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Singlet fission may boost photovoltaic efficiency [by transforming a singlet exciton into two triplet excitons and thereby doubling the number of excited charge carriers. The primary step of singlet fission is the ultrafast creation of the correlated triplet pair. While several mechanisms have been proposed to explain this step, none has emerged as a consensus. The challenge lies in tracking the transient excitonic states. Here we use time- and angle-resolved photoemission spectroscopy to observe the primary step of singlet fission in crystalline pentacene. Our results suggest a charge-transfer mediated mechanism with a hybridization of Frenkel and charge-transfer states in the lowest bright singlet exciton. We gained intimate knowledge about the localization and the orbital character of the exciton wave functions recorded in momentum maps. This allowed us to directly compare the localization of singlet and bitriplet excitons and decompose energetically overlapping states based on their orbital character. Orbital- and localization- resolved many-body dynamics promise deep insights into the mechanics governing molecular systems and topological materials., 24 pages, 4 main figures, 9 supplementary figures

Two-dimensional quantum spin Hall (QSH) insulators are a promising material class for spintronic applications based on topologically-protected spin currents in their edges. Yet, they have not lived up to their technological potential, as experimental realizations are scarce and limited to cryogenic temperatures. These constraints have also severely restricted characterization of their dynamical properties. Here, we report on the electron dynamics of the novel room-temperature QSH candidate bismuthene after photoexcitation using time- and angle-resolved photoemission spectroscopy. We map the transiently occupied conduction band and track the full relaxation pathway of hot photocarriers. Intriguingly, we observe photocarrier lifetimes much shorter than in \red{conventional} semiconductors. This is ascribed to the presence of topological in-gap states already established by local probes. Indeed, we find spectral signatures consistent with these earlier findings. Demonstration of the large band gap and the view into photoelectron dynamics mark a critical step toward optical control of QSH functionalities., Comment: 13 pages, 11 figures

Characterization of the electronic band structure of solid state materials is routinely performed using photoemission spectroscopy. Recent advancements in short-wavelength light sources and electron detectors give rise to multidimensional photoemission spectroscopy, allowing parallel measurements of the electron spectral function simultaneously in energy, two momentum components and additional physical parameters with single-event detection capability. Efficient processing of the photoelectron event streams at a rate of up to tens of megabytes per second will enable rapid band mapping for materials characterization. We describe an open-source workflow that allows user interaction with billion-count single-electron events in photoemission band mapping experiments, compatible with beamlines at 3rd and 4rd generation light sources and table-top laser-based setups. The workflow offers an end-to-end recipe from distributed operations on single-event data to structured formats for downstream scientific tasks and storage to materials science database integration. Both the workflow and processed data can be archived for reuse, providing the infrastructure for documenting the provenance and lineage of photoemission data for future high-throughput experiments. Deutsche Forschungsgemeinschaft (German Research Foundation) https://doi.org/10.13039/501100001659 Villum Fonden (Villum Foundation) https://doi.org/10.13039/100008398 EC | EU Framework Programme for Research and Innovation H2020 | H2020 Priority Excellent Science | H2020 European Research Council (H2020 Excellent Science - European Research Council) https://doi.org/10.13039/100010663 Max-Planck-Gesellschaft (Max Planck Society) https://doi.org/10.13039/501100004189

For solid-state materials, the electronic structure, E(k), is critical in determining a crystal's physical properties. By experimentally detecting the electronic structure, the fundamental physics can be revealed. Angle-resolved photoemission spectroscopy (ARPES) is a powerful technique for directly observing the electronic structure with energy- and momentum-resolved information. Over the past decades, major improvements in the energy and momentum resolution, alongside the extension of ARPES observables to spin (SpinARPES), micrometer or nanometer lateral dimensions (MicroARPES/NanoARPES), and femtosecond timescales (TrARPES), have led to major scientific advances. These advantages have been achieved across a wide range of quantum materials, such as high-temperature superconductors, topological materials, two-dimensional materials and heterostructures. This primer introduces key aspects of ARPES principles, instrumentation, data analysis, and representative scientific cases to demonstrate the power of the method. Perspectives and challenges on future developments are also discussed., Comment: Invited Review article for Nature Reviews Methods Primers

International audience; Crystallization is a fundamental natural phenomenon and the ubiquitous physical process in materials science for the design of new materials. So far, experimental observations of the structural dynamics in crystallization have been mostly restricted to slow dynamics. We present here an exclusive way to explore the dynamics of crystallization in highly controlled conditions (i.e., in the absence of impurities acting as seeds of the crystallites) as it occurs in vacuum. We have measured the early formation stage of solid Xe nanoparticles nucleated in an expanding supercooled Xe jet by means of an X-ray diffraction experiment with 10-fs X-ray free-electron laser (XFEL) pulses. We found that the structure of Xe nanoparticles is not pure face-centered cubic (fcc), the expected stable phase, but a mixture of fcc and randomly stacked hexagonal close-packed (rhcp) structures. Furthermore, we identified the instantaneous coexistence of the comparably sized fcc and rhcp domains in single Xe nanoparticles. The observations are explained by the scenario of structural aging, in which the nanoparticles initially crystallize in the highly stacking-disordered rhcp phase and the structure later forms the stable fcc phase. The results are reminiscent of analogous observations in hard-sphere systems, indicating the universal role of the stacking-disordered phase in nucleation.

Hybridization of electronic states and orbital symmetry in transition metal oxides are generally considered key ingredients in the description of both their electronic and magnetic properties. In the prototypical case of ${\mathrm{La}}_{0.65}{\mathrm{Sr}}_{0.35}{\mathrm{MnO}}_{3}$ (LSMO), a landmark system for spintronics applications, a description based solely on Mn $3d$ and O $2p$ electronic states is reductive. We thus analyzed elemental and orbital distributions in the LSMO valence band through a comparison between density functional theory calculations and experimental photoelectron spectra in a photon energy range from soft to hard x rays. We reveal a number of hidden contributions, arising specifically from La $5p$, Mn $4s$, and O $2s$ orbitals, considered negligible in previous analyses; our results demonstrate that all these contributions are significant for a correct description of the valence band of LSMO and of transition metal oxides in general.

The momentum-dependent orbital character in crystalline solids, referred to as orbital texture, is of capital importance in the emergence of symmetry-broken collective phases, such as charge density waves as well as superconducting and topological states of matter. By performing extreme ultraviolet multidimensional angle-resolved photoemission spectroscopy for two different crystal orientations linked to each other by mirror symmetry, we isolate and identify the role of orbital texture in photoemission from the transition metal dichalcogenide 1T-TiTe2. By comparing our experimental results with theoretical calculations based on both a quantitative one-step model of photoemission and an intuitive tight-binding model, we unambiguously demonstrate the link between the momentum-dependent orbital orientation and the emergence of strong intrinsic linear dichroism in the photoelectron angular distributions. Our results represent an important step towards going beyond band structure (eigenvalues) mapping and learning about electronic wavefunction and orbital texture of solids by exploiting matrix element effects in photoemission spectroscopy.

We performed angle-resolved photoemission spectroscopy (ARPES) of bulk2H-WSe$_2$ for different crystal orientations linked to each other bytime-reversal symmetry. We introduce a new observable called time-reversaldichroism, which quantifies the modulation of the photoemission intensity uponeffective time-reversal operation. We demonstrate that the hiddenorbital-texture of the crystal's electronic structure leaves its imprint ontothe time-reversal dichroism, due to multiple orbitals interference effects inphotoemission. Our experimental results are in quantitative agreement withstate-of-the-art fully relativistic calculations performed using the one-stepmodel of photoemission. While spin-resolved ARPES probes the spin component ofentangled spin-orbital texture in multiorbital systems, we demonstrate thattime-reversal dichroism is sensitive to its orbital-texture counterpart.

Two-dimensional (2D) metallic states induced by oxygen vacancies (${V}_{O}\mathrm{s}$) at oxide surfaces and interfaces provide opportunities for the development of advanced applications, but the ability to control the behavior of these states is still limited. We used angle resolved photoelectron spectroscopy combined with density-functional theory (DFT) to study the reactivity of ${V}_{O}$-induced states at the (001) surface of anatase ${\mathrm{TiO}}_{2}$, where both 2D metallic and deeper lying in-gap states (IGs) are observed. The 2D and IG states exhibit remarkably different evolutions when the surface is exposed to molecular ${\mathrm{O}}_{2}$: while IGs are almost completely quenched, the metallic states are only weakly affected. DFT calculations indeed show that the IGs originate from surface ${V}_{O}\mathrm{s}$ and remain localized at the surface, where they can promptly react with ${\mathrm{O}}_{2}$. In contrast, the metallic states originate from subsurface vacancies whose migration to the surface for recombination with ${\mathrm{O}}_{2}$ is kinetically hindered on anatase ${\mathrm{TiO}}_{2}$ (001), thus making them much less sensitive to oxygen dosing.

Characterizing and controlling the uniformity of nanoparticles is crucial for their application in science and technology because crystalline defects in the nanoparticles strongly affect their unique properties. Recently, ultra-short and ultra-bright X-ray pulses provided by X-ray free-electron lasers (XFELs) opened up the possibility of structure determination of nanometre-scale matter with Å spatial resolution. However, it is often difficult to reconstruct the 3D structural information from single-shot X-ray diffraction patterns owing to the random orientation of the particles. This report proposes an analysis approach for characterizing defects in nanoparticles using wide-angle X-ray scattering (WAXS) data from free-flying single nanoparticles. The analysis method is based on the concept of correlated X-ray scattering, in which correlations of scattered X-ray are used to recover detailed structural information. WAXS experiments of xenon nanoparticles, or clusters, were conducted at an XFEL facility in Japan by using the SPring-8 Ångstrom compact free-electron laser (SACLA). Bragg spots in the recorded single-shot X-ray diffraction patterns showed clear angular correlations, which offered significant structural information on the nanoparticles. The experimental angular correlations were reproduced by numerical simulation in which kinematical theory of diffraction was combined with geometric calculations. We also explain the diffuse scattering intensity as being due to the stacking faults in the xenon clusters., IUCrJ, 7 (2), ISSN:2052-2525

Excitons, Coulomb-bound electron-hole pairs, are the fundamental excitations governing the optoelectronic properties of semiconductors. While optical signatures of excitons have been studied extensively, experimental access to the excitonic wave function itself has been elusive. Using multidimensional photoemission spectroscopy, we present a momentum-, energy- and time-resolved perspective on excitons in the layered semiconductor WSe2. By tuning the excitation wavelength, we determine the energy-momentum signature of bright exciton formation and its difference from conventional single-particle excited states. The multidimensional data allows to retrieve fundamental exciton properties like the binding energy and the exciton-lattice coupling and to reconstruct the real-space excitonic distribution function via Fourier transform. All quantities are in excellent agreement with microscopic calculations. Our approach provides a full characterization of the exciton properties and is applicable to bright and dark excitons in semiconducting materials, heterostructures and devices. The data we uploaded here is the four-dimensional trARPES data used in this paper., This work was funded by the Max Planck Society, the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation and the H2020-EU.1.2.1. FET Open programs (Grant Nos. ERC-2015-CoG-682843, ERC-2015-AdG-694097, and OPTOlogic 899794), the Max Planck Society's Research Network BiGmax on Big-Data-Driven Materials-Science, and the German Research Foundation (DFG) within the Emmy Noether program (Grant No. RE 3977/1), through SFB 951 "Hybrid Inorganic/Organic Systems for Opto-Electronics (HIOS)" (Project No. 182087777, projects B12 and B17), the SFB/TRR 227 "Ultrafast Spin Dynamics" (projects A09 and B07), the Research Unit FOR 1700 "Atomic Wires" (project E5), and the Priority Program SPP 2244 (project 443366970). D.C.thanks the graduate school Advanced Materials (SFB 951) for support. S.B. acknowledges financial support from the NSERC-Banting Postdoctoral Fellowships Program. T.P. acknowledges financial support from the Alexander von Humboldt Foundation.

Time-resolved soft-X-ray photoemission spectroscopy is used to simultaneously measure the ultrafast dynamics of core-level spectral functions and excited states upon excitation of excitons in WSe$_2$. We present a many-body approximation for the Green's function, which excellently describes the transient core-hole spectral function. The relative dynamics of excited-state signal and core levels reveals a delayed core-hole renormalization due to screening by excited quasi-free carriers, revealing an excitonic Mott transition. These findings establish time-resolved core-level photoelectron spectroscopy as a sensitive probe of subtle electronic many-body interactions and an ultrafast electronic phase transition., 6 pages, 4 figures

Hard X-ray photoelectron spectroscopy (HAXPES), aided by the progress of synchrotron radiation (SR) beamlines as well as the development of state-of-the-art electron analyzers, has established a fi...

The knowledge of the picosecond dynamics of the energy level alignment between donor and acceptor materials in organic photovoltaic devices under working conditions is a challenge for fundamental material research. We measured by means of time-resolved Resonant X-ray Photoemission Spectroscopy (RPES) the energy level alignment in ZnPc/C 60 films. We employed 800 nm femtosecond laser pulses to pump the system simulating sunlight excitation and X-rays from the synchrotron as a probe. We measured changes in the valence bands due to pump induced modifications of the interface dipole. Our measurements prove the feasibility of time-resolved RPES with high repetition rate sources.

Theory and experiment are combined to gain an understanding of the electronic properties of OsO2, a poorly studied metallic oxide that crystallizes in the rutile structure. Hard and soft valence-band x-ray photoemission spectra of OsO2 single crystals are in broad agreement with the results of density-functional-theory calculations, aside from a feature shifted to high binding energy of the conduction band. The energy shift corresponds to the conduction electron plasmon energy measured by reflection electron energy loss spectroscopy. The plasmon satellite is reproduced by many-body perturbation theory.

Time-of-flight-based momentum microscopy has a growing presence in photoemission studies, as it enables parallel energy- and momentum-resolved acquisition of the full photoelectron distribution. Here, we report table-top extreme ultraviolet (XUV) time- and angle-resolved photoemission spectroscopy (trARPES) featuring both a hemispherical analyzer and a momentum microscope within the same setup. We present a systematic comparison of the two detection schemes and quantify experimentally relevant parameters, including pump- and probe-induced space-charge effects, detection efficiency, photoelectron count rates, and depth of focus. We highlight the advantages and limitations of both instruments based on exemplary trARPES measurements of bulk WSe2. Our analysis demonstrates the complementary nature of the two spectrometers for time-resolved ARPES experiments. Their combination in a single experimental apparatus allows us to address a broad range of scientific questions with trARPES., Comment: 19 pages, 9 figures. The following article has been submitted to Review of Scientific Instruments / AIP Publishing. After it is published, it will be found at https://aip.scitation.org/journal/rsi

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.

Synopsis We performed a wide-angle X-ray scattering experiment of single Xe nanoparticles using an X-ray free electron laser. We developed a novel analysis method that focuses on the angular correlation between plural Bragg spots in single-shot diffraction patterns. The angular correlations of the Bragg spots encode rich structural information and offer an evidence of twinning and stacking faults in Xe nanoparticles.

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.

The potential of the two-color mode implemented at the FERMI free-electron laser (FEL) source for pumping and probing selectively different atomic species has been demonstrated by time-resolved scattering experiments with permalloy (FeNi alloy) and NiFe 2 O 4 samples. We monitored the ultra-fast demagnetization of Ni induced by the pump FEL pulse, by tuning the linearly-polarized FEL probe pulse to the Ni-3p resonance and measuring the scattered intensity in the transverse magneto-optical Kerr effect geometry. The measurements were performed by varying the intensity of the FEL pump pulse, tuning its wavelength to and off of the Fe-3p resonance, and by spanning the FEL probe pulse delays across the 300–900 fs range. The obtained results have Photonics 2017, 4, 6 2 of 10 evidenced that for the case of NiFe 2 O 4 , there is a sensible difference in the magnetic response at the Ni site when the pump pulse causes electronic excitations at the Fe site.

In this work the experimental uncertainties concerning electron spin polarization (SP) under various realistic measurement conditions are theoretically derived. The accuracy of the evaluation of the SP of the photoelectron current is analysed as a function of the detector parameters and specifications, as well as of the characteristics of the photoexcitation sources. In particular, the different behaviour of single counter or twin counter detectors when the intensity fluctuations of the source are considered have been addressed, leading to a new definition of the SP detector performance. The widely used parameter called the figure of merit is shown to be inadequate for describing the efficiency of SP polarimeters, especially when they are operated with time-structured excitation sources such as free-electron lasers. Numerical simulations have been performed and yield strong implications in the choice of the detecting instruments in spin-polarization experiments, that are constrained in a limited measurement time. Our results are therefore applied to the characteristics of a wide set of state-of-the-art spectroscopy facilities all over the world, and an efficiency diagram for SP experiments is derived. These results also define new mathematical instruments for handling the correct statistics of SP measurements in the presence of source intensity fluctuations.

A new-concept approach to room temperature magnetic gas sensing has been developed, based on newly designed Co/ZnO hybrid nanostructures. The sensor prototype has been demonstrated to be sensitive, reversible, fast and scalable. In this work, the role of the Co/ZnO surface and interface in the gas-sensing mechanism has been clarified. In order to attain a comprehensive understanding of the physics governing the remarkable properties of the Co/ZnO stack, an extensive electronic and structural investigation has been carried out. The reaction at room temperature with target gases involves the surface and the lateral faces of the ZnO nanorods, with the formation of structural defects and vacancies. In particular, it has been discovered that the stress enhancement as well as the change in the polarizability of the ZnO nanorods are transduced by Co in a change of its magnetization. The interplay between these phenomena may provide versatile approaches to tune the intrinsic electronic, magnetic and optical properties of the hybrid nanostructure.

International audience; Femtosecond laser pulses have opened new frontiers for the study of ultrafast phase transitions andnonequilibrium states of matter. In this Letter, we report on structural dynamics in atomic clusters pumpedwith intense near-infrared (NIR) pulses into a nanoplasma state. Employing wide-angle scattering withintense femtosecond x-ray pulses from a free-electron laser source, we find that highly excited xenonnanoparticles retain their crystalline bulk structure and density in the inner core long after the driving NIRpulse. The observed emergence of structural disorder in the nanoplasma is consistent with a propagationfrom the surface to the inner core of the clusters.

We demonstate a non-equilibrium route for ultrafast modification of Fermi surface topology in quantum materials., Fermi surface is at the heart of our understanding of metals and strongly correlated many-body systems. An abrupt change in the Fermi surface topology, also called Lifshitz transition, can lead to the emergence of fascinating phenomena like colossal magnetoresistance and superconductivity. While Lifshitz transitions have been demonstrated for a broad range of materials by equilibrium tuning of macroscopic parameters such as strain, doping, pressure, and temperature, a nonequilibrium dynamical route toward ultrafast modification of the Fermi surface topology has not been experimentally demonstrated. Combining time-resolved multidimensional photoemission spectroscopy with state-of-the-art TDDFT+U simulations, we introduce a scheme for driving an ultrafast Lifshitz transition in the correlated type-II Weyl semimetal Td-MoTe2. We demonstrate that this nonequilibrium topological electronic transition finds its microscopic origin in the dynamical modification of the effective electronic correlations. These results shed light on a previously unexplored ultrafast scheme for controlling the Fermi surface topology in correlated quantum materials.