arXiv subjects

Jean-Pascal Rueff

Publications and source records attributed to Jean-Pascal Rueff.

At least 19 recordsLinked to original sources

arXiv2025

Ultrafast Charge-Transfer and Auger Decay Processes in Aqueous CaCl$_2$ Solution: Insights from Core-Level Spectroscopy

Understanding the interaction between metal ions and their aqueous environment is fundamental in many areas of chemistry, biology, and environmental science. In this study, we investigate the electronic structure of hydrated calcium ions, focusing on how water molecules influence the behavior of the metal ion. We employed advanced X-ray techniques, including X-ray absorption, photoelectron, and Auger spectroscopies, combined with high-level quantum chemical calculations. Our analysis reveals that, alongside normal Auger decay, distinct ultrafast charge transfer processes occur between the calcium ion and surrounding water molecules, underscoring the complex nature of metal-solvent interactions. Two primary mechanisms were identified. The first one involves electron transfer from water to the calcium ion. The second mechanism depends on the photon energy and is tentatively attributed to the decay of photoelectron satellites, the capture of free solvated electrons or electrons from a Cl$^-$ ion in the second solvation shell. Additionally, we observed significant shifts in electron energies due to post-collision interactions and interpreted the Ca 1s-1 photoelectron satellites mainly as originating from inelastic photoelectron scattering (IPES). These findings provide deeper insights into the electronic properties of hydrated metal ions, with potential implications for fields such as catalysis and biochemistry, where metal ions play a crucial role.

physics.chem-ph↗

arXiv2024

Unraveling p-type and n-type interfaces in Superconducting Infinite-Layer Nickelate thin films

After decades of research, superconductivity was finally found in nickel-based analogs of superconducting cuprates, with infinite-layer (IL) structure. These results are so far restricted to thin films in the case of IL-nickelates. Therefore, the nature of the interface with the substrate, and how it couples with the thin film properties is still an open question. Here, using scanning transmission electron microscopy (STEM)- electron energy loss spectroscopy (EELS) and four-dimensional (4D)-STEM, a novel chemically sharp p-type interface is observed in a series of superconducting IL-praseodymium nickelate samples, and a comparative study is carried out with the previously reported n-type interface obtained in other samples. Both interfaces have strong differences, with the p-type interface being highly polar. In combination with ab-initio calculations, we find that the influence of the interface on the electronic structure is local, and does not extend beyond 2-3 unit cells into the thin film. This decouples the direct influence of the interface in driving the superconductivity, and indicates that the IL-nickelate thin films do not have a universal interface model. Insights into the spatial hole-distribution in SC samples, provided by monochromated EELS and total reflection-hard x-ray photoemission spectroscopy, suggest that this particular distribution might be directly influencing superconductivity.

cond-mat.supr-con↗

arXiv2024

A fundamental correlative spectroscopic study on LixNiO2 and NaNiO2

The intimate correlation between the local atomic arrangement and electronic states in Li-ion battery cathode materials plays a crucial role in determining their electrochemical properties, including capacity, cycling stability, and rate capability. Despite almost 30 years of research efforts on high performance cathodes based on Ni rich layered oxides, there is still no consensus on LiNiO2 local atomic and electronic structure. Ni sites could be either Jahn-Teller distorted or bond disproportionated and the role of Ni and oxygen in the charge compensation mechanism remains unclear. In this study, we compare the local and electronic structure of LiNiO2 and NaNiO2, a long-range Jahn-Teller system, using a novel approach which aims at correlating the results from bulk spectroscopy techniques, particularly under operando conditions, obtained on standard samples to ensure sample interoperability and enhance the reliability and robustness of our results. Despite being a site-selective and local technique, XAS is unable to discriminate between the proposed scenarios, as confirmed also by theoretical calculations. On the contrary, Raman spectroscopy show local structural differences between monoclinic distorted NaNiO2 and rhombohedral LiNiO2. Additionally, HAXPES confirms the presence of multiple formal oxidation states for Ni, and RIXS data provides evidence of 3d8 states, confirming the negative charge transfer character of Ni and some degree of bond disproportionation in LiNiO2. Regarding the charge compensation mechanism, XRS and RIXS support the participation of oxygen holes in the redox activity, while Raman spectroscopy does not detect molecular oxygen. By combing several high-fidelity spectroscopy datasets, this study shows the value of correlative characterization workflows to provide insights into complex structural-electrochemical relationships.

cond-mat.mtrl-sci↗

arXiv2024

Depth-resolving the redox compensation mechanism in LixNiO2

The performances of lithium-ion batteries are set by the electrodes materials capacity to exchange lithium ions and electrons faster and reversibly. To this goal Ni-rich layered metal oxides, especially LiNiO2, are attractive electrode candidate to achieve both high voltage and capacities. Despite its attractiveness, several drawbacks for its industrialization are related to different form of surface and bulk instabilities. These instabilities are due to redox process involving the charge transfer between cations and anions. Therefore, a fundamental understanding based on further experimental evidence is required to resolve of charge transfer between the cation and anion from the surface to the bulk in LiNiO2. Herein, we resolve the role of nickel and oxygen in the charge compensation process in LixNiO2 electrodes from the extreme surface down to 30 nm by energy-dependent core-level HAXPES supported by ab initio simulation. We emphasize the central role of oxygen in the bulk charge compensation mechanism from LiNiO2 to NiO2 due to the negative charge transfer and bond/charge-disproportionation characters of LiNiO2. This bulk behavior is in turn responsible for surface deoxygenation and nickel reduction upon delithiation.

cond-mat.mtrl-sci↗

arXiv2023

Emergent electronic landscapes in a novel valence-ordered nickelate with tri-component nickel coordination

The metal-hydride-based topochemical reduction process has produced novel thermodynamically unstable phases across various transition metal oxide series with unusual crystal structures and non-trivial ground states. Here, by such an oxygen (de-) intercalation method we synthesis a novel samarium nickelate with ordered nickel valences associated with tri-component coordination configurations. This structure, with a formula of Sm$_{9}$Ni$_{9}$O$_{22}$ as revealed by four-dimensional scanning transmission electron microscopy, emerges from the intricate planes of {303}$_{\text{pc}}$ ordered apical oxygen vacancies. X-ray spectroscopy measurements and ab-initio calculations show the coexistence of square-planar, pyramidal and octahedral Ni sites with mono-, bi- and tri-valences. It leads to an intense orbital polarization, charge-ordering, and a ground state with a strong electron localization marked by the disappearance of ligand-hole configuration at low-temperature. This new nickelate compound provides another example of previously inaccessible materials enabled by topotactic transformations and presents a unique platform where mixed Ni valence can give rise to exotic phenomena.

cond-mat.mtrl-sci↗

arXiv2023

Charge distribution across capped and uncapped infinite-layer neodymium nickelate thin films

Charge ordering (CO) phenomena have been widely debated in strongly-correlated electron systems mainly regarding their role in high-temperature superconductivity. Here, we elucidate the structural and charge distribution in NdNiO$_{2}$ thin films prepared with and without capping layers, and characterized by the absence and presence of CO. Our microstructural and spectroscopic analysis was done by scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) and hard x-ray photoemission spectroscopy (HAXPES). Capped samples show Ni$^{1+}$, with an out-of-plane (o-o-p) lattice parameter of around 3.30 angstroms indicating good stabilization of the infinite-layer structure. Bulk-sensitive HAXPES on Ni-2p shows weak satellite feature indicating large charge-transfer energy. The uncapped samples evidence an increase of the o-o-p parameter up to 3.65 angstroms on the thin-film top, and spectroscopies show signatures of higher valence in this region (towards Ni$^{2+}$). Here, 4D-STEM demonstrates (3,0,3) oriented stripes which emerge from partially occupied apical oxygen. Those stripes form quasi-2D coherent domains viewed as rods in the reciprocal space with $\Delta\text{q}_{z} \approx 0.24$ r.l.u. extension located at Q = ($\pm \frac{1}{3},0,\pm \frac{1}{3}$) r.l.u. and Q = ($\pm \frac{2}{3},0,\pm \frac{2}{3}$) r.l.u. The stripes associated with oxygen re-intercalation concomitant with hole doping suggests a possible link to the previously reported CO in infinite-layer nickelate thin films.

cond-mat.mtrl-sci↗

arXiv2022

Tuning the dynamics of chiral domain walls of ferrimagnetic films with the magneto-ionic effect

The manipulation of magnetism with a gate voltage is expected to lead the way towards the realization of energy-efficient spintronics devices and high-performance magnetic memories. Exploiting magneto-ionic effects under micro-patterned electrodes in solid-state devices adds the possibility to modify magnetic properties locally, in a non-volatile and reversible way. Tuning magnetic anisotropy, magnetization and Dzyaloshinskii-Moriya interaction allows modifying at will the dynamics of non trivial magnetic textures such as skyrmions and chiral domain walls in magnetic race tracks. In this work, we illustrate efficient magneto-ionic effects in a ferrimagnetic Pt/Co/Tb stack using a ZrO2 thin layer as a solid state ionic conductor. When a thin layer of terbium is deposited on top of cobalt, it acquires a magnetic moment that aligns antiparallel to that of cobalt, reducing the effective magnetization. Below the micro-patterned electrodes, the voltage-driven migration of oxygen ions in a ZrO2 towards the ferrimagnetic stack partially oxidizes the Tb layer, leading to the local variation not only of the spontaneous magnetization, but also of the effective magnetic anisotropy and of the Dzyaloshinskii-Moriya interaction. This leads to a huge increase of the domain wall velocity, which varies from 10 m/s in the pristine state to 250 m/s after gating. This non-volatile and reversible tuning of the domain wall dynamics may lead to applications to reprogrammable magnetic memories or other spintronic devices.

cond-mat.mtrl-sci↗

arXiv2021

Orbital contributions in the element-resolved valence electronic structure of Bi2Se3

In this work, we studied the bulk band structure of a topological insulator (TI) Bi2Se3 and determined the contributions of the Bi and Se orbital states to the valence bands using standing wave-excited hard x-ray photoemission spectroscopy (SW-HAXPES). This SW technique can provide the element-resolved information and extract individual Bi and Se contributions to the Bi2Se3 valence band. Comparisons with density functional theory (DFT) calculations (LDA and GW) reveal that the Bi 6s, Bi 6p, and Se 4p states are dominant in the Bi2Se3 HAXPES valence band. These findings pave a way for studying the element-resolved band structure and orbital contributions of this class of TIs.

cond-mat.mtrl-sci↗

arXiv2021

Dynamical screening in SrVO$_3$: Inelastic x-ray scattering experiments and ab initio calculations

We characterize experimentally and theoretically the high-energy dielectric screening properties of the prototypical correlated metal SrVO$_3$. The dynamical structure factor measured by inelastic x-ray scattering spectroscopy as a function of momentum transfer is in very good agreement with first-principles calculations in the adiabatic local density approximation to time-dependent density-functional theory. Our results reveal the crucial importance of crystal local fields in the charge response function of correlated materials: They lead to depolarization effects for localised excitations and couple spectra from different Brillouin zones.

cond-mat.str-el↗

arXiv2020

Resonant inelastic x-ray scattering study of doping and temperature dependence of low-energy excitations in La$_{1-x}$Sr$_x$VO$_3$

We present a temperature and doping dependent resonant inelastic X-ray scattering experiment at the V L$_{2,3}$ and O K edges in La$_{1-x}$Sr$_x$VO$_3$ for $x=0$ and $x=0.1$. This material is a canonical example of a compound that exhibits a filling control metal-insulator transition and undergoes orbital ordering and antiferromagnetic transitions at low temperature. Temperature dependent measurements at the V L$_{3}$ edge reveal an intra-t$_{2g}$ excitation that blueshifts by 40 meV from room temperature to 30 K at a rate that differs between the para- and antiferromagnetic phases. The lineshape can be partially explained by a purely local model using crystal field theory calculations. At $x=0.1$ the doping is shown to affect the local electronic structure primarily on the O sites, which is in disagreement with a simple Mott-Hubbard picture. We reveal the presence of phonon overtone features at the O K edge, which evidences that the low energy part of the spectrum is dominated by phonon response.

cond-mat.str-el↗

arXiv2020

Spectroscopies and electron microscopies unravel the origin of the first colour photographs

The first colours photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the 19th century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV-visible spectroscopy and low loss EELS). We rule out the two hypotheses (pigment and interferences) that have prevailed since 1848, respectively based on variations in the oxidation degree of the compound forming the sensitized layer and periodically spaced photolytic silver planes. A study of the silver nanoparticles dispersions contained in the coloured layers showed specific localizations and size distributions of the nanoparticles for each colour. These results allow us to formulate a plasmonic hypothesis on the origin of the photochromatic images colours.

physics.app-ph↗

arXiv2020

Edmond Becquerel's colour photographic process involves a Ag/AgCl-based sensitized layer

Edmond Becquerel invented in 1848 the first colour photographic process. The "photochromatic images" he produced raised several questions, among which the photochromic nature of the sensitized layer. Here, we present the first characterization of the sensitized layer created at the surface of a silver plate or a silver foil according to Becquerel's process, which XIX$^{\text{th}}$ century scientists called "silver photochloride". It is constituted by silver nanoparticles dispersed in a micrometric silver chloride grains matrix. It is thus similar to the widely studied Ag/AgCl composites, which suggests new synthesis routes for these photocatalysts. The chemical composition of the sensitized layer has been identified by complementary spectroscopies (EDX, XPS, HAXPES and EXAFS), while its morphology has been studied by electron microscopies (SEM and STEM). These techniques involve X-ray or electron beams, which can have an impact on the silver chloride-based sensitized layer; a large part of this article hence introduces a study of the beam effects and of the way of reducing them.

physics.app-ph↗

arXiv2019

Two-dimensional electron systems in perovskite oxide heterostructures: Role of the polarity-induced substitutional defects

The discovery of a two-dimensional electron system (2DES) at the interfaces of perovskite oxides such as LaAlO3 and SrTiO3 has motivated enormous efforts in engineering interfacial functionalities with this type of oxide heterostructures. However, its fundamental origins are still not understood, e.g. the microscopic mechanisms of coexisting interface conductivity and magnetism. Here we report a comprehensive spectroscopic investigation of the depth profile of 2DES-relevant Ti 3d interface carriers using depth- and element-specific techniques, standing-wave excited photoemission and resonant inelastic scattering. We found that one type of Ti 3d interface carriers, which give rise to the 2DES are located within 3 unit cells from the n-type interface in the SrTiO3 layer. Unexpectedly, another type of interface carriers, which are polarity-induced Ti-on-Al antisite defects, reside in the first 3 unit cells of the opposing LaAlO3 layer (~10 {\AA}). Our findings provide a microscopic picture of how the localized and mobile Ti 3d interface carriers distribute across the interface and suggest that the 2DES and 2D magnetism at the LaAlO3/SrTiO3 interface have disparate explanations as originating from different types of interface carriers.

cond-mat.mtrl-sci↗

arXiv2019

Epsilon-iron as a spin-smectic state

Using x-ray emission spectroscopy, we find appreciable local magnetic moments until 30-40 GPa in the high-pressure phase of iron, however no magnetic order is detected with neutron powder diffraction down to 1.8 K contrary to previous predictions. Our first-principles calculations reveal a "spin-smectic" state lower in energy than previous results. This state forms antiferromagnetic bilayers separated by null spin bilayers, which allows a complete relaxation of the inherent frustration of antiferromagnetism on a hexagonal close-packed lattice. The magnetic bilayers are likely orientationally disordered, owing to the soft interlayer excitations and the near-degeneracy with other smectic phases. This possible lack of long-range correlation agrees with the null results from neutron powder diffraction. An orientationally-disordered, spin-smectic state resolves previously perceived contradictions in high pressure iron and could be integral to explaining its puzzling superconductivity.

cond-mat.mtrl-sci↗

arXiv2018

Charge-transfer effect in hard x-ray 1$s$ and 2$p$ photoemission spectra: LDA+DMFT and cluster-model analysis

We study $1s$ and $2p$ hard x-ray photoemission spectra (XPS) in a series of late transition metal oxides: Fe$_2$O$_3$ (3$d^{5}$), FeTiO$_3$ (3$d^{6}$), CoO (3$d^{7}$) and NiO (3$d^{8}$). The experimental spectra are analyzed with two theoretical approaches: the MO$_6$ cluster model and the local density approximation (LDA) + dynamical mean-field theory (DMFT). Owing to the absence of the core-valence multiplets and spin-orbit coupling, 1$s$ XPS is found to be a sensitive probe of chemical bonding and nonlocal charge-transfer screening, providing complementary information to 2$p$ XPS. The 1$s$ XPS spectra are used to assess the accuracy of the $ab$-initio LDA+DMFT approach, developed recently to study the material-specific charge-transfer effects in core-level XPS.

cond-mat.mtrl-sci↗

arXiv2018

Interface properties and built-in potential profile of a LaCrO$_3$/SrTiO$_3$ superlattice determined by standing-wave excited photoemission spectroscopy

LaCrO$_3$ (LCO) / SrTiO$_3$ (STO) heterojunctions are intriguing due to a polar discontinuity along (001), two distinct and controllable interface structures [(LaO)$^+$/(TiO$_2$)$^0$ and (SrO)$^0$/(CrO$_2$)$^-$], and interface-induced polarization. In this study, we have used soft- and hard x-ray standing-wave excited photoemission spectroscopy (SW-XPS) to generate a quantitative determination of the elemental depth profiles and interface properties, band alignments, and the depth distribution of the interface-induced built-in potentials in the two constituent oxides. We observe an alternating charged interface configuration: a positively charged (LaO)$^+$/(TiO$_2$)$^0$ intermediate layer at the LCO$_\textbf{top}$/STO$_\textbf{bottom}$ interface and a negatively charged (SrO)$^0$/(CrO$_2$)$^-$ intermediate layer at the STO$_\textbf{top}$/LCO$_\textbf{bottom}$ interface. Using core-level SW data, we have determined the depth distribution of species, including through the interfaces, and these results are in excellent agreement with scanning transmission electron microscopy and electron energy loss spectroscopy (STEM-EELS) mapping of local structure and composition. SW-XPS also enabled deconvolution of the LCO-contributed and STO- contributed matrix-element-weighted density of states (MEWDOSs) from the valence band (VB) spectra for the LCO/STO superlattice (SL). Monitoring the VB edges of the deconvoluted MEWDOS shifts with a change in probing profile, the alternating charge- induced built-in potentials are observed in both constituent oxides. Finally, using a two-step simulation approach involving first core-level binding energy shifts and then valence-band modeling, the built-in potential gradients across the SL are resolved in detail and represented by the depth distribution of VB edges.

cond-mat.mtrl-sci↗

arXiv2018

Electronic Structure of the Dilute Magnetic Semiconductor $Ga_{1-x}Mn_xP$ from Hard X-ray Photoelectron Spectroscopy and Hard X-ray Angle-Resolved Photoemission

We have investigated the electronic structure of the dilute magnetic semiconductor (DMS) $Ga_{0.98}Mn_{0.02}P$ and compared it to that of an undoped $GaP$ reference sample, using hard X-ray photoelectron spectroscopy (HXPS) and hard X-ray angle-resolved photoemission spectroscopy (HARPES) at energies of about 3 keV. We present experimental data, as well as theoretical calculations, in order to understand the role of the Mn dopant in the emergence of ferromagnetism in this material. Both core-level spectra and angle-resolved or angle-integrated valence spectra are discussed. In particular, the HARPES experimental data are compared to free-electron final-state model calculations and to more accurate one-step photoemission theory. The experimental results show differences between $Ga_{0.98}Mn_{0.02}P$ and $GaP$ in both angle-resolved and angle-integrated valence spectra. The $Ga_{0.98}Mn_{0.02}P$ bands are broadened due to the presence of Mn impurities that disturb the long-range translational order of the host $GaP$ crystal. Mn-induced changes of the electronic structure are observed over the entire valence band range, including the presence of a distinct impurity band close to the valence-band maximum of the DMS. These experimental results are in good agreement with the one-step photoemission calculations, and a prior HARPES study of $Ga_{0.97}Mn_{0.03}As$ and $GaAs$ (Gray et al. Nature Materials 11, 957 (2012)), demonstrating the strong similarity between these two materials. The Mn 2p and 3s core-level spectra also reveal an essentially identical state in doping both $GaAs$ and $GaP$.

cond-mat.mtrl-sci↗

arXiv2017

Bulk electronic structure of non-centrosymmetric EuTGe3 (T= Co, Ni, Rh, Ir) studied by hard x-ray photoelectron spectroscopy

Non-centrosymmetric EuTGe3 (T=Co, Ni, Rh, and Ir) possesses magnetic Eu2+ ions and antiferromagnetic ordering appears at low temperatures. Transition metal substitution leads to changes of the unit cell volume and of the magnetic ordering. However, the magnetic ordering temperature does not scale with the volume change and the Eu valence is expected to remain divalent. Here we study the bulk electronic structure of non-centrosymmetric EuTGe3 (T=Co, Ni, Rh, and Ir) by hard x-ray photoelectron spectroscopy. The Eu 3d core level spectrum confirms the robust Eu2+ valence state against the transition metal substitution with a small contribution from Eu3+. The estimated Eu mean-valence is around 2.1 in these compounds as confirmed by multiplet calculations. In contrast, the Ge 2p spectrum shifts to higher binding energy upon changing the transition metal from 3d to 4d to 5d elements, hinting of a change in the Ge-T bonding strength. The valence bands of the different compounds are found to be well reproduced by ab initio band structure calculations.

cond-mat.str-el↗