Understanding the magnetic interaction between intrinsic defects and impurity ions in room-temperature ferromagnetic Mg1-xFexO thin films.

Understanding the nature and characteristics of the intrinsic defects and impurities in the dielectric barrier separating the ferromagnetic electrodes in a magnetic tunneling junction is of great importance for understanding the often observed 'barrier-breakdown' therein. In this connection, we present herein systematic experimental (SQUID and synchrotron-radiation-based x-ray absorption spectroscopy) and computational studies on the electronic and magnetic properties of Mg1-xFexO thin films. Our studies reveal: (i) defect aggregates comprised of basic and trimer units (Fe impurity coupled to 1 or 2 Mg vacancies) and (ii) existence of two competing magnetic orders, defect- and dopant-induced, with spin densities aligning anti-parallel if the trimer is present in the oxide matrix. These findings open up new avenues for designing tunneling barriers with high endurance and tunneling effect upon tuning the concentration/distribution of the two magnetic orders.

Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation.

LiFePO4 is a battery cathode material with high safety standards due to its unique electronic structure. We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4 nanoparticles and single crystals. The results clearly show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. We focus on the energy configurations of the occupied states of LiFePO4 and the unoccupied states of FePO4, which are the critical states where electrons are removed and injected during the charge and discharge process, respectively. In LiFePO4, the soft X-ray emission spectroscopy shows that, due to the Coulomb repulsion effect, the occupied Fe-3d states with the minority spin sit close to the Fermi level. In FePO4, the soft X-ray absorption and hard X-ray Raman spectroscopy show that the unoccupied Fe-3d states again sit close to the Fermi level. These critical 3d electron state configurations are consistent with the calculations based on modified Becke and Johnson potentials GGA+U (MBJGGA+U) framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes.

Nanoscale determination of the mass enhancement factor in the lightly doped bulk insulator lead selenide.

Bismuth chalcogenides and lead telluride/selenide alloys exhibit exceptional thermoelectric properties that could be harnessed for power generation and device applications. Since phonons play a significant role in achieving these desired properties, quantifying the interaction between phonons and electrons, which is encoded in the Eliashberg function of a material, is of immense importance. However, its precise extraction has in part been limited due to the lack of local experimental probes. Here we construct a method to directly extract the Eliashberg function using Landau level spectroscopy, and demonstrate its applicability to lightly doped thermoelectric bulk insulator PbSe. In addition to its high energy resolution only limited by thermal broadening, this novel experimental method could be used to detect variations in mass enhancement factor at the nanoscale level. This opens up a new pathway for investigating the local effects of doping and strain on the mass enhancement factor.

Extracting the redox orbitals in Li battery materials with high-resolution x-ray compton scattering spectroscopy.

We present an incisive spectroscopic technique for directly probing redox orbitals based on bulk electron momentum density measurements via high-resolution x-ray Compton scattering. Application of our method to spinel Li_{x}Mn_{2}O_{4}, a lithium ion battery cathode material, is discussed. The orbital involved in the lithium insertion and extraction process is shown to mainly be the oxygen 2p orbital. Moreover, the manganese 3d states are shown to experience spatial delocalization involving 0.16±0.05 electrons per Mn site during the battery operation. Our analysis provides a clear understanding of the fundamental redox process involved in the working of a lithium ion battery.

Dirac mass generation from crystal symmetry breaking on the surfaces of topological crystalline insulators.

The tunability of topological surface states and controllable opening of the Dirac gap are of fundamental and practical interest in the field of topological materials. In the newly discovered topological crystalline insulators (TCIs), theory predicts that the Dirac node is protected by a crystalline symmetry and that the surface state electrons can acquire a mass if this symmetry is broken. Recent studies have detected signatures of a spontaneously generated Dirac gap in TCIs; however, the mechanism of mass formation remains elusive. In this work, we present scanning tunnelling microscopy (STM) measurements of the TCI Pb1-xSnxSe for a wide range of alloy compositions spanning the topological and non-topological regimes. The STM topographies reveal a symmetry-breaking distortion on the surface, which imparts mass to the otherwise massless Dirac electrons-a mechanism analogous to the long sought-after Higgs mechanism in particle physics. Interestingly, the measured Dirac gap decreases on approaching the trivial phase, whereas the magnitude of the distortion remains nearly constant. Our data and calculations reveal that the penetration depth of Dirac surface states controls the magnitude of the Dirac mass. At the limit of the critical composition, the penetration depth is predicted to go to infinity, resulting in zero mass, consistent with our measurements. Finally, we discover the existence of surface states in the non-topological regime, which have the characteristics of gapped, double-branched Dirac fermions and could be exploited in realizing superconductivity in these materials.

Observation of Dirac node formation and mass acquisition in a topological crystalline insulator.

In topological crystalline insulators (TCIs), topology and crystal symmetry intertwine to create surface states with distinct characteristics. The breaking of crystal symmetry in TCIs is predicted to impart mass to the massless Dirac fermions. Here, we report high-resolution scanning tunneling microscopy studies of a TCI, Pb(1-x)Sn(x)Se that reveal the coexistence of zero-mass Dirac fermions protected by crystal symmetry with massive Dirac fermions consistent with crystal symmetry breaking. In addition, we show two distinct regimes of the Fermi surface topology separated by a Van-Hove singularity at the Lifshitz transition point. Our work paves the way for engineering the Dirac band gap and realizing interaction-driven topological quantum phenomena in TCIs.

Reversal of the circular dichroism in angle-resolved photoemission from Bi2Te3.

The helical Dirac fermions at the surface of topological insulators show a strong circular dichroism which has been explained as being due to either the initial-state spin angular momentum, the initial-state orbital angular momentum, or the handedness of the experimental setup. All of these interpretations conflict with our data from Bi(2)Te(3) which depend on the photon energy and show several sign changes. Our one-step photoemission calculations coupled to ab initio theory confirm the sign change and assign the dichroism to a final-state effect. Instead, the spin polarization of the photoelectrons excited with linearly polarized light remains a reliable probe for the spin in the initial state.

Phase transformation and lithiation effect on electronic structure of Li(x)FePO4: an in-depth study by soft X-ray and simulations.

Through soft X-ray absorption spectroscopy, hard X-ray Raman scattering, and theoretical simulations, we provide the most in-depth and systematic study of the phase transformation and (de)lithiation effect on electronic structure in Li(x)FePO(4) nanoparticles and single crystals. Soft X-ray reveals directly the valence states of Fe 3d electrons in the vicinity of Fermi level, which is sensitive to the local lattice distortion, but more importantly offers detailed information on the evolution of electronic states at different electrochemical stages. The soft X-ray spectra of Li(x)FePO(4) nanoparticles evolve vividly with the (de)lithiation level. The spectra fingerprint the (de)lithiation process with rich information on Li distribution, valency, spin states, and crystal field. The high-resolution spectra reveal a subtle but critical deviation from two-phase transformation in our electrochemically prepared samples. In addition, we performed both first-principles calculations and multiplet simulations of the spectra and quantitatively determined the 3d valence states that are completely redistributed through (de)lithiation. This electronic reconfiguration was further verified by the polarization-dependent spectra collected on LiFePO(4) single crystals, especially along the lithium diffusion direction. The evolution of the 3d states is overall consistent with the local lattice distortion and provides a fundamental picture of the (de)lithiation effects on electronic structure in the Li(x)FePO(4) system.

Imaging doped holes in a cuprate superconductor with high-resolution Compton scattering.

The high-temperature superconducting cuprate La(2-x)Sr(x)CuO(4) (LSCO) shows several phases ranging from antiferromagnetic insulator to metal with increasing hole doping. To understand how the nature of the hole state evolves with doping, we have carried out high-resolution Compton scattering measurements at room temperature together with first-principles electronic structure computations on a series of LSCO single crystals in which the hole doping level varies from the underdoped (UD) to the overdoped (OD) regime. Holes in the UD system are found to primarily populate the O 2p(x)/p(y) orbitals. In contrast, the character of holes in the OD system is very different in that these holes mostly enter Cu d orbitals. High-resolution Compton scattering provides a bulk-sensitive method for imaging the orbital character of dopants in complex materials.