Development of a scanning soft X-ray spectromicroscope to investigate local electronic structures on surfaces and interfaces of advanced materials under conditions ranging from low vacuum to helium atmosphere.

A scanning soft X-ray spectromicroscope was recently developed based mainly on the photon-in/photon-out measurement scheme for the investigation of local electronic structures on the surfaces and interfaces of advanced materials under conditions ranging from low vacuum to helium atmosphere. The apparatus was installed at the soft X-ray beamline (BL17SU) at SPring-8. The characteristic features of the apparatus are described in detail. The feasibility of this spectromicroscope was demonstrated using soft X-ray undulator radiation. Here, based on these results, element-specific two-dimensional mapping and micro-XAFS (X-ray absorption fine structure) measurements are reported, as well as the observation of magnetic domain structures from using a reference sample of permalloy micro-dot patterns fabricated on a silicon substrate, with modest spatial resolution (e.g. ∼500 nm). Then, the X-ray radiation dose for Nafion® near the fluorine K-edge is discussed as a typical example of material that is not radiation hardened against a focused X-ray beam, for near future experiments.

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.

Tilting and rotational motions of silver halide crystal with diffracted X-ray blinking.

The dynamic properties of crystalline materials are important for understanding their local environment or individual single-grain motions. A new time-resolved observation method is required for use in many fields of investigation. Here, we developed in situ diffracted X-ray blinking to monitor high-resolution diffraction patterns from single-crystal grains with a 50 ms time resolution. The diffraction spots of single grains of silver halides and silver moved in the θ and χ directions during the photolysis chemical reaction. The movements of the spots represent tilting and rotational motions. The time trajectory of the diffraction intensity reflecting those motions was analysed by using single-pixel autocorrelation function (sp-ACF). Single-pixel ACF analysis revealed significant differences in the distributions of the ACF decay constants between silver halides, suggesting that the motions of single grains are different between them. The rotational diffusion coefficients for silver halides were estimated to be accurate at the level of approximately 0.1 to 0.3 pm2/s. Furthermore, newly formed silver grains on silver halides correlated with their ACF decay constants. Our high-resolution atomic scale measurement-sp-ACF analysis of diffraction patterns of individual grains-is useful for evaluating physical properties that are broadly applicable in physics, chemistry, and materials science.

Skewed electronic band structure induced by electric polarization in ferroelectric BaTiO3.

Skewed band structures have been empirically described in ferroelectric materials to explain the functioning of recently developed ferroelectric tunneling junction (FTJs). Nonvolatile ferroelectric random access memory (FeRAM) and the artificial neural network device based on the FTJ system are rapidly developing. However, because the actual ferroelectric band structure has not been elucidated, precise designing of devices has to be advanced through appropriate heuristics. Here, we perform angle-resolved hard X-ray photoemission spectroscopy of ferroelectric BaTiO3 thin films for the direct observation of ferroelectric band skewing structure as the depth profiles of atomic orbitals. The depth-resolved electronic band structure consists of three depth regions: a potential slope along the electric polarization in the core, the surface and interface exhibiting slight changes. We also demonstrate that the direction of the energy shift is controlled by the polarization reversal. In the ferroelectric skewed band structure, we found that the difference in energy shifts of the atomic orbitals is correlated with the atomic configuration of the soft phonon mode reflecting the Born effective charges. These findings lead to a better understanding of the origin of electric polarization.

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.

Time-resolved HAXPES using a microfocused XFEL beam: From vacuum space-charge effects to intrinsic charge-carrier recombination dynamics.

Time-resolved hard X-ray photoelectron spectroscopy (trHAXPES) using microfocused X-ray free-electron laser (XFEL, hν = 8 keV) pulses as a probe and infrared laser pulses (hν = 1.55 eV) as a pump is employed to determine intrinsic charge-carrier recombination dynamics in La:SrTiO3. By means of a combination of experiments and numerical N-body simulations, we first develop a simple approach to characterize and decrease XFEL-induced vacuum space-charge effects, which otherwise pose a serious limitation to spectroscopy experiments. We then show that, using an analytical mean-field model, vacuum space-charge effects can be counteracted by pump laser-induced photoholes at high excitation densities. This provides us a method to separate vacuum space-charge effects from the intrinsic charge-carrier recombination dynamics in the time domain. Our trHAXPES results thus open a route to studies of intrinsic charge-carrier dynamics on picosecond time scales with lateral spatial resolution on the micrometer scale.

System of laser pump and synchrotron radiation probe microdiffraction to investigate optical recording process.

We have developed a system of laser-pump and synchrotron radiation probe microdiffraction to investigate the phase-change process on a nanosecond time scale of Ge2Sb2Te5 film embedded in multi-layer structures, which corresponds to real optical recording media. The measurements were achieved by combining (i) the pump-laser system with a pulse width of 300 ps, (ii) a highly brilliant focused microbeam with wide peak-energy width (ΔE∕E ~ 2%) made by focusing helical undulator radiation without monochromatization, and (iii) a precise sample rotation stage to make repetitive measurements. We successfully detected a very weak time-resolved diffraction signal by using this system from 100-nm-thick Ge2Sb2Te5 phase-change layers. This enabled us to find the dependence of the crystal-amorphous phase change process of the Ge2Sb2Te5 layers on laser power.

Site-specific synthesis of oxo-bridged mixed-valence binuclear complexes on mesoporous silica.

We report the site-specific synthesis of mixed valence TiIV-O-FeII complexes within the pores of ordered mesoporous silica (SBA-15). By using 6-di- tert-butylpyridine as the selective activator of tripodally linked TiIV-OH groups of Ti-grafted SBA-15, the FeCl2.4H2O complexes reacted selectively with the nucleophilic TiIV-O(-) groups. The formation of Si-O-FeII byproducts, due to the reaction with the abundant Si-OH groups, was successfully restricted and the selectivity for forming the TiIV-O-FeII complexes exceeded 80%. The metal-metal interaction of TiIV-O-FeII complexes was confirmed by the appearance of TiIV/FeII --> TiIII/Fe III metal-to-metal charge transfer band, and their coordination, valency, and spin state were characterized by diffuse transmission UV-vis, Fourier transform IR, and Fe K-edge X-ray absorption fine structure measurements. It was also confirmed that the present methods can be extended to other metal combinations of TiIV-O-NiII and TiIV-O-MnII. The electron transfer processes occurring under photoinduced metal-to-metal charge transfer of oxo-bridged mixed valence complexes on silica supports have recently been proven as a new class of visible-light-sensitive redox centers. Thus, the present synthetic procedure allows the fabrication of a variety of photochemical reaction centers according to the molecular-level design.