arXiv subjects

Francesco Offi

Publications and source records attributed to Francesco Offi.

9 recordsLinked to original sources

arXiv2026

A depth resolved investigation of hydrogen uptake in carbon based nanostructures by soft-to-hard photoemission spectroscopy

Hydrogen chemisorption on graphitic carbon modifies the carbon orbital hybridization from sp2 to sp3, altering both structural and electronic properties. Understanding not only the lateral extent but also the depth distribution of hydrogen uptake in three-dimensional carbon architectures is essential for both fundamental studies and storage applications. To this end, we investigate here the evolution of the C 1s core-level lineshape in nanoporous graphene (NPG) and vertically aligned carbon nanotubes (CNTs) upon hydrogenation, exploiting soft-to-hard X-ray photoemission spectroscopy to achieve a depth-resolved analysis. Decomposition of the C 1s spectra reveals the formation of an sp3 rich overlayer, indicating hydrogen chemisorption limited to the outermost accessible surfaces in both systems. These results clarify the depth distribution of hydrogen in curved and porous graphitic networks and provide quantitative constraints on its chemisorption for carbon-based hydrogen storage applications.

cond-mat.mtrl-sci↗

arXiv2026

Graphene lattice recoil in hard X-ray photoemission: Experiment and Theory

Hard-x-ray C 1s photoemission from monolayer graphene probes a regime in which nuclear recoil and intrinsic electronic asymmetry contribute on comparable energy scales to the observed spectral line shape. Here we combine experiment and modeling over the photon-energy range 0.8 keV--8 keV to resolve this interplay quantitatively. A graphene-specific implementation of the Fujikawa--Takata cumulant formalism, based on an anisotropic vibrational density of states constrained by first-principles phonon calculations, captures the expected recoil scaling with photon energy and emission geometry but fails to reproduce the pronounced asymmetric tails of the measured spectra. To overcome this limitation, we introduce an explicit electronic convolution model in which an intrinsic, photon-energy-independent electronic line shape extracted from near-recoilless 0.8 keV data is convolved with a phonon recoil kernel carrying the full dependence on photon energy and emission angle. This approach reproduces both the measured line-shape evolution and the observed centroid shifts across the explored energy range without refitting the spectra at higher photon energies. The results show that recoil in graphene cannot be described by a baseline treatment in which the phonon recoil kernel is combined only with symmetric lifetime broadening, but must be treated together with the intrinsic many-body electronic response of the C 1s line.

cond-mat.mtrl-sci↗

arXiv2023

Disclosing the nature of asymmetric interface magnetism in Co/Pt multilayers

Nowadays a wide number of applications based on magnetic materials relies on the properties arising at the interface between different layers in complex heterostructures engineered at the nanoscale. In ferromagnetic/heavy metal multilayers, such as the [Co/Pt]$_N$ and [Co/Pd]$_N$ systems, the magnetic proximity effect was demonstrated to be asymmetric, thus inducing a magnetic moment on the Pt(Pd) layer that is typically higher at the top Co/Pt(Pd) interface. In this work, advanced spectroscopic and imaging techniques were combined with theoretical approaches to clarify the origin of this asymmetry both in Co/Pt trilayers and, for the first time, in multilayer systems that are more relevant for practical applications. The different magnetic moment induced at the Co/Pt interfaces was correlated to the microstructural features, which are in turn affected by the growth processes that induce a different intermixing during the film deposition, thus influencing the interface magnetic profile.

cond-mat.mtrl-sci↗

arXiv2023

Revealing the bonding nature and electronic structure of early transition metal dihydrides

Hydrogen as a fuel plays a crucial role in driving the transition to net zero greenhouse gas emissions. To realise its potential, obtaining a means of efficient storage is paramount. One solution is using metal hydrides, owing to their good thermodynamical absorption properties and effective hydrogen storage. Although metal hydrides appear simple compared to many other energy materials, understanding the electronic structure and chemical environment of hydrogen within them remains a key challenge. This work presents a new analytical pathway to explore these aspects in technologically relevant systems using Hard X-ray Photoelectron Spectroscopy (HAXPES) on thin films of two prototypical metal dihydrides: YH$_{2-\delta}$ and TiH$_{2-\delta}$. By taking advantage of the tunability of synchrotron radiation, a non-destructive depth profile of the chemical states is obtained using core level spectra. Combining experimental valence band spectra collected at varying photon energies with theoretical insights from density functional theory (DFT) calculations, a description of the bonding nature and the role of d versus sp contributions to states near the Fermi energy are provided. Moreover, a reliable determination of the enthalpy of formation is proposed by using experimental values of the energy position of metal s band features close to the Fermi energy in the HAXPES valence band spectra.

cond-mat.mtrl-sci↗

arXiv2020

Photoemission from the gas phase using soft x-ray fs pulses: An investigation of the space-charge effects

An experimental and computational investigation of the space-charge effects occurring in ultrafast photoelectron spectroscopy from the gas phase is presented. The target sample CF$_3$I is excited by ultrashort (100 fs) far-ultraviolet radiation pulses produced by a free-electron laser. The modification of the energy distribution of the photoelectrons, i.e. the shift and broadening of the spectral structures, is monitored as a function of the pulse intensity. The experimental results are compared with computational simulations which employ a Barnes-Hut algorithm to calculate the effect of individual Coulomb forces acting among the particles. In the presented model, a survey spectrum acquired at low radiation fluence is used to determine the initial energy distribution of the electrons after the photoemission event. The spectrum modified by the space-charge effects is then reproduced by $N$-body calculations that simulate the dynamics of the photoelectrons subject to the individual mutual Coulomb repulsion and to the attractive force of the positive ions. The employed numerical method accounts for the space-charge effects on the energy distribution and allows to reproduce the complete photoelectron spectrum and not just a specific photoemission structure. The simulations also provide information on the time evolution of the space-charge effects on the picosecond scale. Differences with the case of photoemission from solid samples are highlighted and discussed. The presented simulation procedure, although it omits the analysis of angular distribution, constitutes an effective simplified model that allows to predict and account for space-charge effects on the photoelectron energy spectrum in time-resolved photoemission experiments with high-intensity pulsed sources.

physics.ins-det↗

arXiv2020

Electron correlation effects in the exchange coupling at the Fe/CoO/Ag(001) ferro-/antiferro-magnetic interface

Angle resolved-Auger-photoelectron coincidence spectroscopy (AR-APECS) has been exploited to investigate the role that electron correlation plays in the exchange-coupling at the ferromagnetic/antiferromagnetic interface of a Fe/CoO bilayer growth on Ag(001). The effective correlation energy U$_{\textrm{eff}}$, usually employed to assess the energy distribution of core-valence-valence Auger spectra, has been experimentally determined for each possible combination of the orbital (e$_g$ or t$_{2g}$) and the spin (majority or minority) of the two valence electrons involved in the Auger decay. Coulomb and exchange interactions have been identified and compared with the result obtained on the Fe/Ag system. The presented analysis reveals in the Fe/CoO interface an enhancement of the Coulomb interaction for the e$_g$ orbital and of the exchange interaction for the t$_{2g}$ orbital with respect to the Fe/Ag case that can be associated to the stronger electron confinement and to the exchange coupling between the two layers, respectively.

cond-mat.str-el↗

arXiv2016

Space-charge effects in high-energy photoemission

Pump-and-probe photoelectron spectroscopy (PES) with femtosecond pulsed sources opens new perspectives in the investigation of the ultrafast dynamics of physical and chemical processes at the surfaces and interfaces of solids. Nevertheless, for very intense photon pulses a large number of photoelectrons are simultaneously emitted and their mutual Coulomb repulsion is sufficiently strong to significantly modify their trajectory and kinetic energy. This phenomenon, referred as space-charge effect, determines a broadening and shift in energy for the typical PES structures and a dramatic loss of energy resolution. In this article we examine the effects of space charge in PES with a particular focus on time-resolved hard X-ray (~10 keV) experiments. The trajectory of the electrons photoemitted from pure Cu in a hard X-ray PES experiment has been reproduced through $N$-body simulations and the broadening of the photoemission core-level peaks has been monitored as a function of various parameters (photons per pulse, linear dimension of the photon spot, photon energy). The energy broadening results directly proportional to the number $N$ of electrons emitted per pulse (mainly represented by secondary electrons) and inversely proportional to the linear dimension $a$ of the photon spot on the sample surface, in agreement with the literature data about ultraviolet and soft X-ray experiments. The evolution in time of the energy broadening during the flight of the photoelectrons is also studied. Despite its detrimental consequences on the energy spectra, we found that space charge has negligible effects on the momentum distribution of photoelectrons and a momentum broadening is not expected to affect angle-resolved experiments. Strategy to reduce the energy broadening and the feasibility of hard X-ray PES experiments at the new free-electron laser facilities are discussed.

cond-mat.mtrl-sci↗

arXiv2014

Observation of Distinct Bulk and Surface Chemical Environments in a Topological Insulator under Magnetic doping

The influence of magnetic dopants on the electronic and chemical environments in topological insulators (TIs) is a key factor when considering possible spintronic applications based on topological surface state properties. Here we provide spectroscopic evidence for the presence of distinct chemical and electronic behavior for surface and bulk magnetic doping of Bi2Te3. The inclusion of Mn in the bulk of Bi2Te3 induces a genuine dilute ferromagnetic state, with reduction of the bulk band gap as the Mn content is increased. Deposition of Fe on the Bi2Te3 surface, on the other hand, favors the formation of iron telluride already at coverages as low as 0.07 monolayer, as a consequence of the reactivity of the Te-rich surface. Our results identify the factors that need to be controlled in the realization of magnetic nanosystems and interfaces based on TIs.

cond-mat.mtrl-sci↗

arXiv2011

Insight on Hole-Hole Interaction and Magnetic Order from Dichroic Auger-Photoelectron Coincidence Spectra

The absence of sharp structures in the core-valence-valence Auger line shapes of partially filled bands has severely limited the use of electron spectroscopy in magnetic crystals and other correlated materials. Here by a novel interplay of experimental and theoretical techniques we achieve a combined understanding of the Photoelectron, Auger %$M_{23}M_{45}M_{45}$ and Auger-Photoelectron Coincidence Spectra (APECS) of CoO. This is a prototype antiferromagnetic material in which the recently discovered Dichroic Effect in Angle Resolved (DEAR) APECS reveals a complex pattern in the strongly correlated Auger line shape. A calculation of the \textit{unrelaxed} spectral features explains the pattern in detail, labeling the final states by the total spin. The present theoretical analysis shows that the dichroic effect arises from a spin-dependence of the angular distribution of the photoelectron-Auger electron pair detected in coincidence, and from the selective power of the dichroic technique in assigning different weights to the various spin components. Since the spin-dependence of the angular distribution exists in the antiferromagnetic state but vanishes at the Néel temperature, the DEAR-APECS technique detects the phase transition from its local effects, thus providing a unique tool to observe and understand magnetic correlations in such circumstances, where the usual methods (neutron diffraction, specific heat measurements) are not applicable.

cond-mat.str-el↗