Polarization control with an X-ray phase retarder for high-time-resolution pump-probe experiments at SACLA.

Control of the polarization of an X-ray free-electron laser (XFEL) has been performed using an X-ray phase retarder (XPR) in combination with an arrival timing diagnostic on BL3 of the SPring-8 Angstrom Compact free-electron LAser (SACLA). To combine with the timing diagnostic, a pink beam was incident on the XPR crystal and then monochromated in the vicinity of samples. A high degree of circular polarization of ∼97% was obtained experimentally at 11.567 keV, which agreed with calculations based on the dynamical theory of X-ray diffraction. This system enables pump-probe experiments to be operated using circular polarization with a time resolution of 40 fs to investigate ultrafast magnetic phenomena.

Electronic Structure of Ce-Doped and -Undoped Nd_{2}CuO_{4} Superconducting Thin Films Studied by Hard X-Ray Photoemission and Soft X-Ray Absorption Spectroscopy.

In order to realize superconductivity in cuprates with the T^{'}-type structure, not only chemical substitution (Ce doping) but also postgrowth reduction annealing is necessary. In the case of thin films, however, well-designed reduction annealing alone without Ce doping can induce superconductivity in the T^{'}-type cuprates. In order to unveil the origin of superconductivity in the Ce-undoped T^{'}-type cuprates, we have performed bulk-sensitive hard x-ray photoemission and soft x-ray absorption spectroscopy on superconducting and nonsuperconducting Nd_{2-x}Ce_{x}CuO_{4} (x=0, 0.15, and 0.19) thin films. By postgrowth annealing, core-level spectra exhibited dramatic changes, which we attributed to the enhancement of core-hole screening in the CuO_{2} plane and the shift of chemical potential along with changes in the band filling. The result suggests that the superconducting Nd_{2}CuO_{4} film is doped with electrons despite the absence of the Ce substitution.

Element Selectivity in Second-Harmonic Generation of GaFeO_{3} by a Soft-X-Ray Free-Electron Laser.

Nonlinear optical frequency conversion has been challenged to move down to the extreme ultraviolet and x-ray region. However, the extremely low signals have allowed researchers to only perform transmission experiments of the gas phase or ultrathin films. Here, we report second harmonic generation (SHG) of the reflected beam of a soft x-ray free-electron laser from a solid, which is enhanced by the resonant effect. The observation revealed that the double resonance condition can be met by absorption edges for transition metal oxides in the soft x-ray range, and this suggests that the resonant SHG technique can be applicable to a wide range of materials. We discuss the possibility of element-selective SHG spectroscopy measurements in the soft x-ray range.

Tensile-Strain-Dependent Spin States in Epitaxial LaCoO_{3} Thin Films.

The spin states of Co^{3+} ions in perovskite-type LaCoO_{3}, governed by the complex interplay between the electron-lattice interactions and the strong electron correlations, still remain controversial due to the lack of experimental techniques which can directly detect them. In this Letter, we revealed the tensile-strain dependence of spin states, i.e., the ratio of the high- and low-spin states, in epitaxial thin films and a bulk crystal of LaCoO_{3} via resonant inelastic soft x-ray scattering. A tensile strain as small as 1.0% was found to realize different spin states from that in the bulk.

Photoinduced Demagnetization and Insulator-to-Metal Transition in Ferromagnetic Insulating BaFeO_{3} Thin Films.

We studied the electronic and magnetic dynamics of ferromagnetic insulating BaFeO_{3} thin films by using pump-probe time-resolved resonant x-ray reflectivity at the Fe 2p edge. By changing the excitation density, we found two distinctly different types of demagnetization with a clear threshold behavior. We assigned the demagnetization change from slow (∼150 ps) to fast (<70 ps) to a transition into a metallic state induced by laser excitation. These results provide a novel approach for locally tuning magnetic dynamics. In analogy to heat-assisted magnetic recording, metallization can locally tune the susceptibility for magnetic manipulation, allowing one to spatially encode magnetic information.

Ultrafast spin-switching of a ferrimagnetic alloy at room temperature traced by resonant magneto-optical Kerr effect using a seeded free electron laser.

Ultrafast magnetization reversal of a ferrimagnetic metallic alloy GdFeCo was investigated by time-resolved resonant magneto-optical Kerr effect measurements using a seeded free electron laser. The GdFeCo alloy was pumped by a linearly polarized optical laser pulse, and the following temporal evolution of the magnetization of Fe in GdFeCo was element-selectively traced by a probe free electron laser pulse with a photon energy tuned to the Fe M-edge. The results have been measured using rotating analyzer ellipsometry method and confirmed magnetization switching caused by ultrafast heating.

Observation of a Devil's Staircase in the Novel Spin-Valve System SrCo6O11.

Using resonant soft-x-ray scattering as a function of both temperature and magnetic field, we reveal a large number of almost degenerate magnetic orders in SrCo6O11. The Ising-like spins in this frustrated material in fact exhibit a so-called magnetic devil's staircase. It is demonstrated how a magnetic field induces transitions between different microscopic spin configurations, which is responsible for the magnetoresistance of SrCo6O11. This material therefore constitutes a unique combination of a magnetic devil's staircase and spin-valve effects, yielding a novel type of magnetoresistance system.

Engineering a Spin-Orbital Magnetic Insulator by Tailoring Superlattices.

In 5d Ir oxides with an interplay of spin-orbit coupling and electron correlations, we have tailored a spin-orbital magnetic insulator out of a semimetal SrIrO(3) by tuning the structure through superlattices [(SrIrO(3))(m), SrTiO(3)] (m=1,2,3,4, and ∞). We observed the systematic decrease of the magnetic ordering temperature and the resistivity as a function of m. The transition from the semimetal to the insulator is found to be closely linked to the appearance of magnetism at m≃3. Long range magnetic ordering was realized even in the m=1 single layer superlattice, implying that the design and realization of novel electronic phases is feasible at the level of a single atomic layer in complex Ir oxides.

A time-dependent order parameter for ultrafast photoinduced phase transitions.

Strongly correlated electron systems often exhibit very strong interactions between structural and electronic degrees of freedom that lead to complex and interesting phase diagrams. For technological applications of these materials it is important to learn how to drive transitions from one phase to another. A key question here is the ultimate speed of such phase transitions, and to understand how a phase transition evolves in the time domain. Here we apply time-resolved X-ray diffraction to directly measure the changes in long-range order during ultrafast melting of the charge and orbitally ordered phase in a perovskite manganite. We find that although the actual change in crystal symmetry associated with this transition occurs over different timescales characteristic of the many electronic and vibrational coordinates of the system, the dynamics of the phase transformation can be well described using a single time-dependent 'order parameter' that depends exclusively on the electronic excitation.

Role of oxygen holes in Li(x)CoO(2) revealed by soft X-ray spectroscopy.

The fundamental electronic structure of the widely used battery material Li(x)CoO(2) still remains a mystery. Soft x-ray absorption spectroscopy of Li(x)CoO(2) reveals that holes with strong O 2p character play an essential role in the electronic conductivity of the Co(3+)/Co(4+) mixed valence CoO(2) layer. The oxygen holes are bound to the Co(4+) sites and the Li-ion vacancy, suggesting that the Li-ion flow can be stabilized by oxygen hole back flow. Such an oxygen hole state of Li(x)CoO(2) is unique among the various oxide-based battery materials and is one of the key ingredients to improving their electronic and Li-ion conductivities.

Imprinting magnetic information in manganites with x rays.

The effect of x rays on an orbital and charge ordered epitaxial film of a Pr0.5Ca0.5MnO3 is presented. As the film is exposed to x rays, the antiferromagnetic response increases and concomitantly the conductivity of the film improve. These results are discussed in terms of a persistent x-ray induced doping, leading to a modification of the magnetic structure. This effect allows writing electronic and magnetic information in the film and represents a novel way of manipulating magnetism.

Probing the role of co substitution in the electronic structure of iron pnictides.

The role of Co substitution in the low-energy electronic structure of Ca(Fe(0.944)Co(0.056))(2)As(2) is investigated by resonant photoemission spectroscopy and density-functional theory. The Co 3d state center of mass is observed at 250 meV higher binding energy than that of Fe, indicating that Co possesses one extra valence electron and that Fe and Co are in the same oxidation state. Yet, significant Co character is detected for the Bloch wave functions at the chemical potential, revealing that the Co 3d electrons are part of the Fermi sea determining the Fermi surface. This establishes the complex role of Co substitution in CaFe(2)As(2) and the inadequacy of a rigid-band shift description.

Local structure of LiCoO2 nanoparticles studied by Co K-edge x-ray absorption spectroscopy.

We have studied the local structure of LiCoO(2) nanoparticles by Co K-edge x-ray absorption spectroscopy as a function of particle size. Extended x-ray absorption fine structure data reveal substantial changes in the near neighbor distances and the associated mean square relative displacements with decreasing particle size. X-ray absorption near edge structure spectra show clear local geometrical changes with decreasing particle size, similar to those that appear in the charging (delithiation) process. The results suggest that the LiCoO(2) nanoparticles are characterized by a large atomic disorder confined to the Co-O octahedra, similar to the distortions generated during the delithiation, and this disorder should be the primary limiting factor for a reversible diffusion of Li ions when nanoparticles of LiCoO(2) are used as cathode material in rechargeable Li ion batteries.

Origin of the large polarization in multiferroic YMnO3 thin films revealed by soft- and hard-X-ray diffraction.

We investigated the magnetic structure of an orthorhombic YMnO(3) thin film by resonant soft x-ray and hard x-ray diffraction. We observed a temperature-dependent incommensurate magnetic reflection below 45 K and a commensurate lattice-distortion reflection below 35 K. These results demonstrate that the ground state is composed of coexisting E-type and cycloidal states. Their different ordering temperatures clarify the origin of the large polarization to be caused by the E-type antiferromagnetic states in the orthorhombic YMnO(3) thin film.

An in-vacuum diffractometer for resonant elastic soft x-ray scattering.

We describe the design, construction, and performance of a 4-circle in-vacuum diffractometer for resonant elastic soft x-ray scattering. The diffractometer, installed on the resonant elastic and inelastic x-ray scattering beamline at the Canadian Light Source, includes 9 in-vacuum motions driven by in-vacuum stepper motors and operates in ultra-high vacuum at base pressure of 2 × 10(-10) Torr. Cooling to a base temperature of 18 K is provided with a closed-cycle cryostat. The diffractometer includes a choice of 3 photon detectors: a photodiode, a channeltron, and a 2D sensitive channelplate detector. Along with variable slit and filter options, these detectors are suitable for studying a wide range of phenomena having both weak and strong diffraction signals. Example measurements of diffraction and reflectivity in Nd-doped (La,Sr)(2)CuO(4) and thin film (Ga,Mn)As are shown.

Where are the extra d electrons in transition-metal-substituted iron pnictides?

Transition-metal substitution in Fe pnictides leading to superconductivity is usually interpreted in terms of carrier doping to the system. We report on a density functional calculation of the local substitute electron density and demonstrate that substitutions like Co and Ni for Fe do not carrier dope but rather are isovalent to Fe. We find that the extra d electrons for Co and Ni are almost totally located within the muffin-tin sphere of the substituted site. We suggest that Co and Ni act more like random scatterers scrambling momentum space and washing out parts of the Fermi surface.

Spectroscopic evidence for competing reconstructions in polar multilayers LaAlO3/LaVO3/LaAlO3.

We have studied the valence redistribution of V in LaAlO(3)/LaVO(3)/LaAlO(3) trilayers, which are composed of only polar layers grown on SrTiO3 (001) substrates, by core-level photoemission spectroscopy. We have found that the V valence is intermediate between V3+ and V4+ for thin LaAlO3 cap layers, decreases with increasing cap-layer thickness, and finally recovers the bulk value of V3+ at approximately 10 unit-cell thickness. In order to interpret these results, we propose that the atomic reconstruction of the polar LaAlO3 surface competes with the purely electronic V valence change so that the polar catastrophe is avoided at the cost of minimum energy.

In situ photoemission study of Pr1-xCaxMnO3 epitaxial thin films with suppressed charge fluctuations.

We have performed an in situ photoemission study of Pr1-xCaxMnO3 (PCMO) thin films grown on LaAlO3 (001) substrates and observed the effect of epitaxial strain on the electronic structure. We found that the chemical potential shifted monotonically with doping, unlike bulk PCMO, implying the disappearance of incommensurate charge fluctuations of bulk PCMO. In the valence-band spectra, we found a doping-induced energy shift toward the Fermi level (EF) but there was no spectral weight transfer, which was observed in bulk PCMO. The gap at EF was clearly seen in the experimental band dispersions determined by angle-resolved photoemission spectroscopy and could not be explained by the metallic band structure of the C-type antiferromagnetic state, probably due to localization of electrons along the ferromagnetic chain direction or due to another type of spin-orbital ordering.

Photoemission from buried interfaces in SrTiO3/LaTiO3 superlattices.

We have measured photoemission spectra of SrTiO3/LaTiO3 superlattices with a topmost SrTiO3 layer of variable thickness. A finite coherent spectral weight with a clear Fermi cutoff was observed at chemically abrupt SrTiO3/LaTiO3 interfaces, indicating that an "electronic reconstruction" occurs at the interface between the Mott insulator LaTiO3 and the band insulator SrTiO3. For SrTiO3/LaTiO3 interfaces annealed at high temperatures (approximately 1000 degrees C), which leads to Sr/La atomic interdiffusion and hence to the formation of La(1-x)Sr(x)TiO3-like material, the intensity of the incoherent part was found to be dramatically reduced whereas the coherent part with a sharp Fermi cutoff was enhanced due to the spread of charge. These important experimental features are well reproduced by layer dynamical-mean-field-theory calculation.