Per-Anders Glans

Understanding the electrochemical mechanism of K-αMnO2 for magnesium battery cathodes.

Batteries based on magnesium are an interesting alternative to current state-of-the-art lithium-ion systems; however, high-energy-density cathodes are needed for further development. Here we utilize TEM, EDS, and EELS in addition to soft-XAS to determine electrochemical magnesiation mechanism of a high-energy density cathode, K-αMnO2. Rather than following the typical insertion mechanism similar to Li(+), we propose the gradual reduction of K-αMnO2 to form Mn2O3 then MnO at the interface of the cathode and electrolyte, finally resulting in the formation of K-αMnO2@(Mg,Mn)O core-shell product after discharge of the battery. Understanding the mechanism is a vital guide for future magnesium battery cathodes.

Soft-x-ray spectroscopic investigation of ferromagnetic Co-doped ZnO

The electronic properties of cobalt-doped ZnO were investigated through site-selective and element-sensitive x-ray-absorption spectroscopy in the vicinity of the Co L2,3 edge, the oxygen K edge, and at the Zn L3 edge. The spectroscopic measurements of the ferromagnetic cobalt-doped ZnO films appear to have additional components in the O K edge x-ray-absorption spectrum not observed in the undoped films. The observed features may derive from both hybridization with unoccupied Co 3d states and also from lattice defects such as oxygen vacancies. Only minor changes in the Zn L3 edge spectra were observed. These observations are consistent with a polaron percolation model in which the ferromagnetic coupling is mediated by shallow donor electrons trapped in oxygen vacancies and couples the Co atoms substituted on Zn sites in the hexagonal wurtzite ZnO structure.

Quasiparticle spectra, charge-density waves, superconductivity, and electron-phonon coupling in 2H-NbSe2

High-resolution photoemission has been used to study the electronic structure of the charge-density wave (CDW) and superconducting dichalcogenide, 2H-NbSe2. From the extracted self-energies, important components of the quasiparticle interactions have been identified. In contrast to previously studied TaSe2, the CDW transition does not affect the electronic properties significantly. The electron-phonon coupling is identified as a dominant contribution to the quasiparticle self-energy and is shown to be very anisotropic (k dependent) and much stronger than in TaSe2.

Structural and magnetic properties of (In1−xFex)2O3 (0.0⩽x⩽0.25) system: Prepared by gel combustion method

(In1-xFex)2O3 polycrystalline samples with x = (0.0, 0.05, 0.10, 0.15, 0.20 and 0.25) have been synthesized by a gel combustion method. Reitveld refinement analysis of X raydiffraction data indicated the formation of single phase cubic bixbyite structure without any parasitic phases. This observation is further confirmed by high resolution transmission electron microscopy (HRTEM) imaging, and indexing of the selected-area electron diffraction (SAED) patterns, X-ray Absorption Spectroscopy (XAS) and Raman Spectroscopy. DC Magnetization studies as a function of temperature and field indicatethat they are ferromagnetic with Curie temperature (TC) well above room temperature.

Strain Dependence of Bonding and Hybridization Across the Metal-Insulator Transition of VO2

Soft x-ray spectroscopy is used to investigate the strain dependence of the metal-insulator transition of VO2. Changes in the strength of the V 3d - O 2p hybridization are observed across the transition, and are linked to the structural distortion. Furthermore, although the V-V dimerization is well-described by dynamical mean-field theory, the V-O hybridization is found to have an unexpectedly strong dependence on strain that is not predicted by band theory, emphasizing the relevance of the O ion to the physics of VO2.

Effect of Al3+ co-doping on the dopant local structure, optical properties, and exciton dynamics in Cu+-doped ZnSe nanocrystals.

The dopant local structure and optical properties of Cu-doped ZnSe (ZnSe:Cu) and Cu and Al co-doped ZnSe (ZnSe:Cu,Al) nanocrystals (NCs) were studied with an emphasis on understanding the impact of introducing Al as a co-dopant. Quantum-confined NCs with zinc blende crystal structure and particle size of 6 ± 0.6 Å were synthesized using a wet chemical route. The local structure of the Cu dopant, studied by extended X-ray absorption fine structure, indicated that Cu in ZnSe:Cu NCs occupies a site that is neither substitutional nor interstitial and is adjacent to a Se vacancy. Additionally, we estimated that approximately 25 ± 8% of Cu was located on the surface of the NC. Al(3+) co-doping aids in Cu doping by accounting for the charge imbalance originated by Cu(+) doping and consequently reduces surface Cu doping. The Cu ions remain distorted from the center of the tetrahedron to one of the triangular faces. The lifetime of the dopant-related photoluminescence was found to increase from 550 ± 60 to 700 ± 60 ns after Al co-doping. DFT calculations were used to obtain the density of states of a model system to help explain the optical properties and dynamics processes observed. This study demonstrates that co-doping using different cations with complementary oxidation states is an effective method to enhance optical properties of doped semiconductor NCs of interest for various photonics applications.

Towards understanding the electronic structure of Fe-doped CeO2 nanoparticles with X-ray spectroscopy

This study reports on the electronic structure of Fe-doped CeO2 nanoparticles (NPs), determined by coupled X-ray absorption spectroscopy and X-ray emission spectroscopy. A comparison of the local electronic structure around the Ce site with that around the Fe site indicates that the Fe substitutes for the Ce. The oxygen K-edge spectra that originated from the hybridization between cerium 4f and oxygen 2p states are sensitive to the oxidation state and depend strongly on the concentration of Fe doping. The Ce M(4,5)-edges and the Fe L(2,3)-edges reveal the variations of the charge states of Ce and Fe upon doping, respectively. The band gap is further obtained from the combined absorption-emission spectrum and decreased upon Fe doping, implying Fe doping introduces vacancies. The oxygen vacancies are induced by Fe doping and the spectrum reveals the charge transfer between Fe and Ce. Fe(3+) doping has two major effects on the formation of ferromagnetism in CeO2 nanoparticles. The first, at an Fe content of below 5%, is that the formation of Fe(3+)-Vo-Ce(3+) introduces oxygen deficiencies favoring ferromagnetism. The other, at an Fe content of over 5%, is the formation of Fe(3+)-Vo-Fe(3+), which favors antiferromagnetism, reducing the Ms. The defect structures Fe(3+)-Vo-Ce(3+) and Fe(3+)-Vo-Fe(3+) are crucial to the magnetism in these NPs and the change in Ms can be described as the effect of competitive interactions of magnetic polarons and paired ions.

X-Ray absorption, photoemission spectroscopy, and Raman scattering analysis of amorphous tantalum oxide with a large extent of oxygen nonstoichiometry

The electronic structure and modification of the local interatomic structure of a reactive sputtered amorphous tantalum oxide (a-TaO(x)) thin film with the variation of oxygen nonstoichiometry, x in a-TaO(x) have been investigated by X-ray absorption spectroscopy (XAS), X-ray photoemission spectroscopy (XPS), Raman scattering spectroscopy, and Rutherford back scattering spectroscopy. A parallel chemical shift of Ta4f(7/2) and O1s core levels observed with the variation of x indicates the Fermi level shift by reduction and oxidation in the framework of the rigid band model. Extended X-ray absorption fine structure (EXAFS) suggests both the increase of average coordination number of the first Ta-O shell in polyhedra and a considerable reduction of the average Ta-O bond length with the increase of x. The relative intensity of Raman shift peaks at 670 cm(-1) and 815 cm(-1), corresponding to Ta-O stretching of TaO(6) octahedra and TaO(5) probably with a pyramidal form, respectively, drastically changes between x = 2.47 to 1.86, suggesting the change in the predominant polyhedron from TaO(6) to TaO(5) with a modification in multiplicity of oxygen by the reorganization of the polyhedral network.

An ultra-high vacuum electrochemical flow cell for in situ/operando soft X-ray spectroscopy study

An in situ flow electrochemical cell has been designed and fabricated to allow better seal under UHV chamber thus to achieve a good signal to noise ratio in fluorescence yield detection of X-ray absorption spectra for spectroelectrochemical study. The cell also stabilizes the thin silicon nitride membrane window in an effective manner so that the liquid cell remains intact during X-ray absorption experiments. With the improved design of the liquid cell, electrochemical experiments such as cyclic voltammetry have been performed for 10 cycles with a good stability of sample window. Also an operando electrochemical experiment during photoelectrochemistry has been performed on n-type hematite electrode deposited on silicon nitride window. The experiment allows us to observe the formation of two extra electronic transitions before pre edge of O K-edge spectra.

Soft X-Ray Spectroscopic Study of Dense Strontium-Doped Lanthanum Manganite Cathodes for Solid Oxide Fuel Cell Applications

The evolution of the Mn charge state, chemical composition, and electronic structure of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LSMO) cathodes during the catalytic activation of solid oxide fuel cell (SOFC) has been studies using X-ray spectroscopy of as-processed, exposed, and activated dense thin LSMO films. Comparison of O K-edge and Mn L{sub 3,2}-edge X-ray absorption spectra from the different stages of LSMO cathodes revealed that the largest change after the activation occurred in the Mn charge state with little change in the oxygen environment. Core-level X-ray photoemission spectroscopy and Mn L{sub 3} resonant photoemission spectroscopy studies of exposed and as-processed LSMO determined that the SOFC environment (800 C ambient pressure of O{sub 2}) alone results in La deficiency (severest near the surface with Sr doping >0.55) and a stronger Mn{sup 4+} contribution, leading to the increased insulating character of the cathode prior to activation. Meanwhile, O K-edge X-ray absorption measurements support Sr/La enrichment nearer the surface, along with the formation of mixed Sr{sub x}Mn{sub y}O{sub z} and/or passive MnO{sub x} and SrO species.