Probing lithium mobility at a solid electrolyte surface.

Solid-state electrolytes overcome many challenges of present-day lithium ion batteries, such as safety hazards and dendrite formation1,2. However, detailed understanding of the involved lithium dynamics is missing due to a lack of in operando measurements with chemical and interfacial specificity. Here we investigate a prototypical solid-state electrolyte using linear and nonlinear extreme-ultraviolet spectroscopies. Leveraging the surface sensitivity of extreme-ultraviolet-second-harmonic-generation spectroscopy, we obtained a direct spectral signature of surface lithium ions, showing a distinct blueshift relative to bulk absorption spectra. First-principles simulations attributed the shift to transitions from the lithium 1 s state to hybridized Li-s/Ti-d orbitals at the surface. Our calculations further suggest a reduction in lithium interfacial mobility due to suppressed low-frequency rattling modes, which is the fundamental origin of the large interfacial resistance in this material. Our findings pave the way for new optimization strategies to develop these electrochemical devices via interfacial engineering of lithium ions.

Laser-induced transient magnons in Sr3Ir2O7 throughout the Brillouin zone.

Although ultrafast manipulation of magnetism holds great promise for new physical phenomena and applications, targeting specific states is held back by our limited understanding of how magnetic correlations evolve on ultrafast timescales. Using ultrafast resonant inelastic X-ray scattering we demonstrate that femtosecond laser pulses can excite transient magnons at large wavevectors in gapped antiferromagnets and that they persist for several picoseconds, which is opposite to what is observed in nearly gapless magnets. Our work suggests that materials with isotropic magnetic interactions are preferred to achieve rapid manipulation of magnetism.

Sub-nanometer scale depth patterning on sapphire crystal by femtosecond soft x-ray laser pulse irradiation.

Damage thresholds and structures on a metal aluminum and an aluminum oxide crystal induced by the soft x-ray free electron laser irradiations were evaluated. Distinctive differences in damage thresholds and structures were observed for these materials. On the aluminum oxide crystal surface, in particular, a novel, to the best of our knowledge, surface processing, which we suggest defining as "peeling," was recognized. Surface structures formed by peeling had extremely shallow patterning of sub-nanometer depth. For the newly observed peeling process, we proposed a scission of chemical bond, i.e., binding energy model, in the crystal.

Ultrafast X-Ray Scattering Reveals Composite Amplitude Collective Mode in the Weyl Charge Density Wave Material (TaSe_{4})_{2}I.

We report ultrafast x-ray scattering experiments of the quasi-1D charge density wave (CDW) material (TaSe_{4})_{2}I following ultrafast infrared photoexcitation. From the time-dependent diffraction signal at the CDW sidebands we identify a 0.11 THz amplitude mode derived primarily from a transverse acoustic mode of the high-symmetry structure. From our measurements we determine that this mode interacts with the valence charge indirectly through another collective mode, and that the CDW system in (TaSe_{4})_{2}I has a composite nature supporting multiple dynamically active structural degrees of freedom.

Extreme Ultraviolet Second Harmonic Generation Spectroscopy in a Polar Metal.

The coexistence of ferroelectricity and metallicity seems paradoxical, since the itinerant electrons in metals should screen the long-range dipole interactions necessary for dipole ordering. The recent discovery of the polar metal LiOsO3 was therefore surprising [as discussed earlier in Y. Shi et al., Nat. Mater. 2013, 12, 1024]. It is thought that the coordination preferences of the Li play a key role in stabilizing the LiOsO3 polar metal phase, but an investigation from the combined viewpoints of core-state specificity and symmetry has yet to be done. Here, we apply the novel technique of extreme ultraviolet second harmonic generation (XUV-SHG) and find a sensitivity to the broken inversion symmetry in the polar metal phase of LiOsO3 with an enhanced feature above the Li K-edge that reflects the degree of Li atom displacement as corroborated by density functional theory calculations. These results pave the way for time-resolved probing of symmetry-breaking structural phase transitions on femtosecond time scales with element specificity.

Independent contribution of optical attenuation length in ultrafast laser-induced structural change.

Although laser irradiation with femtosecond pulses is known to generate crystallization and morphological changes, the contribution of optical parameters to material changes is still in discussion. Here, we compare two structures irradiated near Si-L2,3 edges by an extreme ultraviolet femtosecond pulse. Our result implies that, despite the femtosecond irradiation regime, these values of the optical attenuation length between the wavelengths of 10.3-nm and 13.5-nm differ by one order of magnitude. From the structural comparison, the original crystalline state was maintained upon irradiation at 13.5-nm, on the other hand, transition to an amorphous state occurred at 10.3-nm. The difference in optical attenuation length directly influence to the decision of material crystallization or morphological changes, even if the irradiation condition is under the femtosecond regime and same pulse duration. Our result reveals the contribution of optical attenuation length in ultrafast laser-induced structural change.

Polarization-Resolved Extreme-Ultraviolet Second-Harmonic Generation from LiNbO_{3}.

Second harmonic generation (SHG) spectroscopy ubiquitously enables the investigation of surface chemistry, interfacial chemistry, as well as symmetry properties in solids. Polarization-resolved SHG spectroscopy in the visible to infrared regime is regularly used to investigate electronic and magnetic order through their angular anisotropies within the crystal structure. However, the increasing complexity of novel materials and emerging phenomena hampers the interpretation of experiments solely based on the investigation of hybridized valence states. Here, polarization-resolved SHG in the extreme ultraviolet (XUV-SHG) is demonstrated for the first time, enabling element-resolved angular anisotropy investigations. In noncentrosymmetric LiNbO_{3}, elemental contributions by lithium and niobium are clearly distinguished by energy dependent XUV-SHG measurements. This element-resolved and symmetry-sensitive experiment suggests that the displacement of Li ions in LiNbO_{3}, which is known to lead to ferroelectricity, is accompanied by distortions to the Nb ion environment that breaks the inversion symmetry of the NbO_{6} octahedron as well. Our simulations show that the measured second harmonic spectrum is consistent with Li ion displacements from the centrosymmetric position while the Nb─O bonds are elongated and contracted by displacements of the O atoms. In addition, the polarization-resolved measurement of XUV-SHG shows excellent agreement with numerical predictions based on dipole-induced SHG commonly used in the optical wavelengths. Our result constitutes the first verification of the dipole-based SHG model in the XUV regime. The findings of this work pave the way for future angle and time-resolved XUV-SHG studies with elemental specificity in condensed matter systems.

Full-field microscope with twin Wolter mirrors for soft X-ray free-electron lasers.

We developed a full-field microscope with twin Wolter mirrors for soft X-ray free-electron lasers. The Wolter mirrors for a condenser and an objective were fabricated using an electroforming process with a precisely figured master mandrel. In the imaging system constructed at SACLA BL1, sub-micrometer spatial resolution was achieved at wavelengths of 10.3 and 3.4 nm. Single-shot bright-field images were acquired with a maximum illumination intensity of 7×1014 W/cm2.

Ultrafast Subpicosecond Magnetization of a 2D Ferromagnet.

Strong spin-charge interactions in several ferromagnets are expected to lead to subpicosecond (sub-ps) magnetization of the magnetic materials through control of the carrier characteristics via electrical means, which is essential for ultrafast spin-based electronic devices. Thus far, ultrafast control of magnetization has been realized by optically pumping a large number of carriers into the d or f orbitals of a ferromagnet; however, it is extremely challenging to implement by electrical gating. This work demonstrates a new method for sub-ps magnetization manipulation called wavefunction engineering, in which only the spatial distribution (wavefunction) of s (or p) electrons is controlled and no change is required in the total carrier density. Using a ferromagnetic semiconductor (FMS) (In,Fe)As quantum well (QW), instant enhancement, as fast as 600 fs, of the magnetization is observed upon irradiating a femtosecond (fs) laser pulse. Theoretical analysis shows that the instant enhancement of the magnetization is induced when the 2D electron wavefunctions (WFs) in the FMS QW are rapidly moved by a photo-Dember electric field formed by an asymmetric distribution of the photocarriers. Because this WF engineering method can be equivalently implemented by applying a gate electric field, these results open a new way to realize ultrafast magnetic storage and spin-based information processing in present electronic systems.

Determination of sub-ps lattice dynamics in FeRh thin films.

Understanding the ultrashort time scale structural dynamics of the FeRh metamagnetic phase transition is a key element in developing a complete explanation of the mechanism driving the evolution from an antiferromagnetic to ferromagnetic state. Using an X-ray free electron laser we determine, with sub-ps time resolution, the time evolution of the (-101) lattice diffraction peak following excitation using a 35 fs laser pulse. The dynamics at higher laser fluence indicates the existence of a transient lattice state distinct from the high temperature ferromagnetic phase. By extracting the lattice temperature and comparing it with values obtained in a quasi-static diffraction measurement, we estimate the electron-phonon coupling in FeRh thin films as a function of laser excitation fluence. A model is presented which demonstrates that the transient state is paramagnetic and can be reached by a subset of the phonon bands. A complete description of the FeRh structural dynamics requires consideration of coupling strength variation across the phonon frequencies.

Characterization of photoinduced normal state through charge density wave in superconducting YBa2Cu3O6.67.

The normal state of high-Tc cuprates has been considered one of the essential topics in high-temperature superconductivity research. However, compared to the high magnetic field study of it, understanding a photoinduced normal state remains elusive. Here, we explore a photoinduced normal state of YBa2Cu3O6.67 through a charge density wave (CDW) with time-resolved resonant soft x-ray scattering, as well as a high magnetic field x-ray scattering. In the nonequilibrium state where people predict a quenched superconducting state based on the previous optical spectroscopies, we experimentally observed a similar analogy to the competition between superconductivity and CDW shown in the equilibrium state. We further observe that the broken pairing states in the superconducting CuO2 plane via the optical pump lead to nucleation of three-dimensional CDW precursor correlation. Ultimately, these findings provide a critical clue that the characteristics of the photoinduced normal state show a solid resemblance to those under magnetic fields in equilibrium conditions.

Spatially resolved single-shot absorption spectroscopy with x-ray free electron laser pulse.

A new method of spatially resolved single-shot absorption spectroscopy for an x-ray free electron laser (XFEL) pulse has been developed by using a dispersive spectrometer and an elliptical mirror to enhance the spatial resolution. As a demonstration, we performed x-ray absorption near-edge structure measurement of Cu with a pump-probe scheme combining an XFEL pulse and a high-power femtosecond laser pulse. In the experiment, changes of an absorption spectrum in a plasma generated with a laser shot were successfully observed. The method will be a powerful tool for experiments requiring a spatial resolution and/or a single-shot measurement, such as high energy density science using a high-power laser pulse.

Copper electroforming replication process for soft x-ray mirrors.

We developed a copper electroforming replication (CER) process to fabricate precise ellipsoidal mirrors for soft x-ray focusing. Some applications of ellipsoidal mirrors in x-ray microscopy require that all components that are close to samples, including the mirrors, are made of non-magnetic materials. In this study, a non-magnetic copper ellipsoidal mirror was fabricated by replicating a figured and super-polished quartz glass mandrel using an electroforming technique. It was found that the CER process has a high replication accuracy of 8 nm. The focusing performance of the mirror was characterized using a soft x-ray free-electron laser with a photon energy of 100 eV. A small focus size of 370 × 400 nm2 was achieved with a high reflectivity of 65%.

Dirac semimetal phase and switching of band inversion in XMg2Bi2 (X = Ba and Sr).

Topological Dirac semimetals (TDSs) offer an excellent opportunity to realize outstanding physical properties distinct from those of topological insulators. Since TDSs verified so far have their own problems such as high reactivity in the atmosphere and difficulty in controlling topological phases via chemical substitution, it is highly desirable to find a new material platform of TDSs. By angle-resolved photoemission spectroscopy combined with first-principles band-structure calculations, we show that ternary compound BaMg2Bi2 is a TDS with a simple Dirac-band crossing around the Brillouin-zone center protected by the C3 symmetry of crystal. We also found that isostructural SrMg2Bi2 is an ordinary insulator characterized by the absence of band inversion due to the reduction of spin-orbit coupling. Thus, XMg2Bi2 (X = Sr, Ba, etc.) serves as a useful platform to study the interplay among crystal symmetry, spin-orbit coupling, and topological phase transition around the TDS phase.

A novel composite-to-composite adhesive bond mechanism.

The purpose of this study was to determine if adhesion between various resin composites can occur by a chelation reaction of elemental ions. The surface composition of four commercially available resin composites (Beautifil II, Clearfil AP-X, Estelite Σ Quick and Solare) were measured by X-ray fluorescence analysis. Composite-to-composite adhesion with conventional silane coupling treatment was compared to self-etching primer treatment and evaluated by conventional shear bond strength testing. Our results detected Strontium and Barium (alkaline metallic earth ions) on the surface of Beautifil II and Clearfil AP-X resins. The shear bond strength values of self-etching primer treatments of Beautifil II and Clearfil AP-X was significantly higher than Estelite Σ Quick and Solare. Our data suggest that self-etching primer treatment is effective for adhesion of resin composites, depending on their filler composition, due to the chelation adhesion reaction between the acidic monomer and incorporated alkaline metal ions.