroscopy, utilizing the vacuum ultraviolet and soft X-ray synchrotron radiation at an undulator beamline BL-13B at the Photon Factory. Using the high-precision translator, the profile and size of the undulator beam were estimated. They were found to strongly depend on the photon energy but were less affected by the polarization direction. To demonstrate the microscopic measurement capability of an experimental apparatus incorporating a high-precision XYZ translator, the homogeneities of an SnO film and a naturally grown anatase TiO2 single crystal were investigated using X-ray absorption and photoemission spectroscopies. The upgraded system can be used for elemental analyses and electronic structure studies at a spatial resolution in the order of the beam size.

In-gap state generated by La-on-Sr substitutional defects within the bulk of SrTiO3.

Local distortion in the conduction pathway has a significant influence on the conducting properties of oxides. The electronic states induced in the band gap of SrTiO3 by La doping were investigated using photoemission spectroscopy (PES) and soft X-ray emission spectroscopy (SXES); moreover, the local distortion in the conduction pathway was examined using extended X-ray absorption fine structure (EXAFS). An itinerant state and a localized state were observed as a metallic state and an in-gap state, respectively, in the PES spectra and as inelastic peaks in the SXES spectra. This implied that the itinerant state and the in-gap state coexisted within the bulk. From EXAFS results, it was observed that La doped into SrTiO3 substituted Sr and locally distorted the conduction pathway. The results showed that some electrons doped by La-on-Sr substitution are trapped/localized by the local distortion in the conduction pathway, whereas the remaining doped electrons itinerate in the pristine conduction pathway with no distortion.

Element selective oxidation on Rh-Pd bimetallic alloy surfaces.

The interactions between oxygen and Rh-Pd bimetallic alloy surfaces were investigated using surface sensitive experimental techniques and density functional theory calculations. The alloy surfaces were oxidized under 10-5 Torr and 100 mTorr oxygen upon heating above 250 °C. A thin Rh oxide layer was preferentially formed on a Rh1Pd9(100) surface, while a thin Pd oxide layer was formed on a Rh1Pd9(111) surface, though the Rh oxide is thermodynamically more stable irrespective of the surface orientation. Chemical analyses revealed that the initial Rh fraction for the (111) surface was significantly lower than that for the (100) surface, which suggests that the oxidized element on the surface is kinetically selected depending on the near surface initial composition.

Modulation of Electron-Phonon Coupling in One-Dimensionally Nanorippled Graphene on a Macrofacet of 6H-SiC.

Local electron-phonon coupling of a one-dimensionally nanorippled graphene is studied on a SiC(0001) vicinal substrate. We have characterized local atomic and electronic structures of a periodically nanorippled graphene (3.4 nm period) prepared on a macrofacet of the 6H-SiC crystal using scanning tunneling microscopy/spectroscopy (STM/STS) and angle-resolved photoelectron spectroscopy (ARPES). The rippled graphene on the macrofacets distributes homogeneously over the 6H-SiC substrate in a millimeter scale, and thus replica bands are detected by the macroscopic ARPES. The STM/STS results indicate the strength of electron-phonon coupling to the out-of-plane phonon at the K̅ points of graphene is periodically modified in accordance with the ripple structure. We propose an interface carbon nanostructure with graphene nanoribbons between the surface rippled graphene and the substrate SiC that periodically modifies the electron-phonon coupling in the surface graphene.

Angle-Resolved HAXPES Investigation on the Chemical Origin of Adhesion between Natural Rubber and Brass.

Bulk sensitivity of hard X-ray photoelectron spectroscopy (HAXPES) makes this technique suitable for chemical state analysis of bulk and deeply buried interfaces of solid materials. HAXPES is employed in the present study to examine the chemical state of adhesive interfaces between natural rubber and copper-zinc alloy, i.e., brass, while maintaining the adhesion structure in order to understand the chemical mechanism of rubber-to-brass adhesion. Angle-resolved measurements allow to distinguish between chemical species in rubber and those at the adhesive interface. We specially focus on sulfur-containing species because metal sulfides at the interface have been suggested to be crucial for adhesion. Line-shape analysis of S 1s spectra reveals that the interface that exhibits a strong adhesive property is mainly composed of copper sulfides with a predominant amount of CuS. This type of the interfacial chemical state is obtained when a rubber-bonded brass sample is subjected to vulcanization at 170 °C for 10 min. However, prolonged vulcanization leads to a partial dissolution of CuS as well as accumulation of Zn species in the form of ZnO/Zn(OH)2 and ZnS, and as a result, adhesion strength is lowered. The present study paves the way for accurate and detailed discussion on the chemical state of deeply buried interfaces through bulk sensitive in-situ measurements.

Effect of physisorption of inert organic molecules on Au(111) surface electronic states.

The modification of the Au(111) Shockley surface state (SS) by an n-alkane molecule (n-tetratetracontane) monolayer was observed by angle-resolved ultraviolet photoemission spectroscopy. Although there is little chance of chemical interaction in this ideal physisorption system, the volume of the Fermi surface of the SS was significantly reduced accompanied by the formation of large interface electric dipoles. Moreover, Rashba splitting of the SS by spin-orbit interactions was slightly increased upon n-tetratetracontane adsorption, which arose from the decrease in the symmetry of the wave function around the Au nuclei at the surface. The detailed information about the simple physisorption system presented in this paper provides basic knowledge for understanding the electronic structure at the interface between other organic molecules and metal substrates.

In situ removal of carbon contamination from a chromium-coated mirror: ideal optics to suppress higher-order harmonics in the carbon K-edge region.

Carbon-free chromium-coated optics are ideal in the carbon K-edge region (280-330 eV) because the reflectivity of first-order light is larger than that of gold-coated optics while the second-order harmonics (560-660 eV) are significantly suppressed by chromium L-edge and oxygen K-edge absorption. Here, chromium-, gold- and nickel-coated mirrors have been adopted in the vacuum ultraviolet and soft X-ray branch beamline BL-13B at the Photon Factory in Tsukuba, Japan. Carbon contamination on the chromium-coated mirror was almost completely removed by exposure to oxygen at a pressure of 8 × 10(-2) Pa for 1 h under irradiation of non-monochromated synchrotron radiation. The pressure in the chamber recovered to the order of 10(-7) Pa within a few hours. The reflectivity of the chromium-coated mirror of the second-order harmonics in the carbon K-edge region (560-660 eV) was found to be a factor of 0.1-0.48 smaller than that of the gold-coated mirror.

A high-pressure-induced dense CO overlayer on a Pt(111) surface: a chemical analysis using in situ near ambient pressure XPS.

We investigated the high-density CO adsorption phase formed on a Pt(111) surface when exposed to CO gas of pressure ranging from UHV to 100 mTorr using near-ambient-pressure (NAP)-XPS. Combined results from the NAP-XPS measurements and DFT calculations reveal the adsorption structure of CO molecules in the dense CO overlayer, which is stable under realistic conditions.

Width-dependent band gap of arm-chair graphene nanoribbons formed on vicinal SiC substrates by MBE.

Formation and electronic states of graphene nanoribbons with arm-chair edges (AGNR) are studied on the SiC(0001) vicinal surfaces toward the [11-00] direction. The surface step and terrace structures of both 4H and 6H-SiC substrates are used as the growth templates of one-dimensional arrays of AGNRs, which are prepared using the carbon molecular beam epitaxy followed by hydrogen intercalation. A band gap is observed above theπ-band maximum by angle-resolved photoelectron spectroscopy (ARPES) for the both samples. The average widths of the AGNRs are 6 and 10 nm, and the estimated average band gaps are 0.40 and 0.28 eV for the 4H- and 6H- substrates, respectively. A simple and phenomenological inverse relation between the energy gap and AGNR width works in the analyses of the ARPES data.

In situ removal of carbon contamination from optics in a vacuum ultraviolet and soft X-ray undulator beamline using oxygen activated by zeroth-order synchrotron radiation.

Carbon contamination of optics is a serious issue in all soft X-ray beamlines because it decreases the quality of experimental data, such as near-edge X-ray absorption fine structure, resonant photoemission and resonant soft X-ray emission spectra in the carbon K-edge region. Here an in situ method involving the use of oxygen activated by zeroth-order synchrotron radiation was used to clean the optics in a vacuum ultraviolet and soft X-ray undulator beamline, BL-13A at the Photon Factory in Tsukuba, Japan. The carbon contamination of the optics was removed by exposing them to oxygen at a pressure of 10(-1)-10(-4) Pa for 17-20 h and simultaneously irradiating them with zeroth-order synchrotron radiation. After the cleaning, the decrease in the photon intensity in the carbon K-edge region reduced to 2-5%. The base pressure of the beamline recovered to 10(-7)-10(-8) Pa in one day without baking. The beamline can be used without additional commissioning.

Interface Structures and Electronic States of Epitaxial Tetraazanaphthacene on Single-Crystal Pentacene.

The structural and electronic properties of interfaces composed of donor and acceptor molecules play important roles in the development of organic opto-electronic devices. Epitaxial growth of organic semiconductor molecules offers a possibility to control the interfacial structures and to explore precise properties at the intermolecular contacts. 5,6,11,12-tetraazanaphthacene (TANC) is an acceptor molecule with a molecular structure similar to that of pentacene, a representative donor material, and thus, good compatibility with pentacene is expected. In this study, the physicochemical properties of the molecular interface between TANC and pentacene single crystal (PnSC) substrates were analyzed by atomic force microscopy, grazing-incidence X-ray diffraction (GIXD), and photoelectron spectroscopy. GIXD revealed that TANC molecules assemble into epitaxial overlayers of the (010) oriented crystallites by aligning an axis where the side edges of the molecules face each other along the [1¯10] direction of the PnSC. No apparent interface dipole was found, and the energy level offset between the highest occupied molecular orbitals of TANC and the PnSC was determined to be 1.75 eV, which led to a charge transfer gap width of 0.7 eV at the interface.

Quasi-Homoepitaxial Junction of Organic Semiconductors: A Structurally Seamless but Electronically Abrupt Interface between Rubrene and Bis(trifluoromethyl)dimethylrubrene.

Single-crystalline organic semiconductors exhibiting band transport have opened new possibilities for the utilization of efficient charge carrier conduction in organic electronic devices. The epitaxial growth of molecular materials is a promising route for the realization of well-crystallized organic semiconductor p-n junctions for optoelectronic applications enhanced by the improved charge carrier mobility. In this study, the formation of a high-quality crystalline interface upon "quasi-homoepitaxial" growth of bis(trifluoromethyl)dimethylrubrene (fmRub) on the single-crystal surface of rubrene was revealed by using out-of-plane and grazing-incidence X-ray diffraction techniques. Ultraviolet photoelectron spectroscopy results indicated abrupt electronic energy levels and the occurrence of band bending across this quasi-homoepitaxial interface. This study verifies that the minimization of the lattice mismatch enhances the crystalline qualities at the heterojunctions even for van der Waals molecular condensates, potentially opening an untested route for the realization of high-mobility organic semiconductor optoelectronics.

Orientation-Dependent Hindrance to the Oxidation of Pd-Au Alloy Surfaces.

Oxidation of monometallic Pd and bimetallic Pd3Au alloy surfaces are observed by in situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at an elevated pressure (100 mTorr O2 ambient). It is directly evidenced that the alloying with Au hinders the surface oxidation of Pd3Au surfaces compared with monometallic Pd surfaces. Remarkably, the oxidation behavior is clearly different between Pd3Au(111) and (100) surfaces. The (100) surface has a relatively Pd-rich surface composition, and the surface oxide layer is formed, whereas the (111) surface has a Au-rich composition, and the surface oxidation is quite limited. A combined approach of experimental and theoretical techniques reveals that Pd/Au surface composition and atomic arrangement are key factors determining the oxidation behavior.

Initial oxidation of GaAs(100) under near-realistic environments revealed by in situ AP-XPS.

In situ monitoring of initial oxidation of GaAs surfaces was performed under (near-) realistic oxidizing environments, using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). The surface chemical states drastically change with time. The oxidation process at the sub-nano-meter-scale exhibits a significantly small activation energy, which can be regarded as a quasi-barrier-less oxidation.

How Rh surface breaks CO2 molecules under ambient pressure.

Utilization of carbon dioxide (CO2) molecules leads to increased interest in the sustainable synthesis of methane (CH4) or methanol (CH3OH). The representative reaction intermediate consisting of a carbonyl or formate group determines yields of the fuel source during catalytic reactions. However, their selective initial surface reaction processes have been assumed without a fundamental understanding at the molecular level. Here, we report direct observations of spontaneous CO2 dissociation over the model rhodium (Rh) catalyst at 0.1 mbar CO2. The linear geometry of CO2 gas molecules turns into a chemically active bent-structure at the interface, which allows non-uniform charge transfers between chemisorbed CO2 and surface Rh atoms. By combining scanning tunneling microscopy, X-ray photoelectron spectroscopy at near-ambient pressure, and computational calculations, we reveal strong evidence for chemical bond cleavage of O‒CO* with ordered intermediates structure formation of (2 × 2)-CO on an atomically flat Rh(111) surface at room temperature.

A novel organic-rich meteoritic clast from the outer solar system.

The Zag meteorite which is a thermally-metamorphosed H ordinary chondrite contains a primitive xenolithic clast that was accreted to the parent asteroid after metamorphism. The cm-sized clast contains abundant large organic grains or aggregates up to 20 µm in phyllosilicate-rich matrix. Here we report organic and isotope analyses of a large (~10 µm) OM aggregate in the Zag clast. The X-ray micro-spectroscopic technique revealed that the OM aggregate has sp2 dominated hydrocarbon networks with a lower abundance of heteroatoms than in IOM from primitive (CI,CM,CR) carbonaceous chondrites, and thus it is distinguished from most of the OM in carbonaceous meteorites. The OM aggregate has high D/H and 15N/14N ratios (δD = 2,370 ± 74‰ and δ15N = 696 ± 100‰), suggesting that it originated in a very cold environment such as the interstellar medium or outer region of the solar nebula, while the OM is embedded in carbonate-bearing matrix resulting from aqueous activities. Thus, the high D/H ratio must have been preserved during the extensive late-stage aqueous processing. It indicates that both the OM precursors and the water had high D/H ratios. Combined with 16O-poor nature of the clast, the OM aggregate and the clast are unique among known chondrite groups. We further propose that the clast possibly originated from D/P type asteroids or trans-Neptunian Objects.

Construction and evaluation of a miniature electron ion coincidence analyzer mounted on a conflat flange with an outer diameter of 114 mm.

We have developed a miniature electron ion coincidence (EICO) analyzer mounted on a conflat flange with an outer diameter of 114 mm. It consists of a cylindrical mirror analyzer (CMA), a time-of-flight ion mass spectrometer (TOF-MS), a commercially available linear motion feed through, and a tilt adjustment mechanism. Each sample surface was irradiated by synchrotron radiation, and the energies of emitted electrons were analyzed and detected by the CMA, while desorbed ions were collected by the TOF-MS in coincidence with the electrons. The performance of the EICO analyzer was tested by measuring the Auger-electron H+ photoion coincidence spectrum of condensed water at 4a1 <-- O 1s resonance.

Adsorbate-driven reactive interfacial Pt-NiO1-x nanostructure formation on the Pt3Ni(111) alloy surface.

The origin of the synergistic catalytic effect between metal catalysts and reducible oxides has been debated for decades. Clarification of this effect, namely, the strong metal-support interaction (SMSI), requires an understanding of the geometric and electronic structures of metal-metal oxide interfaces under operando conditions. We show that the inherent lattice mismatch of bimetallic materials selectively creates surface segregation of subsurface metal atoms. Interfacial metal-metal oxide nanostructures are then formed under chemical reaction environments at ambient pressure, which thus increases the catalytic activity for the CO oxidation reaction. Our in situ surface characterizations using ambient-pressure scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy exhibit (i) a Pt-skin layer on the Pt-Ni alloyed surface under ultrahigh vacuum, (ii) selective Ni segregation followed by the formation of NiO1-x clusters under oxygen gas, and (iii) the coexistence of NiO1-x clusters on the Pt-skin during the CO oxidation reaction. The formation of interfacial Pt-NiO1-x nanostructures is responsible for a highly efficient step in the CO oxidation reaction. Density functional theory calculations of the Pt3Ni(111) surface demonstrate that a CO molecule adsorbed on an exposed Pt atom with an interfacial oxygen from a segregated NiO1-x cluster has a low surface energy barrier of 0.37 eV, compared with 0.86 eV for the Pt(111) surface.