arXiv subjects

S. Schuppler

Publications and source records attributed to S. Schuppler.

15 recordsLinked to original sources

arXiv2026

From perovskite to infinite-layer nickelates: hole concentration from x-ray absorption

The difficulty of determining cation concentrations and oxygen stoichiometry in infinite-layer nickelate thin films has so far prevented clear experimental identification of the nickel electron configuration in the superconducting phase. We used soft x-ray absorption spectroscopy to study the successive changes in PrNiO$_x$ thin films at various intermediate stages of topotactic reduction with $x=2-3$. By comparing the Ni-$L$ edge spectra to single and double cluster ligand-field calculations, we find that none of our samples exhibit a pure $d^9$ configuration. Our quantitative analysis using the charge sum rule shows that even when films are maximally reduced, the averaged number of nickel $3d$ holes is 1.35. Superconducting samples have even higher values, calling into question the previously assumed limit of hole doping. Concomitant changes in the oxygen $K$-edge absorption spectra upon reduction indicate the presence of oxygen $2p$ holes, even in the most reduced films. Overall, our results suggest a complex interplay of hole doping mechanisms resulting from self-doping effects and oxygen non-stoichiometry.

cond-mat.supr-con↗

arXiv2016

Of Substitution and Doping: Spatial and Electronic Structure in Fe Pnictides

A highly intriguing aspect in iron-pnictide superconductors is the composition-dependent electronic structure, in particular the question if and how charge carriers are introduced to the system upon substitution of Ba by alkali metals or of Fe by other transition metals, TM. We report on a systematic study of spatial structure and electronic states by x-ray diffraction and x-ray absorption on a large number of compositions in the (Ba,K)(Fe,TM)2As2 family. The coherent combination of detailed structural information with an in-depth analysis of the electronic structure allows us to sensitively disentangle (charge-carrier) "doping" effects from "substitutional" effects. Results include a doping character that is site-decoupled, as well as TM 3d energy-level schemes that exhibit non-standard level sequences and even t2-e level crossings. Our study indicates that doping per se seems to play a lesser role than expected for pnictide superconductivity and magnetism.

cond-mat.supr-con↗

arXiv2014

X-ray absorption spectroscopy study of the electronic and magnetic proximity effects in YBa$_2$Cu$_3$O$_{7}$/La$_{2/3}$Ca$_{1/3}$MnO$_3$ and La$_{2-x}$Sr$_x$CuO$_4$/La$_{2/3}$Ca$_{1/3}$MnO$_3$ multilayers

With x-ray absorption spectroscopy we investigated the orbital reconstruction and the induced ferromagnetic moment of the interfacial Cu atoms in YBa$_2$Cu$_3$O$_{7}$/La$_{2/3}$Ca$_{1/3}$MnO$_3$ (YBCO/LCMO) and La$_{2-x}$Sr$_{x}$CuO$_4$/La$_{2/3}$Ca$_{1/3}$MnO$_3$ (LSCO/LCMO) multilayers. We demonstrate that these electronic and magnetic proximity effects are coupled and are common to these cuprate/manganite multilayers. Moreover, we show that they are closely linked to a specific interface termination with a direct Cu-O-Mn bond. We furthermore show that the intrinsic hole doping of the cuprate layers and the local strain due to the lattice mismatch between the cuprate and manganite layers are not of primary importance. These findings underline the central role of the covalent bonding at the cuprate/manganite interface in defining the spin-electronic properties.

cond-mat.str-el↗

arXiv2012

Electronic structure of single-crystalline Mg$_x$Al$_{1-x}$B$_2$ probed by x-ray diffraction multipole refinements and polarization-dependent x-ray absorption spectroscopy

X-ray diffraction multipole refinements of single-crystalline Mg$_x$Al$_{1-x}$B$_2$ and polarization-dependent near-edge x-ray absorption fine structure at the B 1$s$ edge reveal a strongly anisotropic electronic structure. Comparing the data for superconducting compounds ($x= 0.8$, 1.0) with those for the non-superconductor ($x=0$) gives direct evidence for a rearrangement of the hybridizations of the boron $p_z$ bonds and underline the importance of holes in the $σ$-bonded covalent $sp^2$ states for the superconducting properties of the diborides. The data indicate that Mg is approximately divalent in MgB$_2$ and suggest predominantly ionic bonds between the Mg ions and the two-dimensional B rings. For AlB$_2$ ($x=0$), on the other hand, about 1.5 electrons per Al atom are transferred to the B sheets while the residual 1.5 electrons remain at the Al site which suggests significant covalent bonding between the Al ions and the B sheets. This finding together with the static electron deformation density points to almost equivalent electron counts on B sheets of MgB$_2$ and AlB$_2$\@, yet with a completely different electron/hole distribution between the $σ$ and $π$ bonds.

cond-mat.supr-con↗

arXiv2012

Magnetic proximity effect in $\mathbf{YBa_2Cu_3O_7/La_{2/3}Ca_{1/3}MnO_3}$ and $\mathbf{YBa_2Cu_3O_7/LaMnO_{3+δ}}$ superlattices

Using neutron reflectometry and resonant x-ray techniques we studied the magnetic proximity effect (MPE) in superlattices composed of superconducting YBa$_2$Cu$_3$O$_7$ (YBCO) and ferromagnetic-metallic (FM-M) La$_{0.67}$Ca$_{0.33}$MnO$_{3}$ (LCMO) or ferromagnetic-insulating (FM-I) LaMnO$_{3+δ}$ (LMO). We find that the MPE strongly depends on the electronic state of the manganite layers, being pronounced for the FM-M LCMO and almost absent for FM-I LMO. We also detail the change of the magnetic depth profile due to the MPE and provide evidence for its intrinsic nature.

cond-mat.str-el↗

arXiv2012

Electronic structure of single-crystalline Sr(Fe$_{1-x}$Co$_x$)$_2$As$_2$ probed by x-ray absorption spectroscopy: Evidence for isovalent substitution of Fe$^{2+}$ by Co$^{2+}$

The substitutional dependence of valence and spin-state configurations of Sr(Fe$_{1-x}$Co$_x$)$_2$As$_2$ ($x =$ 0, 0.05, 0.11, 0.17, and 0.38) is investigated with near-edge x-ray absorption fine structure at the $L_{2,3}$ edges of Fe, Co, and As. The present data provide direct spectroscopic evidence for an effectively isovalent substitution of Fe$^{2+}$ by Co$^{2+}$, which is in contrast to the widely assumed Co-induced electron-doping effect. Moreover, the data reveal that not only does the Fe valency remain completely unaffected across the entire doping range, but so do the Co and As valencies as well. The data underline a prominent role of the hybridization between (Fe,Co) 3$d_{xy}$, $d_{xz}$, $d_{yz}$ orbitals and As $4s/4p$ states for the band structure in $A$(Fe$_{1-x}$Co$_x$)$_2$As$_2$ and suggest that the covalency of the (Fe,Co)-As bond is a key parameter for the interplay between magnetism and superconductivity.

cond-mat.supr-con↗

arXiv2011

Spectroscopic study of impurities and associated defects in nanodiamonds from Efremovka (CV3) and Orgueil (CI) meteorites

The results of spectroscopic and structural studies of phase composition and of defects in nanodiamonds from Efremovka (CV3) and Orgueil (CI) chondrites indicate that nitrogen atomic environment in meteoritic nanodiamonds (MND) is similar to that observed in synthetic counterparts produced by detonation and by the Chemical Vapour Deposition (CVD)-process. Most of the nitrogen in MND appears to be confined to lattice imperfections, such as crystallite/twin boundaries and other extended defects, while the concentration of nitrogen in the MND lattice is low. It is suggested that the N-rich sub-population of MND grains may have been formed with high growth rates in environments rich in accessible N (i.e., N in atomic form or as weakly bonded compounds). For the first time the silicon-vacancy complex (the "silicon" defect) is observed in MND by photoluminescence spectroscopy.

cond-mat.mes-hall↗

arXiv2010

Orbital-Resolved Partial Charge Transfer from the Methoxy Groups of Substituted Pyrenes in Complexes with Tetracyanoquinodimethane - a NEXAFS Study

It is demonstrated that the near-edge X-ray absorption fine structure (NEXAFS) provides a powerful local probe of functional groups in novel charge transfer (CT) compounds. Microcrystals of tetra- and hexamethoxypyrene as donors with the strong acceptor tetracyanoquinodimethane (TMPx/HMPx - TCNQy) were grown from solution via vapour diffusion in different stoichiometries x:y = 1:1, 1:2 and 2:1. Owing to the element specificity of NEXAFS, the oxygen and nitrogen K-edge spectra are direct spectroscopic fingerprints of the donating and accepting moieties. The orbital selectivity of the NEXAFS resonances allows to precisely elucidate the participation of specific orbitals in the charge-transfer process. In the present case charge is transferred from methoxy-orbitals 2e (PI*) and 6a1 (SIGMA*) to the cyano-orbitals b3g and au (PI*) and - to a weaker extent - to b1g and b2u (SIGMA*). The occupation of 2e reflects the anionic character of the methoxy groups. Surprisingly, the charge transfer increases with increasing HMP content of the complex. As additional indirect signature, all spectral features of the donor and acceptor are shifted to higher and lower photon energies, respectively. Providing quantitative access to the relative occupation of specific orbitals, the approach constitutes the most direct probe of the charge-transfer mechanism in organic salts found so far. Although demonstrated for the specific example of pyrene-derived donors with the classical acceptor TCNQ, the method is very versatile and can serve as routine probe for novel CT-complexes on the basis of functionalized polycyclic aromatic hydrocarbons.

cond-mat.mtrl-sci↗

arXiv2010

YBa$_2$Cu$_3$O$_7$/La$_{0.7}$Ca$_{0.3}$MnO$_3$ bilayers: Interface coupling and electric transport properties

Heteroepitaxially grown bilayers of ferromagnetic La$_{0.7}$Ca$_{0.3}$MnO$_3$ (LCMO) on top of superconducting YBa$_2$Cu$_3$O$_7$ (YBCO) thin films were investigated by focusing on electric transport properties as well as on magnetism and orbital occupation at the interface. Transport measurements on YBCO single layers and on YBCO/LCMO bilayers, with different YBCO thickness $d_Y$ and constant LCMO thickness $d_L=50$\,nm, show a significant reduction of the superconducting transition temperature $T_c$ only for $d_Y<10$\,nm,with only a slightly stronger $T_c$ suppression in the bilayers, as compared to the single layers. X-ray magnetic circular dichroism (XMCD) measurements confirm recently published data of an induced magnetic moment on the interfacial Cu by the ferromagnetically ordered Mn ions, with antiparallel alignment between Cu and Mn moments. However, we observe a significantely larger Cu moment than previously reported, indicating stronger coupling between Cu and Mn at the interface. This in turn could result in an interface with lower transparency, and hence smaller spin diffusion length, that would explain our electric transport data, i.e.smaller $T_c$ suppression. Moreover, linear dichroism measurements did not show any evidence for orbital reconstruction at the interface, indicating that a large change in orbital occupancies through hybridization is not necessary to induce a measurable ferromagnetic moment on the Cu atoms.

cond-mat.supr-con↗

arXiv2009

Soft x-ray magnetic circular dichroism of LaCoO$_{3}$, La$_{0.7}$Ce$_{0.3}$CoO$_{3}$, and La$_{0.7}$Sr$_{0.3}$CoO$_{3}$ films: Evidence for Co valency-dependent magnetism and magnetic anisotropy

Epitaxial thin films of undoped LaCoO$_{3}$\@, of electron-doped La$_{0.7}$Ce$_{0.3}$CoO$_{3}$\@, and of hole-doped La$_{0.7}$Sr$_{0.3}$CoO$_{3}$\@ exhibit ferromagnetic order with a transition temperature $T_{\rm{C}}$ $\approx$ 85 K, 22 K, and 240 K, respectively. The spin-state structure for these compounds was studied by soft x-ray magnetic circular dichroism at the Co $L_{2,3}$ and O $K$ edges. It turns out that a higher spin state of the Co$^{3+}$ ions is responsible for the magnetism in LaCoO$_{3}$\@ while for La$_{0.7}$Ce$_{0.3}$CoO$_{3}$ the Co$^{3+}$ ions are in a low-spin state and the ferromagnetism is predominantly determined by Co$^{2+}$\@. For La$_{0.7}$Sr$_{0.3}$CoO$_{3}$\@, on the other hand, the magnetism originates from higher spin states of Co$^{3+}$ and Co$^{4+}$\@. Moreover, a strong magnetic anisotropy is observed for all systems.

cond-mat.str-el↗

arXiv2008

Suppression of spin-state transition in epitaxially strained LaCoO_{3}

Epitaxial thin films of LaCoO_{3} (E-LCO) exhibit ferromagnetic order with a transition temperature T_c = 85 K, while polycrystalline thin LaCoO_{3} films (P-LCO) remain paramagnetic. The temperature-dependent spin-state structure for both E-LCO and P-LCO was studied by x-ray absorption spectroscopy at the Co L_{2,3} and O K edges. Considerable spectral redistributions over temperature are observed for P-LCO. The spectra for E-LCO, on the other hand, do not show any significant changes for temperatures between 30 K and 450 K at both edges, indicating that the spin state remains constant and that the epitaxial strain inhibits any population of the low-spin (S = 0) state with decreasing temperature. This observation identifies an important prerequisite for ferromagnetism in E-LCO thin films.

cond-mat.str-el↗

arXiv2005

Electronic and vibrational properties of low-dimensional perovskites Sr$_{1-y}$La$_y$NbO$_{3.5-x}$

By angle-resolved photoemission spectroscopy and polarization-dependent infrared reflectivity measurements the electronic and vibrational properties of low-dimensional perovskites Sr$_{1-y}$La$_y$NbO$_{3.5-x}$ were studied along different crystal directions. The electronic behavior strongly depends on the oxygen and La content, including quasi-one-dimensional metallic and ferroelectric insulating behavior. An extremely small energy gap at the Fermi level is found for SrNbO$_{3.41}$ and SrNbO$_{3.45}$ along the conducting direction at low temperature, suggestive for a Peierls-type instability. Despite the similar nominal carrier density, for Sr$_{0.8}$La$_{0.2}$NbO$_{3.50}$ the quasi-one-dimensional metallic character is suppressed and no gap opening is observed, which can be explained by differences in the crystal structure. Electron-phonon interaction appears to play an important role in this series of compounds.

cond-mat.mtrl-sci↗

arXiv2003

Extremely Small Energy Gap in the Quasi-One-Dimensional Conducting Chain Compound SrNbO$_{3.41}$

Resistivity, optical, and angle-resolved photoemission experiments reveal unusual one-dimensional electronic properties of highly anisotropic SrNbO$_{3.41}$. Along the conducting chain direction we find an extremely small energy gap of only a few meV at the Fermi level. A discussion in terms of typical 1D instabilities (Peierls, Mott-Hubbard) shows that neither seems to provide a satisfactory explanation for the unique properties of SrNbO$_{3.41}$.

cond-mat.str-el↗

arXiv2002

Electronic structure of single-crystalline Mg(x)Al(1-x)B(2)

Polarization-dependent x-ray absorption spectroscopy at the B 1s edge of single-crystalline Mg(x)Al(1-x)B(2) reveals a strongly anisotropic electronic structure near the Fermi energy. Comparing spectra for superconducting compounds (x=0.9, 1.0) with those for the non-superconductor x=0.0 gives direct evidence on the importance of an in-plane spectral feature crossing E_F for the superconducting properties of the diborides. Good agreement is found with the projected B 2p density of states from LDA band structure calculations.

cond-mat.supr-con↗

arXiv2000

Hole distribution for (Sr,Ca,Y,La)_14 Cu_24 O_41 ladder compounds studied by x-ray absorption spectroscopy

The unoccupied electronic structure for the Sr_14Cu_24O_41 family of two-leg ladder compounds was investigated for different partial substitutions of Sr^2+ by Ca^2+, leaving the nominal hole count constant, and by Y^3+ or La^3+, reducing the nominal hole count from its full value of 6 per formula unit. Using polarization-dependent x-ray absorption spectroscopy on single crystals, hole states on both the chain and ladder sites could be studied. While for intermediate hole counts all holes reside on O sites of the chains, a partial hole occupation on the ladder sites in orbitals oriented along the legs is observed for the fully doped compound Sr_14Cu_24O_41. On substitution of Ca for Sr orbitals within the ladder planes but perpendicular to the legs receive some hole occupation as well.

cond-mat.str-el↗