Shik Shin

The inhomogeneous structure of water at ambient conditions

Small-angle X-ray scattering (SAXS) is used to demonstrate the presence of density fluctuations in ambient water on a physical length-scale of ≈1 nm; this is retained with decreasing temperature while the magnitude is enhanced. In contrast, the magnitude of fluctuations in a normal liquid, such as CCl4, exhibits no enhancement with decreasing temperature, as is also the case for water from molecular dynamics simulations under ambient conditions. Based on X-ray emission spectroscopy and X-ray Raman scattering data we propose that the density difference contrast in SAXS is due to fluctuations between tetrahedral-like and hydrogen-bond distorted structures related to, respectively, low and high density water. We combine our experimental observations to propose a model of water as a temperature-dependent, fluctuating equilibrium between the two types of local structures driven by incommensurate requirements for minimizing enthalpy (strong near-tetrahedral hydrogen-bonds) and maximizing entropy (nondirectional H-bonds and disorder). The present results provide experimental evidence that the extreme differences anticipated in the hydrogen-bonding environment in the deeply supercooled regime surprisingly remain in bulk water even at conditions ranging from ambient up to close to the boiling point.

High resolution-high energy x-ray photoelectron spectroscopy using third-generation synchrotron radiation source, and its application to Si-high k insulator systems

High-resolution x-ray photoelectron spectroscopy (XPS) at 6 keV photon energy has been realized utilizing high-flux-density x rays from the third generation high-energy synchrotron radiation facility, SPring-8. The method has been applied to analysis of high-k HfO2/interlayer/Si complementary metal–oxide–semiconductor gate-dielectric structures. With the high energy resolution and high throughput of our system, chemical-state differences were observed in the Si 1s, Hf 3d, and O 1s peaks for as-deposited and annealed samples. The results revealed that a SiOxNy interlayer is more effective in controlling the interface structure than SiO2. Our results show the wide applicability of high resolution XPS with hard x rays from a synchrotron source.

Giant Rashba-type spin splitting in bulk BiTeI

There has been increasing interest in phenomena emerging from relativistic electrons in a solid, which have a potential impact on spintronics and magnetoelectrics. One example is the Rashba effect, which lifts the electron-spin degeneracy as a consequence of spin-orbit interaction under broken inversion symmetry. A high-energy-scale Rashba spin splitting is highly desirable for enhancing the coupling between electron spins and electricity relevant for spintronic functions. Here we describe the finding of a huge spin-orbit interaction effect in a polar semiconductor composed of heavy elements, BiTeI, where the bulk carriers are ruled by large Rashba-like spin splitting. The band splitting and its spin polarization obtained by spin- and angle-resolved photoemission spectroscopy are well in accord with relativistic first-principles calculations, confirming that the spin splitting is indeed derived from bulk atomic configurations. Together with the feasibility of carrier-doping control, the giant-Rashba semiconductor BiTeI possesses excellent potential for application to various spin-dependent electronic functions.

Octet-Line Node Structure of Superconducting Order Parameter in KFe2As2

An Eight-Noded Monster In superconductors, electrons are bound into pairs, and the exact form of that pairing and the resulting energy gap can vary, depending on the details of the electron-electron interaction and the band structure of the material. The energy gaps of the recently discovered iron-based superconductors exhibit a variety of pairing functions. KFe2As2 has been suggested to have a d-wave gap, similar to cuprate superconductors. Okazaki et al. (p. 1314) use laser-based angle-resolved photoemission spectroscopy (ARPES) to map out the superconducting gap on three Fermi surfaces (FS) of the compound. They find a different gap structure on each, with the middle FS gap vanishing at eight distinct positions (nodes). It appears that the gap respects the tetragonal symmetry of the crystal, indicating (although the details may vary) the all iron-based superconductors have an extended s-wave–symmetric pairing—a finding that will help understanding of unconventional superconductivity. Laser-based photoemission spectroscopy is used to map out the pairing gap of an iron-based superconductor. In iron-pnictide superconductivity, the interband interaction between the hole and electron Fermi surfaces (FSs) is believed to play an important role. However, KFe2As2 has three zone-centered hole FSs and no electron FS but still exhibits superconductivity. Our ultrahigh-resolution laser angle-resolved photoemission spectroscopy unveils that KFe2As2 is a nodal s-wave superconductor with highly unusual FS-selective multi-gap structure: a nodeless gap on the inner FS, an unconventional gap with “octet-line nodes” on the middle FS, and an almost-zero gap on the outer FS. This gap structure may arise from the frustration between competing pairing interactions on the hole FSs causing the eightfold sign reversal. Our results suggest that the A1g superconducting symmetry is universal in iron-pnictides, in spite of the variety of gap functions.

Definitive experimental evidence for two-band superconductivity in MgB2.

The superconducting-gap of MgB2 has been studied by high-resolution angle-resolved photoemission spectroscopy. The results show that superconducting gaps with values of 5.5 and 2.2 meV open on the sigma band and the pi band, respectively, but both the gaps close at the bulk transition temperature, providing a definitive experimental evidence for the two-band superconductivity with strong interband pairing interaction in MgB2. The experiments validate the role of k-dependent electron-phonon coupling as the origin of multiple-gap superconductivity as well as the high transition temperature of MgB2.

A probe of intrinsic valence band electronic structure: Hard x-ray photoemission

Hard x-ray valence band photoemission spectroscopy (PES) is realized using high-energy and high-brilliance synchrotron radiation. High-energy (∼6 keV) excitation results in larger probing depths of photoelectrons compared to conventional PES, and enables a study of intrinsic electronic property of materials in actual device structures much less influenced by surface condition. With this technique, requirements for surface preparation are greatly reduced, if not eliminated. It is a nondestructive tool to determine electronic structure from surface to genuine bulk as shown by a study on SiO2/Si(100). Electronic structure modification related to the ferromagnetism in the diluted magnetic semiconductor Ga0.96Mn0.04N is also observed.

Photoemission and Bremsstrahlung Isochromat Spectroscopy Studies of TiO2 (Rutile) and SrTiO3

Photoemission and bremsstrahlung isochromat spectra have been measured on TiO 2 (rutile) and SrTiO 3 . The magnitudes of the fundamental band gaps estimated from the combined spectra agree well with the results of the photoabsorption and the energy-band calculations. The profiles of the observed spectra do not reveal the fine structure expected to occur in the density-of-states curves obtained by the energy band calculations, suggesting the existence of a mechanism to smear out the fine structure considerably. The combined spectra are used to interpret the charge-transfer-type satellite manifest in the core-level spectra. For 3 s photoemission, satellite features ascribed to the configuration interaction between the 3 s 3 p 6 and 3 s 2 3 p 4 3 d states in the atomic notation are also observed.

Orbital-dependent modifications of electronic structure across the magnetostructural transition in BaFe2As2.

Laser angle-resolved photoemission spectroscopy (ARPES) is employed to investigate the temperature (T) dependence of the electronic structure in BaFe2As2 across the magnetostructural transition at T{N} approximately 140 K. A drastic transformation in Fermi surface (FS) shape across T{N} is observed, as expected by first-principles band calculations. Polarization-dependent ARPES and band calculations consistently indicate that the observed FSs at k{z} approximately pi in the low-T antiferromagnetic state are dominated by the Fe3d{zx} orbital, leading to the twofold electronic structure. These results indicate that magnetostructural transition in BaFe2As2 accompanies orbital-dependent modifications in the electronic structure.

Nature of the well screened state in hard X-ray mn 2p core-level photoemission measurements of La1-xSrxMnO3 films

Using hard x-ray (HX; hnu=5.95 keV) synchrotron photoemission spectroscopy (PES), we study the intrinsic electronic structure of La(1-x)Sr(x)MnO(3) (LSMO) thin films. Comparison of Mn 2p core-levels with soft x-ray (SX; hnu approximately 1000 eV) PES shows a clear additional well-screened feature only in HX PES. Takeoff-angle dependent data indicate its bulk (> or =20 A) character. The doping and temperature dependence track the ferromagnetism and metallicity of the LSMO series. Cluster model calculations including charge transfer from doping-induced states show good agreement, confirming this picture of bulk properties reflected in Mn 2p core-levels using HX PES.

A versatile system for ultrahigh resolution, low temperature, and polarization dependent Laser-angle-resolved photoemission spectroscopy

We have developed a low temperature ultrahigh resolution system for polarization dependent angle-resolved photoemission spectroscopy (ARPES) using a vacuum ultraviolet (vuv) laser (hnu=6.994 eV) as a photon source. With the aim of addressing low energy physics, we show the system performance with angle-integrated PES at the highest energy resolution of 360 mueV and the lowest temperature of 2.9 K. We describe the importance of a multiple-thermal-shield design for achieving the low temperature, which allows a clear measurement of the superconducting gap of tantalum metal with a T(c)=4.5 K. The unique specifications and quality of the laser source (narrow linewidth of 260 mueV, high photon flux), combined with a half-wave plate, facilitates ultrahigh energy and momentum resolution polarization dependent ARPES. We demonstrate the use of s- and p-polarized laser-ARPESs in studying the superconducting gap on bilayer-split bands of a high T(c) cuprate. The unique features of the quasi-continuous-wave vuv laser and low temperature enables ultrahigh-energy and -momentum resolution studies of the spectral function of a solid with large escape depth. We hope the present work helps in defining polarization dependent laser excited angle-resolved photoemission spectroscopy as a frontier tool for the study of electronic structure and properties of materials at the sub-meV energy scale.