arXiv subjects

Martin Magnuson

Publications and source records attributed to Martin Magnuson.

At least 37 records · Page 2Linked to original sources

arXiv2018

Polarization-dependent resonant inelastic X-ray scattering study at the Cu L and O K-edge of YBa$_2$Cu$_3$O$_{7-x}$

We present a study on the high-Tc superconductor (HTSC) YBa2Cu3O7-x (YBCO) using polarization-dependent X-ray absorption and resonant inelastic X-ray scattering. High-resolution measurements using synchrotron-radiation are compared with calculations using a quasi-atomic multiplet approach performed at the Cu 2p3/2-edge of YBCO. We use a multiplet approach within the single impurity Anderson model to reproduce and understand the character of the localized low-energy excitations in YBCO. We observe a distinct peak at about 0.5 eV in O K RIXS. This peak shows dependence on doping, incident energy, and momentum transfer that suggests that it has a different origin than the previously discussed cuprate bi-magnons. Therefore, we assign it to multi-magnon excitations between the Zhang Rice bands and/or the Upper Hubbard bands, respectively.

cond-mat.mtrl-sci↗

arXiv2018

Chemical bonding in carbide MXene nanosheets

The chemical bonding in the carbide core and the surface chemistry in a new group of transition-metal carbides Tin+1Cn-Tx (n=1,2) called MXenes have been investigated by surface-sensitive valence band X-ray photoelectron spectroscopy. Changes in band structures of stacked nano sheets of different thicknesses are analyzed in connection to known hybridization regions of TiC and TiO2 that affect elastic and transport properties. By employing high excitation energy, the photoelectron cross-section for the C 2s - Ti 3d hybridization region at the bottom of the valence band is enhanced. As shown in this work, the O 2p and F 2p bands are shown to strongly depend both on the bond lengths to the surface groups and the adsorption sites. The effect of surface oxidation and Ar+ sputtering on the electronic structure is also discussed.

cond-mat.mtrl-sci↗

arXiv2018

Chemical Bonding in Epitaxial ZrB2 Studied by X-ray Spectroscopy

The chemical bonding in an epitaxial ZrB2 film is investigated by Zr K-edge (1s) X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies and compared to the ZrB2 compound target from which the film was synthesized as well as a bulk α-Zr reference. Quantitative analysis of X-ray Photoelectron Spectroscopy spectra reveals at the surface: ~5% O in the epitaxial ZrB2 film, ~19% O in the ZrB2 compound target and ~22% O in the bulk α-Zr reference after completed sputter cleaning. For the ZrB2 compound target, X-ray diffraction (XRD) shows weak but visible -111, 111, and 220 peaks from monoclinic ZrO2 together with peaks from ZrB2 and where the intensity distribution for the ZrB2 peaks show a randomly oriented target material. For the bulk α-Zr reference no peaks from any crystalline oxide were visible in the diffractogram recorded from the 0001-oriented metal. The Zr K-edge absorption from the two ZrB2 samples demonstrate more pronounced oscillations for the epitaxial ZrB2 film than in the bulk ZrB2 attributed to the high atomic ordering within the columns of the film. The XANES exhibits no pre-peak due to lack of p-d hybridization in ZrB2, but with a chemical shift towards higher energy of 4 eV in the film and 6 eV for the bulk compared to α-Zr (17.993 keV) from the charge-transfer from Zr to B. The 2 eV larger shift in bulk ZrB2 material suggests higher oxygen content than in the epitaxial film, which is supported by XPS. In EXAFS, the modelled cell-edge in ZrB2 is slightly smaller in the thin film (a=3.165 Å, c=3.520 Å) in comparison to the bulk target material (a=3.175 Å, c=3.540 Å) while in hexagonal closest-packed metal (α-phase, a=3.254 Å, c=5.147 Å).

cond-mat.mtrl-sci↗

arXiv2017

Bonding Structures of ZrHx Thin Films by X-ray Spectroscopy

The variation in local atomic structure and chemical bonding of ZrHx (x=0.15, 0.30, 1.16) magnetron sputtered thin films are investigated by Zr K-edge (1s) X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopies. A chemical shift of the Zr K-edge towards higher energy with increasing hydrogen content is observed due to charge-transfer and an ionic or polar covalent bonding component between the Zr 4d and the H 1s states with increasing valency for Zr. We find an increase in the Zr-Zr bond distance with increasing hydrogen content from 3.160 Å in the hexagonal closest-packed metal (alpha-phase) to 3.395 Å in the understoichiometric delta-ZrHx film (CaF2-type structure) with x=1.16 that largely resembles that of bulk delta-ZrH2. For yet lower hydrogen contents, the structures are mixed alpha and delta-phases, while sufficient hydrogen loading (x>1) yields a pure δ-phase that is understoichiometric, but thermodynamically stable. The change in the hydrogen content and strain is discussed in relation to the corresponding change of bond lengths, hybridizations, and trends in electrical resistivity.

cond-mat.mtrl-sci↗

arXiv2017

Electronic Properties and Bonding in ZrHx Thin Films Investigated by Valence-Band X-ray Photoelectron Spectroscopy

The electronic structure and chemical bonding in reactively magnetron sputtered ZrHx (x=0.15, 0.30, 1.16) thin films with oxygen content as low as 0.2 at% are investigated by 4d valence band, shallow 4p core-level and 3d core-level X-ray photoelectron spectroscopy. With increasing hydrogen content, we observe significant reduction of the 4d valence states close to the Fermi level as a result of redistribution of intensity towards the H 1s - Zr 4d hybridization region at about 6 eV below the Fermi level. For low hydrogen content (x=0.15, 0.30), the films consist of a superposition of hexagonal closest packed metal (alpha-phase)and understoichiometric delta-ZrHx (CaF2-type structure) phases, while for x=1.16, the film form single phase ZrHx that largely resembles that of stoichiometric delta-ZrH2 phase. We show that the cubic delta-ZrHx phase is metastable as thin film up to x=1.16 while for higher H-contents, the structure is predicted to be tetragonally distorted. For the investigated ZrH1.16 film, we find chemical shifts of 0.68 and 0.51 eV towards higher binding energies for the Zr 4p3/2 and 3d5/2 peak positions, respectively. Compared to the Zr metal binding energies of 27.26 and 178.87 eV, this signifies a charge-transfer from Zr to H atoms. The change in the electronic structure, spectral line shapes, and chemical shifts as function of hydrogen content is discussed in relation to the charge-transfer from Zr to H that affects the conductivity by charge redistribution in the valence band.

cond-mat.mtrl-sci↗

arXiv2016

Chemical bonding and electronic-structure in MAX phases as viewed by X-ray spectroscopy and density functional theory

This is a critical review of MAX-phase carbides and nitrides from an electronic-structure and chemical bonding perspective. This large group of nanolaminated materials is of great scientific and technological interest and exhibit a combination of metallic and ceramic features. These properties are related to the special crystal structure and bonding characteristics with alternating strong M-C bonds in high-density MC slabs, and relatively weak M-A bonds between the slabs. Here, we review the trend and relationship between the chemical bonding, conductivity, elastic and magnetic properties of the MAX phases in comparison to the parent binary MX compounds with the underlying electronic structure probed by polarized X-ray spectroscopy. Spectroscopic studies constitute important tests of the results of state-of-the-art electronic structure density functional theory that is extensively discussed and are generally consistent. By replacing the elements on the M, A, or X-sites in the crystal structure, the corresponding changes in the conductivity, elasticity, magnetism and other materials properties makes it possible to tailor the characteristics of this class of materials by controlling the strengths of their chemical bonds.

cond-mat.mtrl-sci↗

arXiv2016

Structure and Bonding in Amorphous Cr1-xCx Nanocomposite Thin Films: X-ray Absorption Spectra and First-Principles Calculation

The local structure and chemical bonding in two-phase amorphous Cr$_{1-x}$C$_{x}$ nanocomposite thin films are investigated by Cr $K$-edge ($1s$) X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies in comparison to theory. By utilizing the computationally efficient \textit{stochastic quenching} (SQ) technique, we reveal the complexity of different Cr-sites in the transition metal carbides, highlighting the need for large scale averaging to obtain theoretical XANES and EXAFS spectra for comparison with measurements. As shown in this work, it is advantageous to use \textit{ab initio} theory as an assessment to correctly model and fit experimental spectra and investigate the trends of bond lengths and coordination numbers in complex amorphous materials. With sufficient total carbon content ($\geq$ 30 at\%), we find that the short-range coordination in the amorphous carbide phase exhibit similarities to that of a Cr$_{7}$C$_{3\pm{}y}$ structure, while excessive carbons assemble in the amorphous carbon phase.

cond-mat.mtrl-sci↗

arXiv2016

Induced magnetism at the interfaces of a Fe/V superlattice investigated by resonant magnetic x-ray scattering

The induced magnetic moments in the V 3d electronic states of interface atomic layers in a Fe(6ML)/V(7ML) superlattice was investigated by x-ray resonant magnetic scattering. The first V atomic layer next to Fe was found to be strongly antiferromagnetically polarized relatively to Fe and the magnetic moments of the next few atomic layers in the interior V region decay exponentially with increasing distance from the interface, while the magnetic moments of the Fe atomic layers largely remain bulk-like. The induced V moments decay more rapidly as observed by x-ray magnetic scattering than in standard x-ray magnetic circular dichroism. The theoretical description of the induced magnetic atomic layer profile in V was found to strongly rely on the interface roughness within the superlattice period. These results provide new insight into interface magnetism by taking advantage of the enhanced depth sensitivity to the magnetic profile over a certain resonant energy bandwidth in the vicinity of the Bragg angles.

cond-mat.mtrl-sci↗

arXiv2015

The origin of anisotropy and high density of states in the electronic structure of Cr$_2$GeC by means of polarized soft X-ray spectroscopy and ab initio calculations

The anisotropy in the electronic structure of the inherently nanolaminated ternary phase Cr$_{2}$GeC is investigated by bulk-sensitive and element selective soft x-ray absorption/emission spectroscopy. The angle-resolved absorption/emission measurements reveal differences between the in-plane and out-of-plane bonding at the (0001) interfaces of Cr$_{2}$GeC. The Cr $L_{2,3}$, C $K$, and Ge $M_{1}$, $M_{2,3}$ emission spectra are interpreted with first-principles density-functional theory (DFT) including core-to-valence dipole transition matrix elements. For the Ge $4s$ states, the x-ray emission measurements reveal two orders of magnitude higher intensity at the Fermi level than DFT within the General Gradient Approximation (GGA) predicts. We provide direct evidence of anisotropy in the electronic structure and the orbital occupation that should affect the thermal expansion coefficient and transport properties. As shown in this work, hybridization and redistribution of intensity from the shallow $3d$ core levels to the $4s$ valence band explain the large Ge density of states at the Fermi level.

cond-mat.mtrl-sci↗

arXiv2015

Structure and bonding in amorphous iron carbide thin films

We investigate the amorphous structure, chemical bonding, and electrical properties of magnetron sputtered Fe1-xCx (0.21<x<0.72) thin films. X-ray, electron diffraction and transmission electron microscopy show that the Fe1-xCx films are amorphous nanocomposites, consisting of a two-phase domain structure with Fe-rich carbidic FeCy, and a carbon-rich matrix. Pair distribution function analysis indicates a close-range order similar to those of crystalline Fe3C carbides in all films with additional graphene-like structures at high carbon content (71.8 at% C). From X-ray photoelectron spectroscopy measurements, we find that the amorphous carbidic phase has a composition of 15-25 at% carbon that slightly increases with total carbon content. X-ray absorption spectra exhibit increasing number of unoccupied 3d states and decreasing number of C 2p states as a function of carbon content. These changes signify a systematic redistribution in orbital occupation due to charge-transfer effects at the domain-size dependent carbide/matrix interfaces. Four-point probe resistivity of the Fe1-xCx films increases exponentially with carbon content from 200 mu-Ohm-cm (x=0.21) to 1200 mu-Ohm-cm (x=0.72), and is found to depend on the total carbon content rather than the composition of the carbide. Our findings open new possibilities for modifying the resistivity of amorphous thin film coatings based on transition metal carbides by control of amorphous domain structures.

cond-mat.mtrl-sci↗

arXiv2014

Self-doping processes between planes and chains in the metal-to-superconductor transition of YBa2Cu3O6.9

The interplay between the quasi 1-dimensional CuO-chains and the 2-dimensional CuO2 planes of YBa2Cu3O6+x (YBCO) has been in focus for a long time. Although the CuO-chains are known to be important as charge reservoirs that enable superconductivity for a range of oxygen doping levels in YBCO, the understanding of the dynamics of its temperature-driven metal-superconductor transition (MST) remains a challenge. We present a combined study using x-ray absorption spectroscopy and resonant inelastic x-ray scattering (RIXS) revealing how a reconstruction of the apical O(4)-derived interplanar orbitals during the MST of optimally doped YBCO leads to substantial hole-transfer from the chains into the planes, i.e. self-doping. Our ionic model calculations show that localized divalent charge-transfer configurations are expected to be abundant in the chains of YBCO. While these indeed appear in the RIXS spectra from YBCO in the normal, metallic, state, they are largely suppressed in the superconducting state and, instead, signatures of Cu trivalent charge-transfer configurations in the planes become enhanced. In the quest for understanding the fundamental mechanism for high-Tc-superconductivity (HTSC) in perovskite cuprate materials, the observation of such an interplanar self-doping process in YBCO opens a unique novel channel for studying the dynamics of HTSC.

cond-mat.supr-con↗

arXiv2014

Crystallization characteristics and chemical bonding properties of nickel carbide thin film nanocomposites

The crystal structure and chemical bonding of magnetron-sputtering deposited nickel carbide Ni$_{1-x}$C$_{x}$ (0.05$\leq$x$\leq$0.62) thin films have been investigated by high-resolution X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and soft X-ray absorption spectroscopy. By using X-ray as well as electron diffraction, we found carbon-containing hcp-Ni (hcp-NiC$_{y}$ phase), instead of the expected rhombohedral-Ni$_{3}$C. At low carbon content (4.9 at\%) the thin film consists of hcp-NiC$_{y}$ nanocrystallites mixed with a smaller amount of fcc-NiC$_{x}$. The average grain size is about 10-20 nm. With the increase of carbon content to 16.3 at\%, the film contains single-phase hcp-NiC$_{y}$ nanocrystallites with expanded lattice parameters. With further increase of carbon content to 38 at\%, and 62 at\%, the films transform to X-ray amorphous materials with hcp-NiC$_{y}$ and fcc-NiC$_{x }$ nanodomain structures in an amorphous carbon-rich matrix. Raman spectra of carbon indicate dominant $sp^{2}$ hybridization, consistent with photoelectron spectra that show a decreasing amount of C-Ni phase with increasing carbon content. The Ni $3d$ - C $2p$ hybridization in the hexagonal structure gives rise to the salient double-peak structure in Ni $2p$ soft X-ray absorption spectra at 16.3 at\% that changes with carbon content. We also show that the resistivity is not only governed by the amount of carbon, but increases by more than a factor of two when the samples transform from crystalline to amorphous.

cond-mat.mtrl-sci↗

arXiv2014

Strain Sensitivity in the Nitrogen 1s NEXAFS Spectra of Gallium Nitride

The Nitrogen 1s near edge X-ray absorption fine structure (NEXAFS) of gallium nitride (GaN) shows a strong natural linear dichroism that arises from its anisotropic wurtzite structure. An additional spectroscopic variation arises from lattice strain in epitaxially grown GaN thin films. This variation is directly proportional to the degree of strain for some spectroscopic features. This strain variation is interpreted with the aid of density functional theory calculations.

cond-mat.mtrl-sci↗

arXiv2013

Electronic correlation effects in the Cr2GeC Mn+1AXn phase

The magnetic properties, electronic band structure and Fermi surfaces of the hexagonal Cr2GeC system have been studied by means of both generalized gradient approximation (GGA) and the +U corrected method (GGA+U). The effective U value has been computed within the augmented plane-wave theoretical scheme by following the constrained density functional theory formalism of Anisimov et al. [1991 Phys. Rev. B 45, 7570]. On the basis of our GGA+U calculations, a compensated anti-ferromagnetic spin ordering of Cr atoms has been found to be the ground state solution for this material, where a Ge-mediated super-exchange coupling is responsible for an opposite spin distribution between the ABA stacked in-plane Cr-C networks. Structural properties have also been tested and found to be in good agreement with the available experimental data. Topological analysis of Fermi surfaces have been used to qualitatively address the electronic transport properties of Cr2GeC and found an important asymmetrical carrier-type distribution within the hexagonal crystal lattice. We conclude that an appropriate description of the strongly correlated Cr-d electrons is an essential issue for interpreting the material properties of this unusual Cr-based MAX-phase.

cond-mat.mtrl-sci↗

arXiv2012

The electronic-structure origin of the anisotropic thermopower of nanolaminated Ti3SiC2 determined by polarized x-ray spectroscopy and Seebeck measurements

Nanolaminated materials exhibit characteristic magnetic, mechanical, and thermoelectric properties, with large contemporary scientific and technological interest. Here, we report on the anisotropic Seebeck coefficient in nanolaminated Ti3SiC2 single-crystal thin films and trace the origin to anisotropies in element-specific electronic states. In bulk polycrystalline form, Ti3SiC2 has a virtually zero Seebeck coefficient over a wide temperature range. In contrast, we find that the in-plane (basal ab) Seebeck coefficient of Ti3SiC2, measured on single-crystal films has a substantial and positive value of 4-6 muV/K. Employing a combination of polarized angle-dependent x-ray spectroscopy and density functional theory we directly show electronic structure anisotropy in inherently nanolaminated Ti3SiC2 single-crystal thin films as a model system. The density of Ti 3d and C 2p states at the Fermi level in the basal ab-plane is about 40 % higher than along the c-axis. The Seebeck coefficient is related to electron and hole-like bands close to the Fermi level but in contrast to ground state density functional theory modeling, the electronic structure is also influenced by phonons that need to be taken into account. Positive contribution to the Seebeck coefficient of the element-specific electronic occupations in the basal plane is compensated by 73 % enhanced Si 3d electronic states across the laminate plane that give rise to a negative Seebeck coefficient in that direction. Strong phonon vibration modes with three to four times higher frequency along the c-axis than along the basal ab-plane also influence the electronic population and the measured spectra by the asymmetric average displacements of the Si atoms. These results constitute experimental evidence explaining why the average Seebeck coefficient of Ti3SiC2 in polycrystals is negligible over a wide temperature range.

cond-mat.mtrl-sci↗

arXiv2012

Electronic Structure and Chemical Bonding of Amorphous Chromium Carbide Thin Films

The microstructure, electronic structure, and chemical bonding of chromium carbide thin films with different carbon contents have been investigated with high-resolution transmission electron microscopy, electron energy loss spectroscopy and soft x-ray absorption-emission spectroscopies. Most of the films can be described as amorphous nanocomposites with non-crystalline CrCx in an amorphous carbon matrix. At high carbon contents, graphene-like structures are formed in the amorphous carbon matrix. At 47 at% carbon content, randomly oriented nanocrystallites are formed creating a complex microstructure of three components. The soft x-ray absorption-emission study shows additional peak structures exhibiting non-octahedral coordination and bonding.

cond-mat.mes-hall↗

arXiv2011

Refractive index of vanadium determined by resonant diffraction of soft x-rays

The dispersive part of the refractive index of vanadium is determined by measuring the angular displacement of the first order diffraction peak of a V/Fe superlattice. The measurements were made using elliptically polarized synchrotron radiation which was scanned through the V L2,3 absorption edges for different incident scattering angles. The x-ray scattering technique provides access to direct determination of the dispersive part of the refractive index through an absorption resonance. The influence of absorption at the resonances is shown by comparing the absorption correction to the dispersion correction. The results demonstrate that 1-δ is larger than unity at the L2,3 resonances of vanadium and the optical consequences are discussed.

cond-mat.mtrl-sci↗

arXiv2011

Anisotropy in the electronic structure of V2GeC investigated by soft x-ray emission spectroscopy and first-principles theory

The anisotropy of the electronic structure of ternary nanolaminate V2GeC is investigated by bulk-sensitive soft x-ray emission spectroscopy. The measured polarization-dependent emission spectra of V L2,3, C K, Ge M1 and Ge M2,3 in V2GeC are compared to those from monocarbide VC and pure Ge. The experimental emission spectra are interpreted with calculated spectra using ab initio density-functional theory including dipole transition matrix elements. Different types of covalent chemical bond regions are revealed; V 3d - C 2p bonding at -3.8 eV, Ge 4p - C 2p bonding at -6 eV and Ge 4p - C 2s interaction mediated via the V 3d orbitals at -11 eV below the Fermi level. We find that the anisotropic effects are high for the 4p valence states and the shallow 3d core levels of Ge, while relatively small anisotropy is detected for the V 3d states. The macroscopic properties of the V2GeC nanolaminate result from the chemical bonds with the anisotropic pattern as shown in this work.

cond-mat.mtrl-sci↗