Development of hard x-ray photoelectron spectroscopy using synchrotron radiation x-ray up to 30 keV.

Hard X-ray photoelectron spectroscopy (HAXPES) is a powerful tool for investigating the chemical and electronic states of bulk and buried interfaces non-destructively due to its large probing depth. To obtain a much larger probing depth and measure deeper regions than conventional HAXPES, we have developed a high-energy HAXPES (HE-HAXPES) system excited by photon energies up to 30 keV. This system is achieved by combining an applied bias voltage on the sample with a conventional hemispherical electron energy analyzer. By utilizing this system, we successfully observed a Si 1s peak from the bulk-Si substrate underneath the 110-nm-thick SiO2 film at a photon energy of 30 keV. Moreover, the system found that the asymmetrical spectral shape of the Si substrate signal originated from the electronic state, which is upward band bending formed at the interface between the SiO2 film and Si substrate. The HE-HAXPES system, excited by photon energy up to 30 keV, could be a very useful tool to yield genuine insights into the chemical and electronic states in deeply buried regions.

BL09XU: an advanced hard X-ray photoelectron spectroscopy beamline of SPring-8.

The BL09XU beamline of SPring-8 has been reorganized into a beamline dedicated for hard X-ray photoelectron spectroscopy (HAXPES) to provide advanced capabilities with upgraded optical instruments. The beamline has two HAXPES analyzers to cover a wide range of applications. Two sets of double channel-cut crystal monochromators with the Si(220) and (311) reflections were installed to perform resonant HAXPES analyses with a total energy resolution of less than 300 meV over a wide energy range (4.9-12 keV) while achieving a fixed-exit condition. A double-crystal X-ray phase retarder using diamond crystals controls the polarization state with a high degree of polarization over 0.9 in the wide energy range 5.9-9.5 keV. Each HAXPES analyzer is equipped with a focusing mirror to provide a high-flux microbeam. The design and performance of the upgraded instruments are presented.

Sulfur poisoning of Pt and PtCo anode and cathode catalysts in polymer electrolyte fuel cells studied by operando near ambient pressure hard X-ray photoelectron spectroscopy.

We have investigated the S adsorption behaviours on Pt (average particle diameter of ∼2.6 nm) and Pt3Co (∼3.0 nm) anode and cathode electrode catalysts in polymer electrolyte fuel cells (PEFCs) under working conditions for the fresh state just after the aging process and also the degraded state after accelerated degradation tests (ADT), by studying near ambient pressure hard X-ray photoelectron spectroscopy (HAXPES). S 1s HAXPES of both the anode and cathode electrodes shows not only the principal S species from the sulfonic acid group (-SO3H) in the Nafion electrolyte but also other characteristic S species such as zero-valent S (S0) adsorbed on the carbon support and anionic S (S2-) adsorbed on the Pt electrode. The S2- species on Pt should be ascribed to S contamination poisoning the Pt catalyst electrode. The S2- species on the cathode can be oxidatively removed by applying a high cathode-anode bias voltage (≥0.8 V) to form SO32-, while at the anode the S2- species cannot be eliminated because of reductive environment in hydrogen gas. The important finding is the difference in S adsorption behaviours between the Pt/C and Pt3Co/C electrodes after ADT. After ADT, the Pt/C anode electrode exhibits much larger S2- adsorption than the Pt3Co/C anode electrode. This indicates that the Pt3Co/C anode is more desirable than the Pt/C one from the viewpoint of S poisoning. The reason for more tolerance of the Pt3Co/C anode catalyst against S poisoning after ADT can be ascribed to the more negative charge of the surface Pt atoms in the Pt3Co/C catalyst than those in the Pt/C one, thus yielding a weaker interaction between the surface Pt and the anionic S species as S2-, SO32-, and SO42-. A similar behaviour was observed also in the cathode catalyst. The present findings will nevertheless provide important information to design novel Pt-based PEFC electrodes with higher performance and longer durability.

SPring-8 BL36XU: Synchrotron Radiation X-Ray-Based Multi-Analytical Beamline for Polymer Electrolyte Fuel Cells under Operating Conditions.

We designed and constructed a beamline BL36XU at the 8 GeV synchrotron radiation facility SPring-8 to provide information required for the development of next-generation polymer electrolyte fuel cells (PEFCs) by clarifying the dynamic aspects of structures and electronic states of cathode catalysts under PEFC operating conditions and in the deterioration processes by accelerated durability test protcols. To investigate the mechanism and degradation process for the cathode electrocatalysis in practical PEFCs, we developed advanced time- and spatially-resolved in-situ/operando X-ray absorption fine structure measurement systems and complementary analytical systems (X-ray emission spectroscopy (XES), X-ray diffraction (XRD), X-ray computer tomography (CT) and hard X-ray photoelectron spectroscopy (HAXPES)) and combined them to develop multi-analytical systems at BL36XU. Multi-analytical systems are very powerful for observing spatial-temporal features of the transient processes occurring in complex systems such as PEFCs. This account describes the design, performance, and research results of the BL36XU and multi-analytical in-situ/operando systems.

Ambient Pressure Hard X-ray Photoelectron Spectroscopy for Functional Material Systems as Fuel Cells under Working Conditions.

Heterogeneous interfaces play important roles in a variety of functional material systems and technologies, such as catalysis, batteries, and devices. A fundamental understanding of efficient functions at interfaces under realistic conditions is crucial for sophisticated designs of useful material systems and novel devices. X-ray photoelectron spectroscopy is one of the most promising and common methods to investigate such material systems. Although X-ray photoelectron spectroscopy is usually conducted under high vacuum because of the requirement of electron detection with the precise measurement of kinetic energies, extensive efforts have been devoted to the measurements in gaseous environments. Very recently, we have succeeded in measuring X-ray photoelectron spectra under real ambient atmosphere (105 Pa), using synchrotron radiation hard X-rays with the photon energy of 8 keV and the windowless electron spectrometer system. In this Account, the novel useful technique of real ambient pressure hard X-ray photoelectron spectroscopy is reviewed. As examples of (near) ambient pressure hard X-ray photoelectron spectroscopy, hydrogen storage of Pd nanoparticles is at first investigated by recording Pd 3d and valence band spectra under hydrogen atmosphere. The Pd 3d and valence band spectra are found to change rather abruptly depending on the hydrogen pressure, demonstrating a behavior like phase transformation. Subsequently, as a main topic in this Account, we describe investigations of the electronic states of platinum nanoparticles on the cathode electrocatalyst in a polymer electrolyte fuel cell (PEFC) under the voltage operating conditions using the near ambient pressure hard X-ray photoelectron spectroscopic system. The Pt 4f and 3d X-ray photoelectron spectra of the cathode Pt/C catalysts clearly show that the oxidized Pt species is at most divalent and the tetravalent Pt species does not exist on the Pt nanoparticles even at the positive cathode-anode voltage of ∼1.4 V. Although the water oxidation reaction may take place at the potential, such a reaction does not lead to a buildup of detectable tetravalent Pt in the PEFC. The voltage-dependent Pt 3d X-ray photoelectron spectra show a clear hysteresis between the voltage increase and decrease processes. The fraction of oxidized Pt species matched the ratio of surface to total Pt atoms in the nanoparticles, which suggests that Pt oxidation occurs as a reaction event at only the first Pt layer of the Pt nanoparticles and the inner Pt atoms do not participate in the reaction practically. The developed technique is a valuable in situ tool for the investigation of the electronic states of PEFCs and other interesting functional material systems and devices under realistic working conditions.

Non-contact electric potential measurements of electrode components in an operating polymer electrolyte fuel cell by near ambient pressure XPS.

Photoelectron spectroscopy has the advantage of providing electric potentials by non-contact measurements based on the kinetic energy shift in component potential. We performed operando hard X-ray photoelectron spectroscopy (HAXPES) measurements with an 8 keV excitation source to measure the shift in electron kinetic energies as a function of the voltages of all the components at the anode and cathode electrodes of a polymer electrolyte fuel cell (PEFC). At the cathode electrode, when we increase the voltage between the cathode and anode from 0.2 to 1.2 V, the O 1s and F 1s peaks shift to a lower binding energy and the magnitude of the energy shift is equal to the voltage. The Pt 3d and C 1s peaks do not shift with the voltage since platinum nanoparticles and carbon supports at the cathode electrode have ground contact. In contrast to the cathode electrode, the peak shifts of all the components at the anode electrode show the same amount of shift as the voltages. It is clear that the change in the potential difference occurs only in an electrical double layer at the interface between the cathode electrode (Pt/C) and the electrolyte (Nafion and water), and that the anode electrode is in equilibrium as a pseudo-hydrogen electrode. Moreover, the electric potential variation of the cathode electrode in a PEFC under a power generation condition was also directly detected by operando HAXPES.

Large-Gap Magnetic Topological Heterostructure Formed by Subsurface Incorporation of a Ferromagnetic Layer.

Inducing magnetism into topological insulators is intriguing for utilizing exotic phenomena such as the quantum anomalous Hall effect (QAHE) for technological applications. While most studies have focused on doping magnetic impurities to open a gap at the surface-state Dirac point, many undesirable effects have been reported to appear in some cases that makes it difficult to determine whether the gap opening is due to the time-reversal symmetry breaking or not. Furthermore, the realization of the QAHE has been limited to low temperatures. Here we have succeeded in generating a massive Dirac cone in a MnBi2Se4/Bi2Se3 heterostructure, which was fabricated by self-assembling a MnBi2Se4 layer on top of the Bi2Se3 surface as a result of the codeposition of Mn and Se. Our experimental results, supported by relativistic ab initio calculations, demonstrate that the fabricated MnBi2Se4/Bi2Se3 heterostructure shows ferromagnetism up to room temperature and a clear Dirac cone gap opening of ∼100 meV without any other significant changes in the rest of the band structure. It can be considered as a result of the direct interaction of the surface Dirac cone and the magnetic layer rather than a magnetic proximity effect. This spontaneously formed self-assembled heterostructure with a massive Dirac spectrum, characterized by a nontrivial Chern number C = -1, has a potential to realize the QAHE at significantly higher temperatures than reported up to now and can serve as a platform for developing future "topotronics" devices.

Controlled Modification of Superconductivity in Epitaxial Atomic Layer-Organic Molecule Heterostructures.

Self-assembled organic molecules can potentially be an excellent source of charge and spin for two-dimensional (2D) atomic-layer superconductors. Here we investigate 2D heterostructures based on In atomic layers epitaxially grown on Si and highly ordered metal-phthalocyanine (MPc, M = Mn, Cu) through a variety of techniques: scanning tunneling microscopy, electron transport measurements, angle-resolved photoemission spectroscopy, X-ray magnetic circular dichroism, and ab initio calculations. We demonstrate that the superconducting transition temperature (Tc) of the heterostructures can be modified in a controllable manner. Particularly, the substitution of the coordinated metal atoms from Mn to Cu is found to reverse the Tc shift from negative to positive directions. This distinctive behavior is attributed to a competition of charge and spin effects, the latter of which is governed by the directionality of the relevant d-orbitals. The present study shows the effectiveness of molecule-induced surface doping and the significance of microscopic understanding of the molecular states in these 2D heterostructures.

In situ study of oxidation states of platinum nanoparticles on a polymer electrolyte fuel cell electrode by near ambient pressure hard X-ray photoelectron spectroscopy.

We performed in situ hard X-ray photoelectron spectroscopy (HAXPES) measurements of the electronic states of platinum nanoparticles on the cathode electrocatalyst of a polymer electrolyte fuel cell (PEFC) using a near ambient pressure (NAP) HAXPES instrument having an 8 keV excitation source. We successfully observed in situ NAP-HAXPES spectra of the Pt/C cathode catalysts of PEFCs under working conditions involving water, not only for the Pt 3d states with large photoionization cross-sections in the hard X-ray regime but also for the Pt 4f states and the valence band with small photoionization cross-sections. Thus, this setup allowed in situ observation of a variety of hard PEFC systems under operating conditions. The Pt 4f spectra of the Pt/C electrocatalysts in PEFCs clearly showed peaks originating from oxidized Pt(ii) at 1.4 V, which unambiguously shows that Pt(iv) species do not exist on the Pt nanoparticles even at such large positive voltages. The water oxidation reaction might take place at that potential (the standard potential of 1.23 V versus a standard hydrogen electrode) but such a reaction should not lead to a buildup of detectable Pt(iv) species. The voltage-dependent NAP-HAXPES Pt 3d spectra revealed different behaviors with increasing voltage (0.6 → 1.0 V) compared with decreasing voltage (1.0 → 0.6 V), showing a clear hysteresis. Moreover, quantitative peak-fitting analysis showed that the fraction of non-metallic Pt species matched the ratio of the surface to total Pt atoms in the nanoparticles, which suggests that Pt oxidation only takes place at the surface of the Pt nanoparticles on the PEFC cathode, and the inner Pt atoms do not participate in the reaction. In the valence band spectra, the density of electronic states near the Fermi edge reduces with decreasing particle size, indicating an increase in the electrocatalytic activity. Additionally, a change in the valence band structure due to the oxidation of platinum atoms was also observed at large positive voltages. The developed apparatus is a valuable in situ tool for the investigation of the electronic states of PEFC electrocatalysts under working conditions.

Direct observation of X-ray induced atomic motion using scanning tunneling microscope combined with synchrotron radiation.

X-ray induced atomic motion on a Ge(111)-c(2 x 8) clean surface at room temperature was directly observed with atomic resolution using a synchrotron radiation (SR)-based scanning tunneling microscope (STM) system under ultra high vacuum condition. The atomic motion was visualized as a tracking image by developing a method to merge the STM images before and after X-ray irradiation. Using the tracking image, the atomic mobility was found to be strongly affected by defects on the surface, but was not dependent on the incident X-ray energy, although it was clearly dependent on the photon density. The atomic motion can be attributed to surface diffusion, which might not be due to core-excitation accompanied with electronic transition, but a thermal effect by X-ray irradiation. The crystal surface structure was possible to break even at a lower photon density than the conventionally known barrier. These results can alert X-ray studies in the near future about sample damage during measurements, while suggesting the possibility of new applications. Also the obtained results show a new availability of the in-situ SR-STM system.

Development of a scanning tunneling microscope for in situ experiments with a synchrotron radiation hard-X-ray microbeam.

A scanning tunneling microscope dedicated to in situ experiments under the irradiation of highly brilliant hard-X-rays of synchrotron radiation has been developed. In situ scanning tunneling microscopy (STM) observation was enabled by developing an accurate alignment system in ultrahigh vacuum. Despite the noisy conditions of the synchrotron radiation facility and the radiation load around the probe tip, STM images were successfully obtained at atomic resolution. Tip-current spectra were obtained for Ge nano-islands on a clean Si(111) surface by changing the incident photon energy across the Ge absorption edge. A current modification was detected at the absorption edge with a spatial resolution of the order of 10 nm.