arXiv subjects

Laura Simonelli

Publications and source records attributed to Laura Simonelli.

8 recordsLinked to original sources

arXiv2025

Unveiling Zn incorporation in CuInS$_2$ quantum dots: X-ray and optical analysis of doping effects, structural modifications and surface passivation

Quantum dots (QDs) exhibit unique properties arising from their reduced size and quantum confinement effects, including exceptionally bright and tunable photoluminescence. Among these, CuInS$_{2}$ QDs have gained significant attention owing to their remarkable broadband emission, making them highly desirable for various optoelectronic applications requiring efficient luminescent nanomaterials. However, maximizing radiative recombination in CuInS$_{2}$ QDs often necessitates minimizing intragap trap states. A common approach involves the introduction of Zn during the synthesis, which typically promotes the formation of a ZnS shell that passivates the QD surface. Despite its importance, the characterization and quantification of Zn incorporation using conventional techniques, such as optical spectroscopy or electron microscopy, remains challenging. In this study, we utilized X-ray absorption spectroscopy (XAS), in both X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectral ranges, to investigate Zn incorporation into CuInS$_{2}$ QDs with element-specific precision. This approach allowed us to detect the formation of a ZnS surface shell and to resolve the spatial distribution of Zn atoms within the QD lattice, distinguishing between Zn as a substituent, or as an interstitial defect. Additionally, we explored the optical and dynamical properties of CuInS$_{2}$ QDs using time-resolved optical spectroscopies, particularly in the presence of electron and hole acceptors. These results provide deeper insights into the role and effectiveness of the Zn-induced passivating layer, paving the way for optimizing QD performance in photoluminescence applications.

cond-mat.mtrl-sci↗

arXiv2024

Local structure and phonon states mediated by intercalation-driven doping in superconducting $Li_{1.0}(C_5H_5N)_yFe_{2-z}Se_2$

Intercalation of two-dimensional (2D) iron chalcogenides with molecular species requires disentangling electronic and structural contributions to understand the puzzling limit to superconducting transition temperature ($T_c$) at the frontier of long interlayer separations. Here, synchrotron X-ray absorption spectroscopy (XAS) at the Se K-edge sheds light on the impact of carrier-doping on the local structure of the high-$T_c$ (~39 K) $Li_{1.0}(C_5H_5N)_yFe_{2-z}Se_2$ phase. This material is derived by annealing the structurally related as-made derivative ($T_c$~ 44 K), with layers being primed apart by [alkali-molecule] guests. Metrics, such as, a reduced filling of Se $4p$ orbitals and shorter Fe-Se bonds in the annealed phase, corroborate to a lower electron doping level with respect to the as-made one. Analysis of the metal-ligand thermal motion, based on the correlated Debye model, further relates the higher $T_c$ intercalates with the softening of the local Fe-Se bond. Beyond electronic effects, intercalation brings forth host-guest interactions that mediate the dynamics of the bulk crystal structure. For this, neutron time-of-flight spectroscopy on the annealed derivative, corroborates to the Se-Fe-Se layer being sensitive to chemical pressure effects imposed by the confined organic guests. This reflects in the phonon density of states, where harder low-energy transverse acoustic matrix phonons and molecular vibrations are witnessed, with respect to the pristine inorganic ($\beta$-FeSe) and organic ($C_5D_5N$) counterparts. On cooling through $T_c$, these excitations arrive without a collective magnetic-resonance mode - essential in unconventional, spin-mediated mechanisms - enquiring about deviations from optimal doping. The work highlights that when the Fe-square planes are tuned far apart, carrier-doping leveraged by intercalation plays a key role in the $T_c$ parametrization.

cond-mat.supr-con↗

arXiv2023

$\rm Li_x(C_5H_5N)_yFe_{2-z}Se_2$: a defect resilient expanded-lattice high-temperature superconductor

Two-dimensional iron-chalcogenide intercalates display a remarkable correlation of the interlayer spacing with the enhancement of the superconducting critical temperature ($T_c$). In this work, synchrotron x-ray absorption ($XAS$, at Fe and Se K edges) and emission ($XES$) spectroscopies, allow to discuss how the important rise of $T_c$ (44 K) in the molecule intercalated $\rm Li_x(C_5H_5N)_yFe_{2-z}Se_2$ relates to the electronic and local structure changes felt by the inorganic host upon doping ($x$). $XES$ shows that widely-separated layers of edge-sharing $\rm FeSe_4$ tetrahedra, carry low-spin moieties with a local Fe magnetic moment slightly reduced compared to the parent $\beta$-$\rm Fe_{2-z}Se_2$. Pre-edge $XAS$ advises on the progressively reduced mixing of metal $3d-4p$ states upon lithiation. Doping-mediated local lattice modifications, probed by conventional $T_c$-optimization measures (cf. anion height and $FeSe_4$ tetrahedra regularity), become less relevant when layers are spaced far away. On the basis of extended x-ray absorption fine structure, such distortions are compensated by a softer Fe-network that relates to Fe-site vacancies, alleviating electron-lattice correlations and superconductivity. Density functional theory ($DFT$) guided modification of isolated $\rm Fe_{2-z}Se_2$ ($z$, vacant sites) planes, resembling the host layers, identify that Fe-site deficiency occurs at low energy cost, giving rise to stretched Fe-sheets, in accord with experiments. The robust high-$T_c$ in $\rm Li_x(C_5H_5N)_yFe_{2-z}Se_2$, arises from the interplay of electron donating spacers and the iron-selenide layers tolerance to defect chemistry, a tool to favorably tune its Fermi surface properties.

cond-mat.supr-con↗

arXiv2022

Li iontronics in single-crystalline T-Nb2O5 thin films with vertical ionic transport channels

The niobium oxide polymorph T-Nb2O5 has been extensively investigated in its bulk form especially for applications in fast-charging batteries and electrochemical (pseudo)capacitors. Its crystal structure that has two-dimensional (2D) layers with very low steric hindrance allows for fast Li-ion migration. However, since its discovery in 1941, the growth of single-crystalline thin films and its electronic applications have not yet been realized, likely due to its large orthorhombic unit cell along with the existence of many polymorphs. Here we demonstrate the epitaxial growth of single-crystalline T-Nb2O5 thin films, critically with the ionic transport channels oriented perpendicular to the film's surface. These vertical 2D channels enable fast Li-ion migration which we show gives rise to a colossal insulator-metal transition where the resistivity drops by eleven orders of magnitude due to the population of the initially empty Nb 4d0 states by electrons. Moreover, we reveal multiple unexplored phase transitions with distinct crystal and electronic structures over a wide range of Li-ion concentrations by comprehensive in situ experiments and theoretical calculations, that allow for the reversible and repeatable manipulation of these phases and their distinct electronic properties. This work paves the way to the exploration of novel thin films with ionic channels and their potential applications.

cond-mat.mtrl-sci↗

arXiv2018

U 5$f$ crystal-field ground state of UO$_2$ probed by directional dichroism in nonresonant inelastic x-ray scattering

Nonresonant inelastic x-ray scattering (NIXS) has been performed on single crystals of UO$_2$ to study the direction dependence of higher-order-multipole scattering from the uranium $O_{4,5}$ edges (90--110 eV). By comparing the experimental results with theoretical calculations the symmetry of the ground state is confirmed directly as the crystal-field (CF) $\Gamma_5$ triplet state within the $J$ = 4 manifold. The results also demonstrate that the directional dichroism of the NIXS spectra is sensitive to the CF strength and establish NIXS as a tool for probing CF interactions quantitatively.

cond-mat.str-el↗

arXiv2013

Temperature dependence of crystal field excitations in CuO

We report a study on the temperature dependence of the charge-neutral crystal field (dd) excitations in cupric oxide, using nonresonant inelastic x-ray scattering (IXS) spectroscopy. Thanks to a very high energy resolution (60 meV), we observe thermal effects on the dd excitation spectrum fine structure between temperatures of 10-320 K. With an increasing temperature, the spectra broaden considerably. We assign the temperature dependence of the dd excitations to the relatively large electron-phonon coupling.

cond-mat.str-el↗

arXiv2013

Temperature dependent local atomic displacements in Ru substituted SmFe_{1-x}Ru_{x}AsO_{0.85}F_{0.15} superconductors

Local structure of SmFe$_{1-x}$Ru$_x$AsO$_{0.85}$F$_{0.15}$ ($x$ = 0.0, 0.05, 0.25 and 0.5) superconductors has been investigated by temperature dependent As $K$-edge extended x-ray absorption fine structure. The effect of Ru substitution remains confined to the iron-arsenide layer but neither the static disorder nor the Fe-As bond strength suffers any change for $x \le$ 0.25. With further Ru substitution the static disorder increases while the Fe-As bond strength remains unchanged. Also, the Ru-As distance ($\sim$2.42 \AA), different from the Fe-As distance ($\sim$2.39 \AA), does not show any change in its force constant with the Ru substitution. These observations suggest that the SmFe$_{1-x}$Ru$_x$AsO$_{0.85}$F$_{0.15}$ system breaks down to coexisting local electronic phases on isoelectric substitution in the active FeAs layer.

cond-mat.supr-con↗

arXiv2012

Large local disorder in the superconducting K_{0.8}Fe_{1.6}Se_{2} studied by extended x-ray absorption fine structure

We have measured local structure of superconducting K_{0.8}Fe_{1.6}Se_{2} chalcogenide (T_{c}=31.8 K) by temperature dependent polarized extended x-ray absorption fine structure (EXAFS) at the Fe and Se K-edges. We find that the system is characterized by a large local disorder. The Fe-Se and Fe-Fe distances are found to be shorter than the distances measured by diffraction, while the corresponding mean square relative displacements reveal large Fe-site disorder and relatively large c-axis disorder. The local force constant for Fe-Se bondlength (k ~ 5.8 eV/\AA^{2}) is similar to the one found in the binary FeSe superconductor, however, the Fe-Fe bondlength appears to get flexible (k ~ 2.1 eV/\AA^{2}) in comparison to the binary FeSe (k ~ 3.5 eV/\AA^{2}), an indication of partly relaxed Fe-Fe networks in K_{0.8}Fe_{1.6}Se_{2}. The results suggest glassy nature of the title system, with the superconductivity being similar to the one in the granular materials.

cond-mat.supr-con↗