Takeharu Sugiyama

Magnetic dichroism in angle-resolved hard x-ray photoemission from buried layers

This work reports the measurement of magnetic dichroism in angular-resolved photoemission from in-plane magnetized buried thin films. The high bulk sensitivity of hard x-ray photoelectron spectroscopy (HAXPES) in combination with circularly polarized radiation enables the investigation of the magnetic properties of buried layers. HAXPES experiments with an excitation energy of 8 keV were performed on exchange-biased magnetic layers covered by thin oxide films. Two types of structures were investigated with the IrMn exchange-biasing layer either above or below the ferromagnetic layer: one with a CoFe layer on top and another with a Co2FeAl layer buried beneath the IrMn layer. A pronounced magnetic dichroism is found in the Co and Fe 2p states of both materials. The localization of the magnetic moments at the Fe site conditioning the peculiar characteristics of the Co2FeAl Heusler compound, predicted to be a half-metallic ferromagnet, is revealed from the magnetic dichroism detected in the Fe 2p states.

Band alignment of InGaZnO4/Si interface by hard x-ray photoelectron spectroscopy

Although amorphous InGaZnO4 has intensively been studied for a semiconductor channel material of thin-film transistors in next-generation flat-panel displays, its electronic structure parameters have not been reported. In this work, the electron affinities (χ) and the ionization potentials (Ip) of crystalline and amorphous InGaZnO4 (c-IGZO and a-IGZO) were measured using bulk-sensitive hard x-ray photoelectron spectroscopy. First, the χ and Ip values of c-IGZO and a-IGZO thin films were estimated by aligning the Zn 2p3/2 core level energies to a literature value for ZnO, which provided χ = 3.90 eV and Ip = 7.58 eV for c-IGZO and 4.31 eV and 7.41 eV for a-IGZO. It was also confirmed that the escape depth of the photoelectrons excited by the photon energy of 5950.2 eV is 3.3 nm for a-IGZO and large enough for directly measuring the interface electronic structure using a-IGZO/c-Si heterojunctions. It provided the valence band offset of ∼2.3 eV, which agrees well with the above data. The present results subst...

Electronic structure of the hole-doped delafossite oxides CuCr 1-xMgxO2

We report the detailed electronic structure of a hole-doped delafossite oxide CuCr_{1-x}Mg_{x}O_{2} (0 <= x <= 0.03) studied by photoemission spectroscopy (PES), soft x-ray absorption spectroscopy (XAS), and band-structure calculations within the local-density approximation +U (LDA+U) scheme. Cr/Cu 3p-3d resonant PES reveals that the near-Fermi-level leading structure has primarily the Cr 3d character with a minor contribution from the Cu 3d through Cu 3d-O 2p-Cr 3d hybridization, having good agreement with the band-structure calculations. This indicates that a doped hole will have primarily the Cr 3d character. Cr 2p PES and L-edge XAS spectra exhibit typical Cr^{3+} features for all x, while the Cu L-edge XAS spectra exhibited a systematic change with x. This indicates now that the Cu valence is monovalent at x=0 and the doped hole should have Cu 3d character. Nevertheless, we surprisingly observed two types of charge-transfer satellites that should be attributed to Cu^{+} (3d^{10}) and Cu^{2+} (3d^{9}) like initial states in Cu 2p-3d resonant PES spectrum for at x=0, while Cu 2p PES spectra with no doubt shows the Cu^{+} character even for the lightly doped samples. We propose that these contradictory results can be understood by introducing no only the Cu 4s state, but also finite Cu 3d,4s-Cr 3d charge transfer via O 2p states in the ground-state electronic configuration.

Empirical relationship between x-ray photoemission spectra and electrical conductivity in a colossal magnetoresistive manganite La1−xSrxMnO3

By using laboratory x-ray photoemission spectroscopy (XPS) and hard x-ray photoemission spectroscopy (HX-PES) at a synchrotron facility, we report an empirical semi-quantitative relationship between the valence/core-level x-ray photoemission spectral weight and electrical conductivity in La1−xSrxMnO3 as a function of x. In the Mn 2p3∕2 HX-PES spectra, we observed the shoulder structure due to the Mn3+ well-screened state. However, the intensity at x = 0.8 was too small to explain its higher electrical conductivity than x = 0.0, which confirms our recent analysis on the Mn 2p3∕2 XPS spectra. The near-Fermi level XPS spectral weight was found to be a measure of the variation of electrical conductivity with x in spite of a far lower energy resolution compared with the energy scale of the quasiparticle (coherent) peak because of the concurrent change of the coherent and incoherent spectral weight.

Spin Polarimetry and Magnetic Dichroism on a Buried Magnetic Layer Using Hard X-ray Photoelectron Spectroscopy

The spin-resolved electronic structure of buried magnetic layers is studied by hard X-ray photoelectron spectroscopy (HAXPES) using a spin polarimeter in combination with a high-energy hemispherical electron analyzer at the high-brilliance BL47XU beamline (SPring-8, Japan). Spin-resolved photoelectron spectra are analyzed in comparison with the results of magnetic linear and circular dichroism in photoelectron emission in the case of buried Co2FeAl0.5Si0.5 layers. The relatively large inelastic mean free path (up to 20 nm) of fast photoelectrons enables us to extend the HAXPES technique with electron-spin polarimetry and to develop spin analysis techniques for buried magnetic multilayers and interfaces.

Laboratory hard X-ray photoelectron spectroscopy of La1−xSrxMnO3

A laboratory hard X-ray photoelectron spectroscopy (HXPS) system equipped with a monochromatic Cr Kα (hν = 5414.7 eV) X-ray source was applied to an investigation of the core-level electronic structure of La1−xSrxMnO3. No appreciable high binding-energy shoulder in the O 1s HXPS spectra were observed while an enhanced low binding-energy shoulder structure in the Mn 2p3/2 HXPS spectra were observed, both of which are manifestation of high bulk sensitivity. Such high bulk sensitivity enabled us to track the Mn 2p3/2 shoulder structure in the full range of x, giving us a new insight into the binding-energy shift of the Mn 2p3/2 core level. Comparisons with the results using the conventional laboratory XPS (hν = 1486.6 eV) as well as those using a synchrotron radiation source (hν = 7939.9 eV) demonstrate that HXPS is a powerful and convenient tool to analyze the bulk electronic structure of a host of different compounds.

The Electronic State of Hydrogen in the α Phase of the Hydrogen‐Storage Material PdH(D)x: Does a Chemical Bond Between Palladium and Hydrogen Exist?

The palladium-hydrogen system is one of the most famous hydrogen-storage systems. Although there has been much research on β-phase PdH(D)x , we comprehensively investigated the nature of the interaction between Pd and H(D) in α-phase PdH(D)x (x<0.03 at 303 K), and revealed the existence of Pd-H(D) chemical bond for the first time, by various in situ experimental techniques and first-principles theoretical calculations. The lattice expansion, magnetic susceptibility, and electrical resistivity all provide evidence. In situ solid-state 1 H and 2 H NMR spectroscopy and first-principles theoretical calculations revealed that a Pd-H(D) chemical bond exists in the α phase, but the bonding character of the Pd-H(D) bond in the α phase is quite different from that in the β phase; the nature of the Pd-H(D) bond in the α phase is a localized covalent bond whereas that in the β phase is a metallic bond.

Discovery of Hexagonal Structured Pd–B Nanocrystals

We report on hexagonal close-packed (hcp) palladium (Pd)-boron (B) nanocrystals (NCs) by heavy B doping into face-centered cubic (fcc) Pd NCs. Scanning transmission electron microscopy-electron energy loss spectroscopy and synchrotron powder X-ray diffraction measurements demonstrated that the B atoms are homogeneously distributed inside the hcp Pd lattice. The large paramagnetic susceptibility of Pd is significantly suppressed in Pd-B NCs in good agreement with the reduction of density of states at Fermi energy suggested by X-ray absorption near-edge structure and theoretical calculations.