SIMES Publications

Abstract

Time-resolved measurements of materials provide a wealth of information on quasiparticle dynamics, and have been the focus of optical studies for decades. In this paper, we develop a theory for explicitly evaluating time-resolved resonant inelastic x-ray scattering (tr-RIXS). We apply the theory to a noninteracting electronic system and reveal the particle-hole spectrum and its evolution during the pump pulse. With a high-frequency pump, the frequency and amplitude dependence analysis of the spectra agrees well with the steady-state assumptions and Floquet excitations. When the pump frequency is low, the spectrum extracts real-time dynamics of the particle-hole continuum in momentum space. These results verify the correctness of our theory and demonstrate the breadth of physical problems that tr-RIXS could shed light on.

Abstract

Electron dynamics at interfaces is a subject of great scientific interest and technological importance. Detailed understanding of such dynamics requires access to the angstrom length scale defining interfaces and the femtosecond time scale characterizing interfacial motion of electrons. In this context, the most precise and general way to remotely measure charge dynamics is through the transient current flow and the associated electromagnetic radiation. Here, we present quantitative measurements of interfacial currents on the subnanometer length and femtosecond time scale by recording the emitted terahertz radiation following ultrafast laser excitation. We apply this method to interlayer charge transfer in heterostructures of two transition metal dichalcogenide monolayers less than 0.7 nm apart. We find that charge relaxation and separation occur in less than 100 fs. This approach allows us to unambiguously determine the direction of current flow, to demonstrate a charge transfer efficiency of order unity, and to characterize saturation effects.

Abstract

Reversible high-voltage redox chemistry is an essential component of many electrochemical technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4 V versus Li/Li+ in a variety of oxide materials. However, oxidation of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li2−xIr1−ySnyO3 model system, which exhibits tunable oxidation state and structural evolution with yupon cycling, we reveal that this structure–redox coupling arises from the local stabilization of short approximately 1.8 Å metal–oxygen π bonds and approximately 1.4 Å O–O dimers during oxygen redox, which occurs in Li2−xIr1−ySnyO3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighbouring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochemical properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chemistry.

Abstract

We study the band structure of twinned and detwinned BaFe2As2 using angle-resolved photoemission spectroscopy. The combination of measurements in the ordered and normal states along four high-symmetry momentum directions Γ/Z−X/Y enables us to identify the complex reconstructed band structure in the ordered state in great detail. We clearly observe the nematic splitting of the dxz and dyzorbitals as well as folding due to magnetic order with a wave vector of (π,π,π). We are able to assign all observed bands. In particular we suggest an assignment of the electron bands different from previous reports. The high-quality spectra allow us to achieve a comprehensive understanding of the band structure of BaFe2As2.

Abstract

Topological quantum materials exhibit fascinating properties1,2,3, with important applications for dissipationless electronics and fault-tolerant quantum computers4,5. Manipulating the topological invariants in these materials would allow the development of topological switching applications analogous to switching of transistors6. Lattice strain provides the most natural means of tuning these topological invariants because it directly modifies the electron–ion interactions and potentially alters the underlying crystalline symmetry on which the topological properties depend7,8,9. However, conventional means of applying strain through heteroepitaxial lattice mismatch10 and dislocations11 are not extendable to controllable time-varying protocols, which are required in transistors. Integration into a functional device requires the ability to go beyond the robust, topologically protected properties of materials and to manipulate the topology at high speeds. Here we use crystallographic measurements by relativistic electron diffraction to demonstrate that terahertz light pulses can be used to induce terahertz-frequency interlayer shear strain with large strain amplitude in the Weyl semimetal WTe2, leading to a topologically distinct metastable phase. Separate nonlinear optical measurements indicate that this transition is associated with a symmetry change to a centrosymmetric, topologically trivial phase. We further show that such shear strain provides an ultrafast, energy-efficient way of inducing robust, well separated Weyl points or of annihilating all Weyl points of opposite chirality. This work demonstrates possibilities for ultrafast manipulation of the topological properties of solids and for the development of a topological switch operating at terahertz frequencies.

Abstract

Many ultrafast solid phase transitions are treated as chemical reactions that transform the structures between two different unit cells along a reaction coordinate, but this neglects the role of disorder. Although ultrafast diffraction provides insights into atomic dynamics during such transformations, diffraction alone probes an averaged unit cell and is less sensitive to randomness in the transition pathway. Using total scattering of femtosecond x-ray pulses, we show that atomic disordering in photoexcited vanadium dioxide (VO2) is central to the transition mechanism and that, after photoexcitation, the system explores a large volume of phase space on a time scale comparable to that of a single phonon oscillation. These results overturn the current understanding of an archetypal ultrafast phase transition and provide new microscopic insights into rapid evolution toward equilibrium in photoexcited matter.

Abstract

High-temperature copper oxide superconductors consist of stacked CuO2 planes, with electronic band structures and magnetic excitations that are primarily two-dimensional, but with superconducting coherence that is three-dimensional. This dichotomy highlights the importance of out-of-plane charge dynamics, which has been found to be incoherent in the normal state within the limited range of momenta accessible by optics. Here we use resonant inelastic X-ray scattering to explore the charge dynamics across all three dimensions of the Brillouin zone. Polarization analysis of recently discovered collective excitations (modes) in electron-doped copper oxides reveals their charge origin, that is, without mixing with magnetic components. The excitations disperse along both the in-plane and out-of-plane directions, revealing its three-dimensional nature. The periodicity of the out-of-plane dispersion corresponds to the distance between neighbouring CuO2 planes rather than to the crystallographic c-axis lattice constant, suggesting that the interplane Coulomb interaction is responsible for the coherent out-of-plane charge dynamics. The observed properties are hallmarks of the long-sought ‘acoustic plasmon’, which is a branch of distinct charge collective modes predicted for layered systems and argued to play a substantial part in mediating high-temperature superconductivity

Abstract

It has recently been shown that the Schottky barrier height (SBH) formed at metal-semiconductor perovskite oxide heterojunctions can be dramatically tuned by the insertion of atomic-scale dipole layers at the interface. However, in idealized form, this would only allow for specific values of the SBH, discretized by the dipole layer thickness. Here, we examine the effect of fractional unit cell LaAlO3 dipoles inserted between SrRuO3 and Nb:SrTiO3 in (001) Schottky junctions, as a function of their in-plane lateral distribution. When the LaAlO3 dipoles are finely dispersed, we observe uniformly rectifying junctions, with SBHs reflecting the fractional LaAlO3 coverage. For larger length-scale distributions, the junction characteristics reflect the inhomogeneous combination of regions with and without the interface dipole. The characteristic length scale dividing the two regimes corresponds to the semiconductor depletion width scaled by the dipole potential, determining the effective scale for which the SBH can be continuously tuned.

Abstract

We have examined the intrinsic spin-orbit coupling and orbital depairing in thin films of Nb-doped SrTiO3 by superconducting tunneling spectroscopy. The orbital depairing is geometrically suppressed in the two-dimensional limit, enabling a quantitative evaluation of the Fermi level spin-orbit scattering using Maki’s theory. The response of the superconducting gap under in-plane magnetic fields demonstrates short spin-orbit scattering times τso≤1.1  ps. Analysis of the orbital depairing indicates that the heavy electron band contributes significantly to pairing. These results suggest that the intrinsic spin-orbit scattering time in SrTiO3 is comparable to those associated with Rashba effects in SrTiO3 interfacial conducting layers and can be considered significant in all forms of superconductivity in SrTiO3.

Abstract

Using Cu-L3 edge resonant inelastic x-ray scattering (RIXS) we measured the dispersion and damping of spin excitations (magnons and paramagnons) in the high-Tc superconductor (Bi,Pb)2(Sr,La)2CuO6+δ (Bi2201), for a large doping range across the phase diagram (0.03 p 0.21). Selected measurements with full polarization analysis unambiguously demonstrate the spin-flip character of these excitations, even in the overdoped sample. We find that the undamped frequencies increase slightly with doping for all accessible momenta, while the damping grows rapidly, faster in the (0, 0) → (0.5, 0.5) nodal direction than in the (0, 0) → (0.5, 0) antinodal direction. We compare the experimental results to numerically exact determinant quantum Monte Carlo (DQMC) calculations that provide the spin dynamical structure factor S(Q, ω) of the three-band Hubbard model. The theory reproduces well the momentum and doping dependence of the dispersions and spectral weights of magnetic excitations. These results provide compelling evidence that paramagnons, although increasingly damped, persist across the superconducting dome of the cuprate phase diagram; this implies that long-range antiferromagnetic correlations are quickly washed away, while short-range magnetic interactions are little affected by doping