Development of dual-beamline photoelectron momentum microscopy for valence orbital analysis.

The soft X-ray photoelectron momentum microscopy (PMM) experimental station at the UVSOR Synchrotron Facility has been recently upgraded by additionally guiding vacuum ultraviolet (VUV) light in a normal-incidence configuration. PMM offers a very powerful tool for comprehensive electronic structure analyses in real and momentum spaces. In this work, a VUV beam with variable polarization in the normal-incidence geometry was obtained at the same sample position as the soft X-ray beam from BL6U by branching the VUV beamline BL7U. The valence electronic structure of the Au(111) surface was measured using horizontal and vertical linearly polarized (s-polarized) light excitations from BL7U in addition to horizontal linearly polarized (p-polarized) light excitations from BL6U. Such highly symmetric photoemission geometry with normal incidence offers direct access to atomic orbital information via photon polarization-dependent transition-matrix-element analysis.

Fermiology and Origin of T_{c} Enhancement in a Kagome Superconductor Cs(V_{1-x}Nb_{x})_{3}Sb_{5}.

Kagome metals AV_{3}Sb_{5} (A=K, Rb, and Cs) exhibit a characteristic superconducting ground state coexisting with a charge density wave (CDW), whereas the mechanisms of the superconductivity and CDW have yet to be clarified. Here we report a systematic angle-resolved photoemission spectroscopy (ARPES) study of Cs(V_{1-x}Nb_{x})_{3}Sb_{5} as a function of Nb content x, where isovalent Nb substitution causes an enhancement of superconducting transition temperature (T_{c}) and the reduction of CDW temperature (T_{CDW}). We found that the Nb substitution shifts the Sb-derived electron band at the Γ point downward and simultaneously moves the V-derived band around the M point upward to lift up the saddle point (SP) away from the Fermi level, leading to the reduction of the CDW-gap magnitude and T_{CDW}. This indicates a primary role of the SP density of states to stabilize the CDW. The present result also suggests that the enhancement of superconductivity by Nb substitution is caused by the cooperation between the expansion of the Sb-derived electron pocket and the recovery of the V-derived density of states at the Fermi level.

Spatial Control of Charge Doping in n-Type Topological Insulators.

Spatially controlling the Fermi level of topological insulators and keeping their electronic states stable are indispensable processes to put this material into practical use for semiconductor spintronics devices. So far, however, such a method has not been established yet. Here we show a novel method for doping a hole into n-type topological insulators Bi2X3 (X= Se, Te) that overcomes the shortcomings of the previous reported methods. The key of this doping is to adsorb H2O on Bi2X3 decorated with a small amount of carbon, and its trigger is the irradiation of a photon with sufficient energy to excite the core electrons of the outermost layer atoms. This method allows controlling the doping amount by the irradiation time and acts as photolithography. Such a tunable doping makes it possible to design the electronic states at the nanometer scale and, thus, paves a promising avenue toward the realization of novel spintronics devices based on topological insulators.

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.

Surface science at the PEARL beamline of the Swiss Light Source.

The Photo-Emission and Atomic Resolution Laboratory (PEARL) is a new soft X-ray beamline and surface science laboratory at the Swiss Light Source. PEARL is dedicated to the structural characterization of local bonding geometry at surfaces and interfaces of novel materials, in particular of molecular adsorbates, nanostructured surfaces, and surfaces of complex materials. The main experimental techniques are soft X-ray photoelectron spectroscopy, photoelectron diffraction, and scanning tunneling microscopy (STM). Photoelectron diffraction in angle-scanned mode measures bonding angles of atoms near the emitter atom, and thus allows the orientation of small molecules on a substrate to be determined. In energy scanned mode it measures the distance between the emitter and neighboring atoms; for example, between adsorbate and substrate. STM provides complementary, real-space information, and is particularly useful for comparing the sample quality with reference measurements. In this article, the key features and measured performance data of the beamline and the experimental station are presented. As scientific examples, the adsorbate-substrate distance in hexagonal boron nitride on Ni(111), surface quantum well states in a metal-organic network of dicyano-anthracene on Cu(111), and circular dichroism in the photoelectron diffraction of Cu(111) are discussed.

Observation of hidden atomic order at the interface between Fe and topological insulator Bi2Te3.

To realize spintronic devices based on topological insulators (TIs), well-defined interfaces between magnetic metals and TIs are required. Here, we characterize atomically precisely the interface between the 3d transition metal Fe and the TI Bi2Te3 at different stages of its formation. Using photoelectron diffraction and holography, we show that after deposition of up to 3 monolayers Fe on Bi2Te3 at room temperature, the Fe atoms are ordered at the interface despite the surface disorder revealed by our scanning-tunneling microscopy images. We find that Fe occupies two different sites: a hollow adatom deeply relaxed into the Bi2Te3 quintuple layers and an interstitial atom between the third (Te) and fourth (Bi) atomic layers. For both sites, our core-level photoemission spectra and density-functional theory calculations demonstrate simultaneous chemical bonding of Fe to both Te and Bi atoms. We further show that upon deposition of Fe up to a thickness of 20 nm, the Fe atoms penetrate deeper into the bulk forming a 2-5 nm interface layer containing FeTe. In addition, excessive Bi is pushed down into the bulk of Bi2Te3 leading to the formation of septuple layers of Bi3Te4 within a distance of ∼25 nm from the interface. Controlling the magnetic properties of the complex interface structures revealed by our work will be of critical importance when optimizing the efficiency of spin injection in TI-based devices.

Selective detection of angular-momentum-polarized Auger electrons by atomic stereography.

When a core level is excited by circularly polarized light, the angular momentum of light is transferred to the emitted photoelectron, which can be confirmed by the parallax shift of the forward focusing peak (FFP) direction in a stereograph of atomic arrangement. No angular momentum has been believed to be transferred to normal Auger electrons resulting from the decay process filling core hole after photoelectron ejection. We succeeded in detecting a non-negligible circular dichroism contrast in a normal Auger electron diffraction from a nonmagnetic Cu(001) surface far off from the absorption threshold. Moreover, we detected angular-momentum-polarized Cu L(3)M(4,5)M(4,5) Auger electrons at the L(3) absorption threshold, where the excited core electron is trapped at the conduction band. From the kinetic energy dependence of the Auger electron FFP parallax shift, we found that the angular momentum is transferred to the Auger electron most effectively in the case of the (1)S(0) two-hole creation.

Surface aligned magnetic moments and hysteresis of an endohedral single-molecule magnet on a metal.

The interaction between the endohedral unit in the single-molecule magnet Dy_{2}ScN@C_{80} and a rhodium (111) substrate leads to alignment of the Dy 4f orbitals. The resulting orientation of the Dy_{2}ScN plane parallel to the surface is inferred from comparison of the angular anisotropy of x-ray absorption spectra and multiplet calculations in the corresponding ligand field. The x-ray magnetic circular dichroism is also angle dependent and signals strong magnetocrystalline anisotropy. This directly relates geometric and magnetic structure. Element specific magnetization curves from different coverages exhibit hysteresis at a sample temperature of ∼4 K. From the measured hysteresis curves, we estimate the zero field remanence lifetime during x-ray exposure of a submonolayer to be about 30 seconds.

Chemical vapor deposition and characterization of aligned and incommensurate graphene/hexagonal boron nitride heterostack on Cu(111).

Two limiting factors for a new technology of graphene-based electronic devices are the difficulty of growing large areas of defect-free material and the integration of graphene with an atomically flat and insulating substrate material. Chemical vapor deposition (CVD) on metal surfaces, in particular on copper, may offer a solution to the first problem, while hexagonal boron nitride (h-BN) has been identified as an ideal insulating substrate material. The bottom-up growth of graphene/h-BN stacks on copper surfaces appears therefore as a promising route for future device fabrication. As an important step, we demonstrate the consecutive growth of well-aligned graphene on h-BN, both as single layers, by low-pressure CVD on Cu(111) in an ultrahigh vacuum environment. The resulting films show a largely predominant orientation, defined by the substrate, where the graphene lattice aligns parallel to the h-BN lattice, while each layer maintains its own lattice constant. The lattice mismatch of 1.6% between h-BN and graphene leads to a moiré pattern with a periodicity of about 9 nm, as observed with scanning tunneling microscopy. Accordingly, angle-resolved photoemission data reveal two slightly different Brillouin zones for electronic states localized in graphene and in h-BN, reflecting the vertical decoupling of the two layers. The graphene appears n-doped and shows no gap opening at the K[overline] point of the two-dimensional Brillouin zone.

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.

Semiconductor-metal transition in Bi2Se3 caused by impurity doping.

Doping a typical topological insulator, Bi2Se3, with Ag impurity causes a semiconductor-metal (S-M) transition at 35 K. To deepen the understanding of this phenomenon, structural and transport properties of Ag-doped Bi2Se3 were studied. Single-crystal X-ray diffraction (SC-XRD) showed no structural transitions but slight shrinkage of the lattice, indicating no structural origin of the transition. To better understand electronic properties of Ag-doped Bi2Se3, extended analyses of Hall effect and electric-field effect were carried out. Hall effect measurements revealed that the reduction of resistance was accompanied by increases in not only carrier density but carrier mobility. The field-effect mobility is different for positive and negative gate voltages, indicating that the EF is located at around the bottom of the bulk conduction band (BCB) and that the carrier mobility in the bulk is larger than that at the bottom surface at all temperatures. The pinning of the EF at the BCB is found to be a key issue to induce the S-M transition, because the transition can be caused by depinning of the EF or the crossover between the bulk and the top surface transport.

Soft x-ray photoelectron momentum microscope for multimodal valence band stereography.

The photoelectron momentum microscope (PMM) in operation at BL6U, an undulator-based soft x-ray beamline at the UVSOR Synchrotron Facility, offers a new approach for µm-scale momentum-resolved photoelectron spectroscopy (MRPES). A key feature of the PMM is that it can very effectively reduce radiation-induced damage by directly projecting a single photoelectron constant energy contour in reciprocal space with a radius of a few Å-1 or real space with a radius of a few 100 µm onto a two-dimensional detector. This approach was applied to three-dimensional valence band structure E(k) and E(r) measurements ("stereography") as functions of photon energy (hν), its polarization (e), detection position (r), and temperature (T). In this study, we described some examples of possible measurement techniques using a soft x-ray PMM. We successfully applied this stereography technique to µm-scale MRPES to selectively visualize the single-domain band structure of twinned face-centered-cubic Ir thin films grown on Al2O3(0001) substrates. The photon energy dependence of the photoelectron intensity on the Au(111) surface state was measured in detail within the bulk Fermi surface. By changing the temperature of 1T-TaS2, we clarified the variations in the valence band dispersion associated with chiral charge-density-wave phase transitions. Finally, PMMs for valence band stereography with various electron analyzers were compared, and the advantages of each were discussed.

Photoemission Tomography of a One-Dimensional Row Structure of a Flat-Lying Picene Multilayer on Ag(110).

We applied photoemission tomography (PT) to a unique one-dimensional row structure of a picene multilayer realized on an anisotropic Ag(110) surface. Taking advantage of the simplified structure of the multilayer film, we successfully deconvoluted the photoelectron momentum maps of three frontier orbitals of picene. Thereafter, the clearly deconvoluted experimental momentum maps were compared to the Fourier transform simulation of the molecular orbitals of picene in detail, enabling not only the evaluation of the electronic structure of the picene in the multilayer but also the determination of the molecular orientation in the multilayer within a few degrees. In addition, the PT results indicated the orientation of the molecules in all layers to be flat-lying. The successful demonstration of PT of the multilayer molecular film marks an important step toward the wide-range utilization of the PT technique.

Projection-type electron spectroscopy collimator analyzer for charged particles and x-ray detections.

We developed a compact sized device for angular and energy analysis of charged particles in a wide acceptance cone angle of nearly 1π steradian. This device is configured from an electrostatic lens comprising an axisymmetric aspherical mesh, which has a concave shape viewed from the point source, a set of axisymmetric electrodes, planar grids, microchannel plates, and a fluorescent screen positioned coaxially. The potentials of electrodes are adjusted so that the trajectories of the electrons with arbitrarily set kinetic energy are substantially parallelized by the electrostatic lens and enter the planar grid perpendicularly. Instead of the planar grid, a collimator plate with parallel holes can be used as an energy band-pass filter. The angular distribution of electrons with the selected kinetic energy is projected directly onto the fluorescent screen without converging and passing through a pinhole. This is a simple but significant electron-optical design to obtain wide-range angular distribution with high angular resolution, and the analyzer can be suitably used for the two-dimensional angular distribution measurements of electrons and ions emitted from surfaces.

Acceptance-cone-tunable electron spectrometer for highly-efficient constant energy mapping.

We have developed an acceptance-cone-tunable (ACT) electron spectrometer for the highly efficient constant-energy photoelectron mapping of functional materials. The ACT spectrometer consists of the hemispherical deflection analyzer with the mesh-type electrostatic lens near the sample. The photoelectron trajectory can be converged by applying a negative bias to the sample and grounding the mesh lens and the analyzer entrance. The performance of the present ACT spectrometer with neither rotating nor tilting of the sample is demonstrated by the wide-angle observation of the well-known π-band dispersion of a single crystalline graphite over the Brillouin zone. The acceptance cone of the spectrometer is expanded by a factor of 3.30 when the negative bias voltage is 10 times as high as the kinetic energy of photoelectrons.

Fermi level tuning of Ag-doped Bi2Se3 topological insulator.

The temperature dependence of the resistivity (ρ) of Ag-doped Bi2Se3 (AgxBi2-xSe3) shows insulating behavior above 35 K, but below 35 K, ρ suddenly decreases with decreasing temperature, in contrast to the metallic behavior for non-doped Bi2Se3 at 1.5-300 K. This significant change in transport properties from metallic behavior clearly shows that the Ag doping of Bi2Se3 can effectively tune the Fermi level downward. The Hall effect measurement shows that carrier is still electron in AgxBi2-xSe3 and the electron density changes with temperature to reasonably explain the transport properties. Furthermore, the positive gating of AgxBi2-xSe3 provides metallic behavior that is similar to that of non-doped Bi2Se3, indicating a successful upward tuning of the Fermi level.

Approach for simultaneous measurement of two-dimensional angular distribution of charged particles. III. Fine focusing of wide-angle beams in multiple lens systems.

This paper provides a way of focusing wide-angle charged-particle beams in multiple lens systems. In previous papers [H. Matsuda, Phys. Rev. E 71, 066503 (2005); 74, 036501 (2006)], it was shown that an ellipsoidal mesh, combined with electrostatic lenses, enables correction of spherical aberration over wide acceptance angles up to +/-60 degrees . In this paper, practical situations where ordinary electron lenses are arranged behind the wide-angle electrostatic lenses are taken into account using ray tracing calculation. For practical realization of the wide-angle lens systems, the acceptance angle is set to +/-50 degrees . We note that the output beams of the wide-angle electrostatic lenses have somewhat large divergence angles which cause unacceptable or non-negligible spherical aberration in additional lenses. A solution to this problem is presented showing that lens combinations to cancel spherical aberration are available, whereby wide-angle charged-particle beams can be finely focused with considerably reduced divergence angles less than +/-5 degrees .

Strain Engineering for Anion Arrangement in Perovskite Oxynitrides.

Mixed-anion perovskites such as oxynitrides, oxyfluorides, and oxyhydrides have flexibility in their anion arrangements, which potentially enables functional material design based on coordination chemistry. However, difficulty in the control of the anion arrangement has prevented the realization of this concept. In this study, we demonstrate strain engineering of the anion arrangement in epitaxial thin films of the Ca1-xSrxTaO2N perovskite oxynitrides. Under compressive epitaxial strain, the axial sites in TaO4N2 octahedra tend to be occupied by nitrogen rather than oxygen, which was revealed by N and O K-edge linearly polarized X-ray absorption near-edge structure (LP-XANES) and scanning transmission electron microscopy combined with electron energy loss spectroscopy. Furthermore, detailed analysis of the LP-XANES indicated that the high occupancy of nitrogen at the axial sites is due to the partial formation of a metastable trans-type anion configuration. These results are expected to serve as a guide for the material design of mixed-anion compounds based on their anion arrangements.

Photoelectron Holographic Atomic Arrangement Imaging of Cleaved Bimetal-intercalated Graphite Superconductor Surface.

From the C 1s and K 2p photoelectron holograms, we directly reconstructed atomic images of the cleaved surface of a bimetal-intercalated graphite superconductor, (Ca, K)C8, which differed substantially from the expected bulk crystal structure based on x-ray diffraction (XRD) measurements. Graphene atomic images were collected in the in-plane cross sections of the layers 3.3 Å and 5.7 Å above the photoelectron emitter C atom and the stacking structures were determined as AB- and AA-type, respectively. The intercalant metal atom layer was found between two AA-stacked graphenes. The K atomic image revealing 2 × 2 periodicity, occupying every second centre site of C hexagonal columns, was reconstructed, and the Ca 2p peak intensity in the photoelectron spectra of (Ca, K)C8 from the cleaved surface was less than a few hundredths of the K 2p peak intensity. These observations indicated that cleavage preferentially occurs at the KC8 layers containing no Ca atoms.

Atomic-layer resolved magnetic and electronic structure analysis of ni thin film on a Cu(001) surface by diffraction spectroscopy.

Up until now there has been no direct method for detecting the electronic and magnetic structure of each atomic layer at the surface, which is an essential analysis technique for nanotechnology. For this purpose, we have developed a new method, diffraction spectroscopy, based on the photon energy dependence of the angular distribution of Auger electron emission. We have applied this method to analyze the magnetic structure of a Ni ultrathin film on a Cu(001) surface around the spin reorientation transition. Atomic-layer resolved x-ray absorption and magnetic circular dichroism spectra were obtained. Surface and interior core-level shifts and magnetic moments are determined for each atomic layer individually.