RESUMO
We study the electronic structure of bulk single crystals and epitaxial films of Fe_{3}O_{4}. Fe 2p core level spectra show clear differences between hard x-ray (HAX) and soft x-ray photoemission spectroscopy (PES). The bulk-sensitive spectra exhibit temperature (T) dependence across the Verwey transition, which is missing in the surface-sensitive spectra. By using an extended impurity Anderson full-multiplet model-and in contrast to an earlier peak assignment-we show that the two distinct Fe species (A and B site) and the charge modulation at the B site are responsible for the newly found double peaks in the main peak above T_{V} and its T-dependent evolution. The Fe 2p HAXPES spectra show a clear magnetic circular dichroism (MCD) in the metallic phase of magnetized 100-nm-thick films. The model calculations also reproduce the MCD and identify the contributions from magnetically distinct A and B sites. Valence band HAXPES shows a finite density of states at E_{F} for the polaronic half metal with a remnant order above T_{V} and a clear gap formation below T_{V}. The results indicate that the Verwey transition is driven by changes in the strongly correlated and magnetically active B-site electronic states, consistent with resistivity and optical spectra.
RESUMO
The newly installed BL28XU beamline at SPring-8 is dedicated to in situ structural and electronic analysis of rechargeable batteries. It supports the time range (1â ms to 100â s) and spatial range (1â µm to 1â mm) needed for battery analysis. Electrochemical apparatus for battery charging and discharging are available in experimental hutches and in a preparation room. Battery analysis can be carried out efficiently and effectively using X-ray diffraction, X-ray absorption fine-structure analysis and hard X-ray photoelectron spectroscopy. Here, the design and performance of the beamline are described, and preliminary results are presented.
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The electronic structure of doped Mn in (Ga,Mn)As is studied by resonant inelastic x-ray scattering. From configuration-interaction cluster-model calculations, the line shapes of the Mn L3 resonant inelastic x-ray scattering spectra can be explained by d-d excitations from the Mn ground state dominated by charge-transferred states, in which hole carriers are bound to the Mn impurities, rather than a pure acceptor Mn2+ ground state. Unlike archetypical d-d excitation, the peak widths are broader than the experimental energy resolution. We attribute the broadening to a finite lifetime of the d-d excitations, which decay rapidly to electron-hole pairs in the host valence and conduction bands through the hybridization of the Mn 3d orbital with the ligand band.
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A Si(111) winged crystal has been designed to minimize anticlastic bending and improve sagittal focusing efficiency. The crystal was thin with wide stiffening wings. The length-to-width ratio of the crystal was optimized by finite element analysis, and the optimal value was larger than the `golden value'. The analysis showed that the slope error owing to anticlastic bending is less than the Darwin width. The X-rays were focused two-dimensionally using the crystal and a tangentially bent mirror. The observed profiles of the focal spot agreed well with the results of a ray-tracing calculation in the energy range from 8 to 17.5â keV. X-ray diffraction measurements with a high signal-to-noise ratio using this focusing system were demonstrated for a small protein crystal.
Assuntos
Muramidase/química , Difração de Raios X/métodos , Animais , Cristalização/instrumentação , Desenho de Equipamento , SíncrotronsRESUMO
We study the surface and bulk electronic structure of the room-temperature ferromagnet Coâ¶TiO(2) anatase films using soft- and hard-x-ray photoemission spectroscopy with probe sensitivities of â¼1 and â¼10 nm, respectively. We obtain direct evidence of metallic Ti(3+) states in the bulk, which get suppressed to give a surface semiconductor, thus indicating the difference in electronic structure between surface and bulk. X-ray absorption and resonant photoemission spectroscopy reveal Ti(3+) electrons at the Fermi level (E(F)) and high-spin Co(2+) electrons occurring away from E(F). The results show the importance of the charge neutrality condition: Co(2+)+V(O)(2-)+2Ti(4+)âCo(2+)+2Ti(3+) (V(O) is oxygen vacancy), which gives rise to the elusive Ti 3d carriers mediating ferromagnetism via the Co 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals.
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Nonlinear, three-photon double excitation of He in intense extreme ultraviolet free-electron laser fields (â¼24.1 eV, â¼5 TW/cm2) is presented. Resonances to the doubly excited states converging to the He+ N=3 level are revealed by the shot-by-shot photoelectron spectroscopy and identified by theoretical calculations based on the time-dependent Schrödinger equation for the two-electron atom under a laser field. It is shown that the three-photon double excitation is enhanced by intermediate Rydberg states below the first ionization threshold, giving a greater contribution to the photoionization yields than the two-photon process by more than 1 order of magnitude.
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Epitaxial ultrathin Fe films on fcc Cu(001) exhibit a spin spiral (SS), in contrast to the ferromagnetism of bulk bcc Fe. We study the in-plane (IP) and out-of-plane (OP) Fermi surfaces (FSs) of the SS in 8 monolayer Fe/Cu(001) films using energy-dependent soft-x-ray momentum-resolved photoemission spectroscopy. We show that the SS originates in nested regions confined to OP FSs, which are drastically modified compared to IP FSs. From precise reciprocal-space maps in successive zones, we obtain the associated real space compressive strain of 1.5+/-0.5% along c axis. An autocorrelation analysis quantifies the incommensurate ordering vector q=(2pi/a)(0,0, approximately 0.86), favoring a SS and consistent with magneto-optic Kerr effect experiments. The results reveal the importance of IP and OP FS mapping for ultrathin films.
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Photoelectron spectroscopy has been performed to study the multiphoton double ionization of Ar in an intense extreme ultraviolet laser field (hν â¼ 21 eV, â¼ 5 TW/cm²), by using a free electron laser (FEL). Three distinct peaks identified in the observed photoelectron spectra clearly show that the double ionization proceeds sequentially via the formation of Ar(+): Ar+hνâAr (+) + eâ» and Ar²(+) + 2hνâAr(+) + eâ». Shot-by-shot recording of the photoelectron spectra allows simultaneous monitoring of FEL spectrum and the multiphoton process for each FEL pulse, revealing that the two-photon ionization from Ar(+) is significantly enhanced by intermediate resonances in Ar(+).
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We investigate the electronic structure of chromium nitride (CrN) across the first-order magnetostructural transition at T(N)â¼286 K. Resonant photoemission spectroscopy (PES) shows a gap in the 3d partial density of states at the Fermi level and an on-site Coulomb energy Uâ¼4.5 eV, indicating strong electron-electron correlations. Bulk-sensitive high-resolution (6 meV) laser PES reveals a clear Fermi edge indicating an antiferromagnetic metal below T(N). Hard x-ray Cr 2p core-level PES shows T-dependent changes across T(N) which originate from screening due to coherent states as substantiated by cluster model calculations using the experimentally observed U. Electrical resistivity confirms an insulator above T(N) (E(g)â¼70 meV) becoming a disordered metal below T(N). Thus, CrN transforms from a correlated insulator to an antiferromagnetic metal, coupled to the magnetostructural transition.
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The Magnéli phase Ti(4)O(7) exhibits two sharp jumps in resistivity with coupled structural transitions as a function of temperature at T(c1) approximately 142 K and T(c2) = 154 K. We have studied electronic structure changes across the two transitions using 7 eV laser, soft x-ray, and hard x-ray (HX) photoemission spectroscopy (PES). Ti 2p-3d resonant PES and HX PES show a clear metallic Fermi edge and mixed valency above T(c2). The low temperature phase below T(c1) shows a clear insulating gap of approximately 100 meV. The intermediate phase between T(c1) and T(c2) indicates a pseudogap coexisting with remnant coherent states. HX PES and complementary calculations have confirmed the coherent screening in the strongly correlated intermediate phase. The results suggest the existence of a highly anomalous state sandwiched between the mixed-valent Fermi liquid and charge ordered Mott-insulating phase in Ti(4)O(7).
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Spectroscopic photoemission and low energy electron microscope (SPELEEM) improved its performance after installation at BL17SU/SPring-8, where a multipolarization-mode undulator is employed to produce circularly and linearly polarized soft x rays. This undulator enables us to study the domain structures of ferromagnetic and antiferromagnetic materials by x-ray magnetic circular dichroism and x-ray magnetic linear dichroism. SPELEEM is used to study light elements (C, N, and O), 3d transition-metal elements and 4f rare earth elements, utilizing a wide range of photon energies. The two cylindrical mirrors adopted in front of SPELEEM ensure an illumination area of 14 x 14 microm(2) on the samples. The lateral resolution of a secondary electron photoemission electron microscope image is estimated to be better than 85 nm, whereas the energy resolution of the instrument is better than 0.4 eV.
Assuntos
Microscopia Eletrônica/instrumentação , Refratometria/instrumentação , Espectrometria por Raios X/instrumentação , Desenho de Equipamento , Análise de Falha de Equipamento , Microscopia Eletrônica/métodos , Refratometria/métodos , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Espectrometria por Raios X/métodosRESUMO
Cytokeratin expression in subungual squamous cell carcinoma was investigated in order to evaluate the origin and state of differentiation of the tumour. The tumour nests contained cytokeratin 14, 16 and 17, which were also expressed in the nail bed. Therefore, cytokeratin expression in subungual squamous cell carcinoma may reflect its indolent clinical prognosis.
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Carcinoma de Células Escamosas/metabolismo , Queratinas/metabolismo , Doenças da Unha/metabolismo , Neoplasias Cutâneas/metabolismo , Idoso de 80 Anos ou mais , Biomarcadores Tumorais/metabolismo , Carcinoma de Células Escamosas/patologia , Carcinoma de Células Escamosas/cirurgia , Humanos , Masculino , Doenças da Unha/patologia , Neoplasias Cutâneas/patologia , Neoplasias Cutâneas/cirurgia , PolegarAssuntos
Cisto Epidérmico/patologia , Hamartoma/patologia , Proteínas de Filamentos Intermediários/metabolismo , Queratinas/metabolismo , Glândulas Sebáceas/patologia , Dermatopatias/patologia , Idoso , Diagnóstico Diferencial , Cisto Epidérmico/metabolismo , Neoplasias Faciais/metabolismo , Neoplasias Faciais/patologia , Proteínas Filagrinas , Hamartoma/metabolismo , Humanos , Masculino , Glândulas Sebáceas/metabolismo , Dermatopatias/metabolismoRESUMO
A new method using ESR spin trapping was proposed for measuring the scavenging activity of antioxidants for the hydroxyl (OH) radical. (-)-Epigallocatechin gallate (EGCg) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO) were used as the antioxidant and spin trapping agent, respectively. The conventional method using a Fenton reaction had problems associated with the estimation of activity, because the antioxidant disturbs the system for generating OH radical by coordinating on Fe2+ and by consuming H2O2, besides scavenging the spin adduct (DMPO-OH). Intense gamma-irradiation was therefore used to generate OH radicals, and the intensity decrease in DMPO-OH after irradiation was followed to obtain the rate constant for the scavenging of DMPO-OH by EGCg. The intensities were extrapolated to zero time to estimate the quantity of DMPO-OH formed during gamma-irradiation. By using these values, the reaction rate constant between OH radical and EGCg was calculated as a ratio to that of DMPO. It was shown that this method is useful for comparing the OH radical-scavenging activity of various antioxidants.
Assuntos
Antioxidantes/efeitos da radiação , Catequina/análogos & derivados , Catequina/efeitos da radiação , Sequestradores de Radicais Livres/análise , Radical Hidroxila/análise , Antioxidantes/química , Catequina/química , Óxidos N-Cíclicos/química , Espectroscopia de Ressonância de Spin Eletrônica/métodos , Radicais Livres , Raios gama , Marcadores de Spin , Detecção de SpinRESUMO
The effect of sodium N-benzyl-D-glucamine dithiocarbamate (NBG-DTC) on the distribution and excretion of cadmium in rats exposed to cadmium and the chemical form and intestinal reabsorption of cadmium compound excreted in the bile were studied. Rats were injected intraperitoneally with 109CdCl2 (1 mg Cd and 10 microCi 109Cd/kg) and 24 h later, they were injected with NBG-DTC (400 or 1200 mumol/kg). The biliary excretion of cadmium was remarkably increased by intraperitoneally injection of NBG-DTC, while there was only a small increase in urinary excretion of cadmium. Such an enhancement effect of NBG-DTC on the biliary excretion of cadmium was much larger at the high dose (1200 mumol/kg) of NBG-DTC. The treatment with NBG-DTC significantly decreased the cadmium content in the liver at the dose of 1200 mumol/kg and did not result in the undesirable redistribution of cadmium to the tissues, such as brain, testes, heart and lung. In addition, it was found that the cadmium compound excreted in the bile was mainly characterized as cadmium-NBG-DTC and which was not reabsorbed from the intestinal tracts.
Assuntos
Cádmio/metabolismo , Rim/metabolismo , Fígado/metabolismo , Sorbitol/análogos & derivados , Tiocarbamatos/farmacologia , Animais , Injeções Intraperitoneais , Absorção Intestinal , Rim/efeitos dos fármacos , Fígado/efeitos dos fármacos , Masculino , Metalotioneína/análise , Ratos , Ratos Endogâmicos , Distribuição TecidualRESUMO
In order to achieve nondestructive observation of the three-dimensional spatially resolved electronic structure of solids, we have developed a scanning photoelectron microscope system with the capability of depth profiling in electron spectroscopy for chemical analysis (ESCA). We call this system 3D nano-ESCA. For focusing the x-ray, a Fresnel zone plate with a diameter of 200 µm and an outermost zone width of 35 nm is used. In order to obtain the angular dependence of the photoelectron spectra for the depth-profile analysis without rotating the sample, we adopted a modified VG Scienta R3000 analyzer with an acceptance angle of 60° as a high-resolution angle-resolved electron spectrometer. The system has been installed at the University-of-Tokyo Materials Science Outstation beamline, BL07LSU, at SPring-8. From the results of the line-scan profiles of the poly-Si/high-k gate patterns, we achieved a total spatial resolution better than 70 nm. The capability of our system for pinpoint depth-profile analysis and high-resolution chemical state analysis is demonstrated.
Assuntos
Elétrons , Microscopia Eletrônica de Varredura/instrumentação , Nanotecnologia/instrumentação , Análise Espectral/instrumentaçãoRESUMO
We have developed an ultrahigh-vacuum instrument for resonant diffraction experiments using polarized soft x rays in the energy range of hnu=300-2000 eV at beamline BL17SU of SPring-8. The diffractometer consists of modified differentially pumped rotary feedthroughs for theta-2theta stages, a sample manipulator with motor-controlled x-y-z-, tilt (chi)-, and azimuth (phi)-axes, and a liquid helium flow-type cryostat for temperature dependent measurements between 30 and 300 K. Test results indicate that the diffractometer exhibits high reproducibility (better than 0.001 degrees ) for a Bragg reflection of alpha-quartz 100 at a photon energy of hnu=1950 eV. Typical off- and on-resonance Bragg reflections in the energy range of 530-1950 eV could be measured using the apparatus. The results show that x-ray diffraction experiments with energy-, azimuth-, and incident photon polarization-dependence can be reliably measured using soft x rays in the energy range of approximately 300-2000 eV. The facility can be used for resonant diffraction experiments across the L-edge of transition metals, M-edge of lanthanides, and up to the Si K-edge of materials.
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We study the electronic structure of the filled skutterudite CeOs4Sb12 using photoemission spectroscopy (PES). Soft x-ray excited Ce 3d-4f resonant PES confirms the existence of Ce 4f states at the Fermi level (EF). Temperature dependent high-resolution laser-PES spectra reveal a pseudogap formation around EF, which can be explained in terms of the hybridization gap. Simultaneously, a sharp feature is formed just above EF with decreasing temperature. The heavy-fermion-like specific heat is attributed to the occupation of this feature. The results identify the origin of the anomalous coexistence of heavy-fermion and pseudogap behavior in terms of a symmetry dependent hybridization.
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We have reexamined the valence-band (VB) and core-level electronic structure of NiO by means of hard and soft x-ray photoemission spectroscopies. The spectral weight of the lowest energy state was found to be enhanced in the bulk sensitive Ni 2p core-level spectrum. A configuration-interaction model including a bound state screening has shown agreement with the core-level spectrum and off- and on-resonance VB spectra. These results identify the lowest energy states in the core-level and VB spectra as the Zhang-Rice (ZR) doublet bound states, consistent with the spin-fermion model and recent ab initio calculations within dynamical mean-field theory. The results indicate that the ZR character first ionization (the lowest hole-addition) states are responsible for transport properties in NiO and doped NiO.
RESUMO
High energy resolution photoelectron spectroscopy of conduction electrons in the vicinity of the Fermi edge in Al and Au at excitation energies of 880 and 7940 eV was carried out using synchrotron radiation. For the excitation energy of 7940 eV, the observed Fermi energy of Al shows a remarkable shift to higher binding energy as compared with that of Au, with accompanying broadening. This is due to the recoil effect of the emitted photoelectrons. The observed spectra are well reproduced by a simple model of Bloch electrons based on the isotropic Debye model.