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The semiconductor ReSe$_2$ is characterized by a strongly anisotropic optical absorption and is therefore promising as an optically active component in two-dimensional heterostructures. However, the underlying femtosecond dynamics of photoinduced excitations in such materials has not been sufficiently explored. Here, we apply an infrared optical excitation to single-layer ReSe$_2$ grown on a bilayer graphene substrate and monitor the temporal evolution of the excited state signal using time- and angle-resolved photoemission spectroscopy. We measure an optical gap of $(1.53 \pm 0.02)$ eV, consistent with resonant excitation of the lowest exciton state. The exciton distribution is tunable via the linear polarization of the pump pulse and exhibits a biexponential decay with time constants given by $\tau_1 = (110 \pm 10)$ fs and $\tau_2 = (650 \pm 70)$ fs, facilitated by recombination via an in-gap state that is pinned at the Fermi level. By extracting the momentum-resolved exciton distribution we estimate its real-space radial extent to be greater than 17.1 \AA, implying significant exciton delocalization due to screening from the bilayer graphene substrate., Comment: 6 pages, 4 figures

The scope of this paper is to outline the main marks and performances of the MagneDyn beamline, which was designed and built to perform ultrafast magnetodynamic studies in solids. Open to users since 2019, MagneDyn operates with variable circular and linear polarized femtosecond pulses delivered by the externally laser-seeded FERMI free-electron laser (FEL). The very high degree of polarization, the high pulse-to-pulse stability, and the photon energy tunability in the 50-300 eV range allow performing advanced time-resolved magnetic dichroic experiments at the K-edge of light elements, e.g., carbon and at the M- and N-edge of the 3d-transition-metals and rare earth elements, respectively. To this end, two experimental end-stations are available. The first is equipped with an in situ dedicated electromagnet, a cryostat, and an extreme ultraviolet Wollaston-like polarimeter. The second, designed for carry-in user instruments, hosts also a spectrometer for pump-probe resonant x-ray emission and inelastic spectroscopy experiments with a sub-eV energy resolution. A Kirkpatrick-Baez active optics system provides a minimum focus of similar to 20x20 mu m(2) FWHM at the sample. A pump laser setup, synchronized with the FEL-laser seeding system, delivers sub-picosecond pulses with photon energies ranging from the mid-IR to near-UV for optical pump-FEL probe experiments with a minimal pump-probe jitter of few femtoseconds. The overall combination of these features renders MagneDyn a unique state-of-the-art tool for studying ultrafast magnetic and resonant emission phenomena in solids. Published under an exclusive license by AIP Publishing.

Dimensionality plays a key role in the emergence of ordered phases, such as charge density-waves (CDW), which can couple to, and modulate, the topological properties of matter. In this work, we study the out-of-equilibrium dynamics of the paradigmatic quasi-one-dimensional material (TaSe

Wide-band-gap insulators such as NiO offer the exciting prospect of coherently manipulating electronic correlations with strong optical fields. Contrary to metals where rapid dephasing of optical excitation

The presence of the term $\left(\case{v}{c}\right)$ that characterizes the electrodynamic retarded potentials, also known as Li\'enard-Wiechert potentials, is thought to be reminiscent of a Doppler effect. Here, we show that these potentials are consistent with the Doppler shifted electromagnetic (e.m.) field generated by a charge moving along a generic trajectory with respect to the laboratory reference frame. Of course, the retarded potentials derived here are formally the same as those reported in the current literature. Nonetheless, this work sheds a new light on the origin of the electrodynamics retarded fields, while offering a direct physical interpretation of the term $\left(\case{v}{c}\right)$ characterizing the related potentials., Comment: 11 pages, 1 figure

Faraday discussions 237, 300 - 316 (2022). doi:10.1039/d2fd00005a, Wide-band-gap insulators such as NiO offer the exciting prospect of coherently manipulating electronic correlations with strong optical fields. Contrary to metals where rapid dephasing of optical excitation via electronic processes occurs, the sub-gap excitation in charge-transfer insulators has been shown to couple to low-energy bosonic excitations. However, it is currently unknown if the bosonic dressing field is composed of phonons or magnons. Here we use the prototypical charge-transfer insulator NiO to demonstrate that 1.5 eV sub-gap optical excitation leads to a renormalised NiO band-gap in combination with a significant reduction of the antiferromagnetic order. We employ element-specific X-ray reflectivity at the FLASH free-electron laser to demonstrate the reduction of the upper band-edge at the O 1s–2p core–valence resonance (K-edge) whereas the antiferromagnetic order is probed via X-ray magnetic linear dichroism (XMLD) at the Ni 2p–3d resonance (L$_2$-edge). Comparing the transient XMLD spectral line shape to ground-state measurements allows us to extract a spin temperature rise of 65 ± 5 K for time delays longer than 400 fs while at earlier times a non-equilibrium spin state is formed. We identify transient mid-gap states being formed during the first 200 fs accompanied by a band-gap reduction lasting at least up to the maximum measured time delay of 2.4 ps. Electronic structure calculations indicate that magnon excitations significantly contribute to the reduction of the NiO band gap., Published by Soc., Cambridge [u.a.]

Understanding how a spin current flows across metal-semiconductor interfaces at pico- and femtosecond time scales is of paramount importance for ultrafast spintronics, data processing, and storage applications. However, the possibility to directly access the propagation of spin currents, within such time scales, has been hampered by the simultaneous lack of both ultrafast element-specific magnetic sensitive probes and tailored well-built and characterized metal-semiconductor interfaces. Here, by means of a novel free-electron laser-based element-sensitive ultrafast time-resolved Kerr spectroscopy, we reveal different magnetodynamics for the Ni M 2 , 3 and Si L 2 , 3 absorption edges. These results are assumed to be the experimental evidence of photoinduced spin currents propagating at a speed of ∼ 0.2 nm/fs across the Ni/Si interface.

In this work, we study the out-of-equilibrium dynamics of the paradigmatic quasi-one-dimensional material (TaSe$_4$)$_2$I, that exhibits a transition into an incommensurate CDW phase when cooled just below room temperature, namely at T$_{\rm{CDW}} $= 263 K. We make use of both optical laser and free-electron laser (FEL) based time-resolved spectroscopies in order to study the effect of a selective excitation on the normal-state and on the CDW phases, by probing the near-infrared/visible optical properties both along and perpendicularly to the direction of the CDW, where the system is metallic and insulating, respectively. Excitation of the core-levels by ultrashort X-ray FEL pulses at 47 eV and 119 eV induces reflectivity transients resembling those recorded when only exciting the valence band of the compound - by near-infrared pulses at 1.55 eV - in the case of the insulating sub-system. Conversely, the metallic sub-system displays a relaxation dynamics which depends on the energy of photo-excitation. Moreover, excitation of the CDW amplitude mode is recorded only for excitation at low-photon-energy. This fact suggests that the coupling of light to ordered states of matter can predominantly be achieved when directly injecting delocalized carriers in the valence band, rather than localized excitations in the core levels. On a complementary side, table-top experiments allow us to prove the quasi-unidirectional nature of the CDW phase in (TaSe$_4$)$_2$I, whose fingerprints are detected along its $c$-axis only. Our results provide new insights on the symmetry of the ordered phase of (TaSe$_4$)$_2$I perturbed by a selective excitation, and suggest a novel approach based on complementary table-top and FEL spectroscopies for the study of complex materials., Comment: 24 pages, 7 figures

The statistical features of the radiation emitted by Free-Electron Lasers (FELs), either by Self-Amplified Spontaneous Emission (SASE-FELs) or by seeded emission (seeded-FELs), are attracting increasing attention because of the use of such light in probing high energy states of matter and their dynamics. While the experimental studies conducted so far have mainly concentrated on correlation functions, here we shift the focus towards reconstructing the distribution of the occupation numbers of the radiation energy states. In order to avoid the various drawbacks related to photon counting techniques when large numbers of photons are involved, we propose a Maximum Likelihood reconstruction of the diagonal elements of the FEL radiation states in the energy eigenbasis based on the statistics of no-click events. The ultimate purpose of such a novel approach to FEL radiation statistics is the experimental confirmation that SASE-FEL radiation exhibits thermal occupation number statistics, while seeded-FEL light Poissonian statistics typical of coherent states and thus of laser light. In this framework, it is interesting to note that the outcome of this work can be extended to any process of harmonic generation from a coherent light pulse, unlocking the gate to the study of the degree to which the original distinctive quantum features deduced from the statistical photon number fluctuations are preserved in non-linear optical processes., Comment: 8 + 10 pages, 5 figures

Here, we report on the conceptual design, the hardware realization, and the first experimental results of a novel and compact x-ray polarimeter capable of a single-pulse linear polarization angle detection in the extreme ultraviolet photon energy range. The polarimeter is tested by performing time resolved pump-probe experiments on a Ni80Fe20 Permalloy film at the M-2,M-3 Ni edge at an externally seeded free-electron laser source. Comparison with similar experiments reported in the literature shows the advantages of our approach also in view of future experiments.

FeSe x Te 1 − x compounds display a rich phase diagram, ranging from the nematicity of FeSe to the ( π , π ) magnetism of FeTe. We focus on FeSe0.4Te0.6, and exploit tr-ARPES to study its ultrafast electron dynamics following photoexcitation by near-infrared pump pulses. By exploiting probe-polarization-dependent matrix element effects, we reveal a photoinduced long-lived state, lasting for a few tens of picoseconds, showing features compatible with a nematic state. The possibility to induce a long-lived state in this compound by using ultra-short pulses might shed a new light on the driving force behind the nematic symmetry breaking in iron-based superconductors. With the aid of a phenomenological model, we illustrate how our results possibly question the common belief that a low-energy coupling with fluctuations is a necessary condition to stabilize the nematic order. On the contrary, the tendency towards orbital differentiation due to strong electronic correlations induced by the Hund’s coupling could be at the origin of the nematic order in iron-based superconductors.

Time-resolved optical spectroscopy (TR-OS) has emerged as a fundamental spectroscopic tool for probing complex materials, to both investigate ground-state-related properties and trigger phase transitions among different states with peculiar electronic and lattice structures. We describe a versatile approach to perform polarization-resolved TR-OS measurements, by combining broadband detection with the capability to simultaneously probe two orthogonal polarization states. This method allows us to probe, with femtoseconds resolution, the frequency-resolved reflectivity or transmittivity variations along two mutually orthogonal directions, matching the principal axis of the crystal structure of the material under scrutiny. We report on the results obtained by acquiring the polarization-dependent transient reflectivity of two polytypes of the MoTe2 compound, with 2H and 1T’ crystal structures. We reveal marked anisotropies in the time-resolved reflectivity signal of 1T’-MoTe2, which are connected to the crystal structure of the compound. Polarization- and time- resolved spectroscopic measurements can thus provide information about the nature and dynamics of both the electronic and crystal lattice subsystems, advancing the comprehension of their inter-dependence, in particular in the case of photoinduced phase transitions; in addition, they provide a broadband measurement of transient polarization rotations.

The quest for mapping the femtosecond dynamics of the electronic band structure of complex materials over their full first Brillouin zone is pushing the development of schemes to efficiently generate ultrashort photon pulses in the VUV energy range. At present, the critical aspect in time- and angle-resolved photoelectron spectroscopy (TR-ARPES) is to combine a high photon energy with high photoemission count rates and a narrow pulse-bandwidth, necessary to achieve high energy resolution, while preserving a good time resolution and mitigating space-charge effects. Here we describe a novel approach to produce light pulses at 10.8 eV, combining high repetition rate operation (1–4 MHz), high energy resolution ( ∼ 26 meV) and space-charge free operation, with a time-resolution of ∼ 700 fs. These results have been achieved by generating the ninth harmonic of a Yb fiber laser, through a phase-matched process of third harmonic generation in Xenon of the laser third harmonic. The full up-conversion process is driven by a seed pulse energy as low as 10 μ J, hence is easily scalable to multi-MHz operation. This source opens the way to TR-ARPES experiments for the investigation of the electron dynamics over the full first Brillouin zone of most complex materials, with unprecedented energy and momentum resolutions and high count rates. The performances of the setup are tested by TR-ARPES on the topological insulator Bi 2 Se 3 .

Here we demonstrate that the 0-dimensional confinement of Ge2Sb2Te5 results in a drastic reduction of the minimum critical fluence required for optical-induced amorphization when compared to the thin-film cases. We show that by using single-shot laser pulses, the investigated nanoparticles display a crystalline-to-amorphous transition, satisfying a mandatory requirement of a bit-memory element. These unprecedented results open a viable route to boost energy efficient phase-change processes.

Spectroscopy in the femtosecond time domain can both reveal fundamental insight in the properties of materials and provide relevant experimental tests for functional systems. [...]

Unveiling the physics that governs the intertwining between the nanoscale self-organization and the dynamics of insulator-to-metal transitions (IMTs) is key for controlling on demand the ultrafast switching in strongly correlated materials and nanodevices. A paradigmatic case is the IMT in ${\mathrm{V}}_{2}{\mathrm{O}}_{3}$, for which the mechanism that leads to the nucleation and growth of metallic nanodroplets out of the supposedly homogeneous Mott insulating phase is still a mystery. Here, we combine x-ray photoemission electron microscopy and ultrafast nonequilibrium optical spectroscopy to investigate the early-stage dynamics of isolated metallic nanodroplets across the IMT in ${\mathrm{V}}_{2}{\mathrm{O}}_{3}$ thin films. Our experiments show that the low-temperature monoclinic antiferromagnetic insulating phase is characterized by the spontaneous formation of striped polydomains, with different lattice distortions. The insulating domain boundaries accommodate the birth of metallic nanodroplets, whose nonequilibrium expansion can be triggered by the photoinduced change of the $3d$-orbital occupation. We address the relation between the spontaneous nanotexture of the Mott insulating phase in ${\mathrm{V}}_{2}{\mathrm{O}}_{3}$ and the timescale of the metallic seeds growth. We speculate that the photoinduced metallic growth can proceed along a nonthermal pathway in which the monoclinic lattice symmetry of the insulating phase is partially retained.

Author(s): Malvestuto, M; Caretta, A; Casarin, B; Ciprian, R; Dell'Angela, M; Laterza, S; Chuang, YD; Wurth, W; Revcolevschi, A; Wray, LA; Parmigiani, F | Abstract: Using high resolution resonant inelastic x-ray scattering measurements, we have observed that the orbital excitations of the quasi-1D spin chain compound CuGeO3 has nontrivial and noticeable orbital mixing effects from 3d valence spin-orbit coupling. In particular, the SOC leads to a significant correction of dz2 state, which has a direct interplay with the low energy physics of cuprates. Guided by atomic multiplet based modeling, our results strongly support a 3d spin-orbit mixing scenario and explore in detail the nature of these excitations.

Here we show how time-resolved broadband optical spectroscopy can be used to quantify, with femtometer resolution, the oscillation amplitudes of coherent phonons through a displacive model without free tuning parameters, except an overall scaling factor determined by comparison between experimental data and density functional theory calculations. $WTe_2$ is used to benchmark this approach. In this semimetal, the response is anisotropic and provides the spectral fingerprints of two $A_1$ optical phonons at $\sim$8 and $\sim$80 $cm^-$$^1$. In principle, this methodology can be extended to any material in which an ultrafast excitation triggers coherent lattice modes modulating the high-energy optical properties., Comment: Main Text 5 pages 4 figures, Supplemental Material 20 pages 18 figures

In the last two decades, non-equilibrium spectroscopies have evolved from avant-garde studies to crucial tools for expanding our understanding of the physics of strongly correlated materials. The possibility of obtaining simultaneously spectroscopic and temporal information has led to insights that are complementary to (and in several cases beyond) those attainable by studying the matter at equilibrium. Multiple phase transitions and new orders arising from competing interactions are benchmark examples where the interplay among electrons, lattice, and spin dynamics can be disentangled because of the different timescales that characterize the recovery of the initial ground state. The nature of the broken-symmetry phases and of the bosonic excitations that mediate the electronic interactions, eventually leading to superconductivity or other exotic states, can be revealed by observing the sub-picosecond dynamics of impulsively excited states. Recent experimental developments have made possible to monitor the time-evolution of both the single-particle and collective excitations under extreme conditions, such as those arising from strong and selective photo-stimulation. Here, we review the most recent achievements in the experimental and theoretical studies of the non-equilibrium electronic, optical, structural and magnetic properties of correlated materials. The focus will be mainly on the prototypical case of correlated oxides that exhibit unconventional superconductivity or other exotic phases, even though the discussion will extend also to other topical systems. The necessity of extending the actual experimental capabilities and the numerical and analytic tools to microscopically treat the non-equilibrium phenomena beyond the simple phenomenological approaches represents one of the most challenging new frontier in physics., Review, to appear in Advances in physics. 188 pages, 637 references, 77 figures

The future Magneto Dynamics (MagneDyn) beamline will be devoted to study the electronic states and the local magnetic properties of excited and transient states of complex systems by means of the time-resolved X-ray absorption spectroscopy technique. The beamline will use FERMI's high-energy source covering the wavelength range from 60 nm down to 1.3 nm. An on-line photon energy spectrometer will allow spectra to be measured with high resolution while delivering most of the beam to the end-stations. Downstream the beam will be possibly split and delayed, by means of a delay line, and then focused with a set of active Kirkpatrick–Baez mirrors. These mirrors will be able to focus the radiation in one of the two MagneDyn experimental chambers: the electromagnet end-station and the resonant inelastic X-ray scattering end-station. After an introduction of the MagneDyn scientific case, the layout will be discussed showing the expected performances of the beamline.

Here, we report on a novel narrowband High Harmonic Generation (HHG) light source designed for ultrafast photoelectron spectroscopy (PES) on solids. Notably, at 16.9 eV photon energy, the harmonics bandwidth equals 19 meV. This result has been obtained by seeding the HHG process with 230 fs pulses at 515 nm. The ultimate energy resolution achieved on a polycrystalline Au sample at 40 K is ∼22 meV at 16.9 eV. These parameters set a new benchmark for narrowband HHG sources and have been obtained by varying the repetition rate up to 200 kHz and, consequently, mitigating the space charge, operating with ≈ 3 × 10 7 electrons/s and ≈ 5 × 10 8 photons/s. By comparing the harmonics bandwidth and the ultimate energy resolution with a pulse duration of ∼105 fs (as retrieved from time-resolved experiments on bismuth selenide), we demonstrate a new route for ultrafast space-charge-free PES experiments on solids close to transform-limit conditions.Here, we report on a novel narrowband High Harmonic Generation (HHG) light source designed for ultrafast photoelectron spectroscopy (PES) on solids. Notably, at 16.9 eV photon energy, the harmonics bandwidth equals 19 meV. This result has been obtained by seeding the HHG process with 230 fs pulses at 515 nm. The ultimate energy resolution achieved on a polycrystalline Au sample at 40 K is ∼22 meV at 16.9 eV. These parameters set a new benchmark for narrowband HHG sources and have been obtained by varying the repetition rate up to 200 kHz and, consequently, mitigating the space charge, operating with ≈ 3 × 10 7 electrons/s and ≈ 5 × 10 8 photons/s. By comparing the harmonics bandwidth and the ultimate energy resolution with a pulse duration of ∼105 fs (as retrieved from time-resolved experiments on bismuth selenide), we demonstrate a new route for ultrafast space-charge-free PES experiments on solids close to transform-limit conditions.

Staphylococcus epidermidis (S. epidermidis) is one of the leading nosocomial pathogens, particularly associated with periprosthetic infections of biomedical implants. Silicon nitride (Si3N4), a nonoxide biomaterial widely used in spinal implants, has shown bacteriostatic effects against both gram-positive and gram-negative bacteria; however, the physicochemical interactions between Si3N4 and bacteria yet remain conspicuously unexplored. In situ time-lapse Raman spectroscopic experiments were conducted by exposing S. epidermidis for 12, 24, and 48 h to Si3N4 substrates to understand the evolution of bacterial metabolism and to elucidate the ceramics antimicrobial behavior. The Raman probe captured an initial metabolic response of the bacteria to the adverse chemistry of the Si3N4 surface, which included peroxidation of membrane phospholipids and protein structural modifications to adjust for survivorship. However, beyond 24 h of exposure, the Raman signals representing DNA, lipids, proteins, and carbohydrates showed clear fingerprints of bacterial lysis. Bands related to biofilm formation completely disappeared or underwent drastically reduced intensity. Bacterial lysis was confirmed by conventional fluorescence microscopy methods. Spectroscopic experiments suggested that a pH change at the Si3N4’s surface induced variations in the membrane structure and D-alanylation of teichoic acids in its peptidoglycan layer. Concurrent stimulation of peptidoglycan hydrolase (i.e., an enzyme involved with autolysis) ultimately led to membrane degradation and cellular death. An additional finding was that modulating the Si3N4 surface by increasing the population of amine groups improved the efficiency of the substrate against S. epidermidis, thus suggesting that optimization of the near-surface (alkaline) conditions may be a viable approach to bacterial reduction.

A novel ultrafast photoemission technique unveils the Mottness of antinodal quasiparticles in superconducting copper oxides., Many puzzling properties of high–critical temperature (Tc) superconducting (HTSC) copper oxides have deep roots in the nature of the antinodal quasiparticles, the elementary excitations with wave vector parallel to the Cu–O bonds. These electronic states are most affected by the onset of antiferromagnetic correlations and charge instabilities, and they host the maximum of the anisotropic superconducting gap and pseudogap. We use time-resolved extreme-ultraviolet photoemission with proper photon energy (18 eV) and time resolution (50 fs) to disclose the ultrafast dynamics of the antinodal states in a prototypical HTSC cuprate. After photoinducing a nonthermal charge redistribution within the Cu and O orbitals, we reveal a dramatic momentum-space differentiation of the transient electron dynamics. Whereas the nodal quasiparticle distribution is heated up as in a conventional metal, new quasiparticle states transiently emerge at the antinodes, similarly to what is expected for a photoexcited Mott insulator, where the frozen charges can be released by an impulsive excitation. This transient antinodal metallicity is mapped into the dynamics of the O-2p bands, thus directly demonstrating the intertwining between the low- and high-energy scales that is typical of correlated materials. Our results suggest that the correlation-driven freezing of the electrons moving along the Cu–O bonds, analogous to the Mott localization mechanism, constitutes the starting point for any model of high-Tc superconductivity and other exotic phases of HTSC cuprates.

The study of ultrafast magnetodynamics has entered a new era thanks to the groundbreaking technological advances in free-electron laser (FEL) light sources. The advent of these light sources has made possible unprecedented experimental schemes for time-resolved x-ray magneto-optic spectroscopies, which are now paving the road for exploring the ultimate limits of out-of-equilibrium magnetic phenomena. In particular, these studies will provide insights into elementary mechanisms governing spin and orbital dynamics, therefore contributing to the development of ultrafast devices for relevant magnetic technologies. This topical review focuses on recent advancement in the study of non-equilibrium magnetic phenomena from the perspective of time-resolved extreme ultra violet (EUV) and soft x-ray spectroscopies at FELs with highlights of some important experimental results.

Here we report a giant, completely reversible magneto-electric coupling of 100 nm polycrystalline Co layer in contact with ZnO nanorods. When the sample is under an applied bias of ±2 V, the Co magnetic coercivity is reduced by a factor 5 from the un-poled case, with additionally a reduction of total magnetic moment in Co. Taking into account the chemical properties of ZnO nanorods measured by X-rays absorption near edge spectroscopy under bias, we conclude that these macroscopic effects on the magnetic response of the Co layer are due to the microstructure and the strong strain-driven magneto-electric coupling induced by the ZnO nanorods, whose nanostructuration maximizes the piezoelectric response under bias.

Here we report on experiments performed by linear-dichroism angle resolved photoelectron spectroscopy (LD-ARPES) on septuple layers (SL) topological insulator GeBi2Te4. The linear dichroic signals, both for the valence band states and in the topologically protected surface state are interpreted as a probe of the symmetry of the states. The observation of a change in the LD-ARPES spectrum at the top of VB is attributed to the band parity inversion which is predicted by theory for all materials entering the topologically protected phase. Finally, the opening of a gap in the surface state dispersion along the non-high symmetry direction is reported. This is proposed to originated from the interaction between the surface state and the VB, leading to the formation of surface resonances.

We have performed optical microscopy, micro-photoelectron spectroscopy, and micro-Raman scattering measurements on Y$_{0.63}$Ca$_{0.37}$TiO$_3$ single crystals in order to clarify the interplay between the microstructure and the temperature dependent electronic transport mechanisms in this material. Optical microscopy observations reveal dark and bright domain patterns on the surface with length scales of the order of several to a hundred micrometers showing a pronounced temperature dependent evolution. Spatially resolved photoelectron spectroscopy measurements show the different electronic character of these domains. Using micro-Raman spectroscopy, we observe a distinct temperature dependence of the crystal structure of these domains. On the basis of these findings the different domains are assigned to insulating and metallic volume fractions, respectively. By decreasing the temperature, the volume fraction of the conducting domains increases, hence allowing the electrons to percolate through the sample at temperatures lower than $\sim$150 K., Comment: 6 pages, 4 figures

The design and characterization of a HHG source conceived for Time and Angle Resolved PhotoElectron Spectroscopy (TR-ARPES) experiments are presented. The harmonics are selected through a grating monochromator with an innovative design able to provide XUV radiation for two distinct TR-ARPES setups. © OSA 2018.

Femtosecond laser excitations in half-metal (HM) compounds are theoretically predicted to induce an exotic picosecond spin dynamics. In particular, conversely to what is observed in conventional metals and semiconductors, the thermalization process in HMs leads to a long living partially thermalized configuration characterized by three Fermi-Dirac distributions for the minority, majority conduction, and majority valence electrons, respectively. Remarkably, these distributions have the same temperature but different chemical potentials. This unusual thermodynamic state is causing a persistent nonequilibrium spin polarization only well above the Fermi energy. Femtosecond spin dynamics experiments performed on Fe3O4 by time- and spin-resolved photoelectron spectroscopy support our model. Furthermore, the spin polarization response proves to be very robust and it can be adopted to selectively test the bulk HM character in a wide range of compounds. Funding Agencies|UK EPSRC Grant [GR/M50447]; STFC; FERMI FEL project; Austrian Science Fund (FWF) through Lise Meitner Grant [M1925-N28]; Nanyang Technological University, NAP-SUG; CEDAMNF [CZ 02.1.01/0.0/0.0/15_003/0000358]; ERDF

Multiorbital correlated materials are often on the verge of multiple electronic phases (metallic, insulating, superconducting, charge and orbitally ordered), which can be explored and controlled by small changes of the external parameters. The use of ultrashort light pulses as a mean to transiently modify the band population is leading to fundamentally new results. In this paper we will review recent advances in the field and we will discuss the possibility of manipulating the orbital polarization in correlated multi-band solid state systems. This technique can provide new understanding of the ground state properties of many interesting classes of quantum materials and offers a new tool to induce transient emergent properties with no counterpart at equilibrium. We will address: the discovery of high-energy Mottness in superconducting copper oxides and its impact on our understanding of the cuprate phase diagram; the instability of the Mott insulating phase in photoexcited vanadium oxides; the manipulation of orbital-selective correlations in iron-based superconductors; the pumping of local electronic excitons and the consequent transient effective quasiparticle cooling in alkali-doped fullerides. Finally, we will discuss a novel route to manipulate the orbital polarization in a a k-resolved fashion. © 2018 COPYRIGHT SPIE. Downloading of the abstract is permitted for personal use only.

Nowadays cutting edge femtosecond EUV and soft X-rays radiation sources are the driving force of groundbreaking time resolved X-ray spectroscopies. These new light sources are allowing pioneering experiments in the field of ultrafast phenomena and disclosing new insights about the physics of the out-of-equilibrium matter. Here we report an introductory and concise outlook about some possible perspectives in this field. (C) 2015 Elsevier B.V. All rights reserved.

The photoisomerization of the all-trans protonated Schiff base of retinal (SBR+) in solution is highly inefficient. The present theoretical and experimental investigation aims at disclosing the mechanisms of ultrafast, non-reactive relaxation of SBR+ that lead to the drastic decrease in the isomerization yield in non- polar solvents. Our pump–probe measurements demonstrate the sensitivity of the all-trans SBR+ excited-state dynamics on the electrostatic interaction with the surrounding counterions and the crucial importance of the chromophore microenvironment. Our computational study focuses for the first time on the retinal chromophore–counterion pairs that are formed in non-polar solvents. By employing TDDFT-based nonadiabatic dynamics simulations and ADC(2) reaction paths calculations we found that internal conversion from the initially excited state to an inter- molecular charge transfer state with excitation localized on the counterion, leads to dissociation of the chromophore–counterion pair and to the abortion of isomerization. Barriers to conical intersection with the inter-molecular charge transfer state were found in the range 0.42–0.67 eV at the ADC(2) level. The existence of a barrier along the non-reactive relaxation pathways explains the observation that in solution the excitation on the blue edge of the SBR+ absorption leads to decrease in the isomerization yield with respect to the excitation at the red edge.

The interaction between phonons and high-energy excitations of electronic origin in cuprates and their role in the superconducting mechanisms is still controversial. Here we use coherent vibrational time-domain spectroscopy together with density functional and dynamical mean-field theory calculations to establish a direct link between the c-axis phonon modes and the in-plane electronic charge excitations in optimally doped YBCO. The non-equilibrium Raman tensor is measured by means of the broadband 'coherent-phonon' response in pump-probe experiments and is qualitatively described by our model using DFT in frozen phonon approximation plus single band DMFT to account for the electronic correlations. The major outcome of our experimental and theoretical study is to establish the link between out-of-plane copper ions displacements and the in-plane electronic correlations, and to estimate at few unit cells the correlation length of the associated phonon mode. The approach introduced here could help revealing the complex interplay between fluctuations of different nature and spatial correlation in several strongly-correlated materials.

The prediction of Weyl fermions in the low-temperature noncentrosymmetric $1{T}^{\ensuremath{'}}$ phase of ${\mathrm{MoTe}}_{2}$ still awaits clear experimental confirmation. Here, we report angle-resolved photoemission (ARPES) data and ab initio calculations that reveal a surface state arc dispersing between the valence and the conduction band, as expected for a Weyl semimetal. However, we find that the arc survives in the high-temperature centrosymmetric $1{T}^{\ensuremath{'}\ensuremath{'}}$ phase. Therefore, a surface Fermi arc is not an unambiguous fingerprint of a topologically nontrivial phase. We have also investigated the surface state spin texture of the $1{T}^{\ensuremath{'}}$ phase by spin-resolved ARPES, and identified additional topologically trivial spin-split states within the projected band gap at higher binding energies.

Physical review / B 96(24), 241408 (2017). doi:10.1103/PhysRevB.96.241408, $MoTe_2$ has recently been shown to realize in its low-temperature phase the type-II Weyl semimetal (WSM). We investigated by time- and angle- resolved photoelectron spectroscopy (tr-ARPES) the possible influence of the Weyl points on the electron dynamics above the Fermi level $E_F$, by comparing the ultrafast response of $MoTe_2$in the trivial and topological phases. In the low-temperature WSM phase, we report an enhanced relaxation rate of electrons optically excited to the conduction band, which we interpret as a fingerprint of the local gap closure when Weyl points form. By contrast, we find that the electron dynamics of the related compound $WTe_2$is slower and temperature independent, consistent with a topologically trivial nature of this material. Our results shows that tr-ARPES is sensitive to the small modifications of the unoccupied band structure accompanying the structural and topological phase transition of $MoTe_2$., Published by Inst., Woodbury, NY

The electronic structure of ZrTe5 has been matter of renewed interest aimed at clarifying, along with its topological character, the temperature dependence of the unusual transport properties of this material. Here, we report an extensive high resolution Angle Resolved Photoelectron Spectroscopy (ARPES) study unveiling a non-monotonic shift of the bands, when the sample temperature is varied between 16 K and 300 K. Moreover, the present conventional ARPES and circularly dichroic ARPES measurements reveal the presence of two states at the top of the valence band. The strong ARPES dichroic signal detected in proximity of the Fermi energy has been interpreted as the indication of the presence of spin polarized states, in agreement with the predicted strong topological character of this material. published

Physical review / B 96(18), 184420 (2017). doi:10.1103/PhysRevB.96.184420, We report a high-resolution resonant inelastic extreme ultraviolet (EUV) scattering study of the quantum Heisenberg antiferromagnet KCoF$_3$. By tuning the EUV photon energy to the cobalt M$_{23}$ edge, a complete set of low-energy 3d spin-orbital excitations is revealed. These low-lying electronic excitations are modeled using an extended multiplet-based mean-field calculation to identify the roles of lattice and magnetic degrees of freedom in modifying the resonant inelastic x-ray scattering (RIXS) spectral line shape. We have demonstrated that the temperature dependence of RIXS features upon the antiferromagnetic ordering transition enables us to probe the energetics of short-range spin correlations in this material., Published by APS, Woodbury, NY

Currently, there is a flurry of research interest on materials with an unconventional electronic structure, and we have already seen significant progress in their understanding and engineering towards real-life applications. The interest erupted with the discovery of graphene and topological insulators in the previous decade. The electrons in graphene simulate massless Dirac Fermions with a linearly dispersing Dirac cone in their band structure, while in topological insulators, the electronic bands wind non-trivially in momentum space giving rise to gapless surface states and bulk bandgap. Weyl semimetals in condensed matter systems are the latest addition to this growing family of topological materials. Weyl Fermions are known in the context of high energy physics since almost the beginning of quantum mechanics. They apparently violate charge conservation rules, displaying the ‘chiral anomaly’, with such remarkable properties recently theoretically predicted and experimentally verified to exist as low energy quasiparticle states in certain condensed matter systems. Not only are these new materials extremely important for our fundamental understanding of quantum phenomena, but also they exhibit completely different transport phenomena. For example, massless Fermions are susceptible to scattering from non-magnetic impurities. Dirac semimetals exhibit non-saturating extremely large magnetoresistance as a consequence of their robust electronic bands being protected by time reversal symmetry. These open up whole new possibilities for materials engineering and applications including quantum computing. In this review, we recapitulate some of the outstanding properties of WTe2, namely, its non-saturating titanic magnetoresistance due to perfect electron and hole carrier balance up to a very high magnetic field observed for the very first time. It also indicative of hosting Lorentz violating type-II Weyl Fermions in its bandstructure, again first predicted candidate material to host such a remarkable phase. We primarily focus on the findings of our ARPES, spin-ARPES, and time-resolved ARPES studies complemented by first-principles calculations.

Electronic band structures of two novel semiconducting nitrides of the group-IV elements of Th3P4-type crystal structure, c-M3N4, where M[DOUBLE BOND]Zr or Hf, is investigated using an element specific soft X-ray spectroscopy for the first time. From the pairs of N 1s X-ray absorption and N 2p [RIGHTWARDS ARROW] 1s resonant X-ray emission spectra partial densities of states (PDOS) of nitrogen, predicted to be strongly hybridized with those of the metals, are obtained for both compounds. From these data the electronic band gaps of oxygen bearing c-Zr3N4 and of c-Hf3N4, predicted before to be direct or nearly direct, are derived to be Eg = 1.6 eV and Eg = 1.8 eV, respectively. While the experimentally determined Eg for c-Hf3N4 agrees with the theoretical one obtained using the local density approximation (LDA) method, the Eg measured for oxygen bearing c-Zr3N4 is significantly higher than those calculated using both the LDA and the generalized gradient approximation method. The examined compounds, having high hardness, elastic moduli and oxidation resistance, appear to be multifunctional materials suitable also for applications as (opto)electronic materials. Band gap evolution in c-M3N4 nitrides as a function of the cation type, Zr or Hf.

Scientific reports 6, 38796 (2016). doi:10.1038/srep38796, In the past few years, we have been witnessing an increased interest for studying materials properties under non-equilibrium conditions. Several well established spectroscopies for experiments in the energy domain have been successfully adapted to the time domain with sub-picosecond time resolution. Here we show the realization of high resolution resonant inelastic X-ray scattering (RIXS) with a stable ultrashort X-ray source such as an externally seeded free electron laser (FEL). We have designed and constructed a RIXS experimental endstation that allowed us to successfully measure the d-d excitations in KCoF3 single crystals at the cobalt M$_{2,3}$-edge at FERMI FEL (Elettra-Sincrotrone Trieste, Italy). The FEL-RIXS spectra show an excellent agreement with the ones obtained from the same samples at the MERIXS endstation of the MERLIN beamline at the Advanced Light Source storage ring (Berkeley, USA). We established experimental protocols for performing time resolved RIXS experiments at a FEL source to avoid X ray-induced sample damage, while retaining comparable acquisition time to the synchrotron based measurements. Finally, we measured and modelled the influence of the FEL mixed electromagnetic modes, also present in externally seeded FELs, and the beam transport with ~120 meV experimental resolution achieved in the presented RIXS setup., Published by Nature Publishing Group, London

A long-standing question for avant-garde data storage technology concerns the nature of the ultrafast photoinduced phase transformations in the wide class of chalcogenide phase-change materials (PCMs). Overall, a comprehensive understanding of the microstructural evolution and the relevant kinetics mechanisms accompanying the out-of-equilibrium phases is still missing. Here, after overheating a phase-change chalcogenide superlattice by an ultrafast laser pulse, we indirectly track the lattice relaxation by time resolved x-ray absorption spectroscopy (tr-XAS) with a sub-ns time resolution. The approach to the tr-XAS experimental results reported in this work provides an atomistic insight of the mechanism that takes place during the cooling process; meanwhile a first-principles model mimicking the microscopic distortions accounts for a straightforward representation of the observed dynamics. Finally, we envisage that our approach can be applied in future studies addressing the role of dynamical structural strain in PCMs.

We study the photoinduced insulator-metal transition in V O2, correlating its threshold and dynamics with excitation wavelength. In single crystals, switching can only be induced with photon energies above the 670 meV gap. This contrasts with the case of polycrystalline films, where formation of the metallic state can be initiated also with photon energies as low as 180 meV, which are well below the bandgap. Perfection of this process may become conducive to schemes for optical switches, limiters, and detectors operating at room temperature in the mid-infrared. © 2008 American Institute of Physics.

The extraordinary electronic and optical properties of the crystal-to-amorphous transition in phase-change materials have led to important developments in memory applications. A promising outlook is offered by nanoscaling such phase-change structures. Following this research line, we study the interband optical transmission spectra of nanoscaled $\text{GeTe}/{\mathrm{Sb}}_{2}{\mathrm{Te}}_{3}$ chalcogenide superlattice films. We determine, for films with varying stacking sequence and growth methods, the density and scattering time of the free carriers, and the characteristics of the valence-to-conduction transition. It is found that the free carrier density decreases with increasing GeTe content, for sublayer thicknesses below $\ensuremath{\sim}3$ nm. A simple band model analysis suggests that GeTe and ${\mathrm{Sb}}_{2}{\mathrm{Te}}_{3}$ layers mix, forming a standard GeSbTe alloy buffer layer. We show that it is possible to control the electronic transport properties of the films by properly choosing the deposition layer thickness, and we derive a model for arbitrary film stacks.

The non-equilibrium approach to correlated electron systems is often based on the paradigm that different degrees of freedom interact on different timescales. In this context, photo-excitation is treated as an impulsive injection of electronic energy that is transferred to other degrees of freedom only at later times. Here, by studying the ultrafast dynamics of quasi-particles in an archetypal strongly correlated charge-transfer insulator (La2CuO4+delta), we show that the interaction between electrons and bosons manifests itself directly in the photo-excitation processes of a correlated material. With the aid of a general theoretical framework (Hubbard-Holstein Hamiltonian), we reveal that sub-gap excitation pilots the formation of itinerant quasi-particles, which are suddenly dressed by an ultrafast reaction of the bosonic field.

By tuning the laser photon energy in the non-linear two-photons photoemission at a single-layer graphene/Cu(111) interface, it is possible to observe a strong resonance at h upsilon = 3.5 eV along with a weaker one at h upsilon = 3.85 eV. The main resonance photon energy is consistent with a direct optical transition between the occupied Cu(111) Shockley surface state and the n = 1 image potential state, located in the real gap-space between the single-layer graphene and the Cu( Ill) surface. The large amplitude of this resonance unveils a high value of the electric dipole matrix element integral that governs this transition. Furthermore, the Lorentzian shape of this resonance implies that these two states are decoupled from the continuum of states and the lifetime of the image potential state can be estimated. (C) 2015 Elsevier B.V. All rights reserved.

The complex electronic properties of ${\mathrm{ZrTe}}_{5}$ have recently stimulated in-depth investigations that assigned this material to either a topological insulator or a 3D Dirac semimetal phase. Here we report a comprehensive experimental and theoretical study of both electronic and structural properties of ${\mathrm{ZrTe}}_{5}$, revealing that the bulk material is a strong topological insulator (STI). By means of angle-resolved photoelectron spectroscopy, we identify at the top of the valence band both a surface and a bulk state. The dispersion of these bands is well captured by ab initio calculations for the STI case, for the specific interlayer distance measured in our x-ray diffraction study. Furthermore, these findings are supported by scanning tunneling spectroscopy revealing the metallic character of the sample surface, thus confirming the strong topological nature of ${\mathrm{ZrTe}}_{5}$.

Solid Si under intense femtosecond irradiation is investigated over a wide range of fluences below the melting transition by supercontinuum light (400--800 nm) transient reflectivity. By solving a system of time-dependent equations, the fast and slow components of the energy and carriers diffusion can be disentangled from the reflectivity data, providing considerable insight into the nonequilibrium phase-change dynamics. The study of the fluence values immediately preceding the dramatic melting transition can be useful for discriminating between the thermal and electronic origins of the disordering of the structure by looking at the modification of the solid-state properties of the Si surface.

We present equilibrium and out-of-equilibrium studies of the Verwey transition in magnetite. In the equilibrium optical conductivity, we find a steplike change at the phase transition for photon energies below about 2 eV. The possibility of triggering a nonequilibrium transient metallic state in insulating magnetite by photo excitation was recently demonstrated by an x-ray study. Here we report a full characterization of the optical properties in the visible frequency range across the nonequilibrium phase transition. Our analysis of the spectral features is based on a detailed description of the equilibrium properties. The out-of-equilibrium optical data bear the initial electronic response associated to localized photoexcitation, the occurrence of phase separation, and the transition to a transient metallic phase for excitation density larger than a critical value. This allows us to identify the electronic nature of the transient state, to unveil the phase transition dynamics, and to study the consequences of phase separation on the reflectivity, suggesting a spectroscopic feature that may be generally linked to out-of-equilibrium phase separation.