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Uwe Bovensiepen

Publications and source records attributed to Uwe Bovensiepen.

At least 19 recordsLinked to original sources

Nanoscale Confinement Enhances Ultrafast Demagnetization

Nanoscale miniaturization has revolutionized the field of spintronics by enabling exponential growth in areal bit density. A similar leap is also expected in device speeds through successfully harnessing femtosecond magnetization dynamics. However, combining this with the miniaturization of realistic devices is challenging. To address this, we studied the effect of dimensional confinement on the femtosecond demagnetization of Fe. By gradually increasing the level of confinement while keeping excitation conditions constant, we found that Fe layers thinner than 10 nm exhibit enlarged demagnetization amplitudes, reaching a $\sim75\%$ increase at 2 nm. By combining ultrafast experiments sensitive to the spins, the charge carriers, and the phonons, we establish that this finite$\text{-}$size effect is magnetic in origin and is not phonon$\text{-}$driven. With the support of ab$\text{-}$initio calculations and atomistic spin dynamics simulations, we identify the enhancement effect as due to local weakening of spin order at the Fe$\text{'}$s interface, which becomes significant upon increased confinement.

cond-mat.mes-hall

Tunable competing optical excitation pathways in the topological surface states of Bi$_2$Te$_3$

Understanding coherent optical responses of topological surface states (TSSs) requires disentangling excitation pathways from the electronic band structure. Here, using angle-resolved two-photon photoemission spectroscopy, we identify two distinct excitation pathways in the TSSs of Bi$_2$Te$_3$: an off-resonant transition via virtual states and a resonant transition via unoccupied intermediate states. A pronounced modulation of the spectral response is observed, revealing a competition between the two coherent pathways. This competition is tunable via temperature-induced shifts of the chemical potential, which selectively modify the resonant channel. These results provide microscopic insight into the optical excitation mechanisms of TSSs and highlight the potential for controlling their optical responses, relevant for future spintronic devices.

cond-mat.mtrl-sci

Disorder-induced localisation in the Mott-Hubbard model

For the Fermi-Hubbard model in the Mott insulator phase, we employ the hierarchy of correlations to study how doublon and holon quasi-particle excitations are affected by adding disorder to the system. We study two types of disorder: charge disorder, in the form of on-site potential randomness; and spin disorder, in the form of a fixed, randomly generated background spin arrangement. By analysing the quasi-particle eigen-spectra and quantifying the degree to which the corresponding eigen-states localise, we find both an energetic and spatial separation between localised and delocalised states in the charge disorder. In contrast, the spin disorder results in localised states throughout the quasi-particle bands. Finally, we repeat our calculations using strong-coupling perturbation theory, and compare the results obtained from both methods.

cond-mat.str-el

Femtosecond spin-state switching dynamics of spin-crossover molecules condensed in thin films

The photoinduced switching of Fe(II)-based spin-crossover complexes from singlet to quintet takes place at ultrafast time scales. This a priori spin-forbidden transition triggered numerous time-resolved experiments of solvated samples to elucidate the mechanism at play. The involved intermediate states remain uncertain. We apply ultrafast x-ray spectroscopy in molecular films as a method sensitive to spin, electronic, and nuclear degrees of freedom. Combining the progress in molecule synthesis and film growth with the opportunities at x-ray free-electron lasers, we analyze the transient evolution of the Fe L3 fine structure at room temperature. Our measurements and calculations indicate the involvement of an Fe triplet intermediate state. The high-spin state saturates at half of the available molecules, limited by molecule-molecule interaction within the film.

cond-mat.mes-hall

Distinct amplitude mode dynamics upon resonant and off-resonant excitation across the charge density wave energy gap in LaTe3 investigated by time- and angle-resolved photoemission spectroscopy

Non-equilibrium states generated by ultrafast laser pulses are characterized by specific phenomena that are not accessible in static measurements. Previous time- and angle-resolved photoemission spectroscopy (TARPES) studies on rare-earth tritelluride materials have revealed the laser-driven melting of the charge density wave order as well as its collective amplitude mode excitation. Variation of the excess energy deposited by optical pumping in the material promises pathways to control the dynamic material response. To this end, we use an optical parametric amplifier to generate a tunable pump photon energy. Studying LaTe3 we compare the dynamics driven by pumping resonantly across the charge density wave energy gap with the effect of pumping at a twice higher photon energy in a TARPES pump-probe experiment. We clearly identify a pump photon energy dependent behavior. At the larger pump photon energy, the excess electronic energy generates lattice heating mediated by e-ph coupling and softening of the amplitude mode frequency from 3 to 2 THz. Remarkably, the resonant pumping across the CDW gap results in a time-independent amplitude mode frequency. We conclude that the resonant excitation across the energy gap excites the amplitude mode selectively while additional electronic excess energy deposited at higher pump photon energy modifies the crystal properties transiently by incoherent dissipative processes.

cond-mat.str-el

Ultrafast Electronic Structure Engineering in 1$T$-TaS$_2$: Role of Doping and Amplitude Mode Dynamics

In strongly correlated transition metal dichalcogenides, an intricate interplay of polaronic distortions, stacking arrangement, and electronic correlations determines the nature of the insulating state. Here, we study the response of the electronic structure to optical excitations to reveal the effect of chemical electron doping on this complex interplay. Transient changes in pristine and electron-doped 1$T$ -TaS$_2$ are measured by femtosecond time-resolved photoelectron spectroscopy and compared to theoretical modeling based on non-equilibrium dynamical mean-field theory and density functional theory. The fine changes in the oscillatory signal of the charge density wave amplitude mode indicate phase-dependent modifications in the Coulomb interaction and the hopping. Furthermore, we find an enhanced fraction of monolayers in the doped system. Our work demonstrates how the combination of time-resolved spectroscopy and advanced theoretical modeling provides insights into the physics of correlated transition metal dichalcogenides.

cond-mat.str-el

Analysis of long-lived effects in high-repetition-rate stroboscopic transient X-ray absorption experiments on thin films

Time-resolved X-ray absorption spectroscopy (tr-XAS) has been shown to be a versatile measurement technique for investigating non-equilibrium dynamics. Novel X-ray free electron laser (XFEL) facilities like the European XFEL offer increased repetition rates for stroboscopic XAS experiments through a burst operation mode, which enables measurements with up to 4.5 MHz. These higher repetition rates lead to higher data acquisition rates but can also introduce long-lived excitations that persist and thus build up during each burst. Here, we report on such long-lived effects in Ni and NiO thin film samples that were measured at the European XFEL. We disentangle the long-lived excitations from the initial pump-induced change and perform a detailed modelling-based analysis of how they modify transient X-ray spectra. As a result, we link the long-lived effects in Ni to a local temperature increase, as well as the effects in NiO to excited charge carrier trapping through polaron formation. In addition, we present possible correction methods, as well as discuss ways in which the effects of these long-lived excitations could be minimized for future time-resolved X-ray absorption spectroscopy measurements.

cond-mat.mtrl-sci

Photo-induced charge-transfer renormalization in NiO

Photo-doped states in strongly correlated charge transfer insulators are characterized by $d$-$d$ and $d$-$p$ interactions and the resulting intertwined dynamics of charge excitations and local multiplets. Here we use femtosecond x-ray absorption spectroscopy in combination with dynamical mean-field theory to disentangle these contributions in NiO. Upon resonant optical excitation across the charge transfer gap, the Ni $L_3$ and O $K$ absorption edges red-shift for $>10$ ps, associated with photo-induced changes in the screening environment. An additional signature below the Ni $L_3$ edge is identified for $<1$ ps, reflecting a transient nonthermal population of local many-body multiplets. We employ a nonthermal generalization of the multiplet ligand field theory to show that the feature originates from $d$-$d$ transitions. Overall, the photo-doped state differs significantly from a chemically doped state. Our results demonstrate the ability to reveal excitation pathways in correlated materials by x-ray spectroscopies, which is relevant for ultrafast materials design.

cond-mat.str-el

Femtosecond electron transfer dynamics across the D$_2$O/Cs$^+$/Cu(111) interface: The impact of hydrogen bonding

Hydrogen bonding is essential in electron transfer processes at water-electrode interfaces. We study the impact of the H-bonding of water as a solvent molecule on real-time electron transfer dynamics across a Cs+-Cu(111) ion-metal interface using femtosecond time-resolved two-photon photoelectron spectroscopy. We distinguish in the formed water-alkali aggregates two regimes below and above two water molecules per ion. Upon crossing the boundary of these regimes, the lifetime of the excess electron localized transiently at the Cs+ ion increases from 40 to 60 femtoseconds, which indicates a reduced alkali-metal interaction. Furthermore, the energy transferred to a dynamic structural rearrangement due to hydration is reduced from 0.3 to 0.2 eV concomitantly. These effects are a consequence of H-bonding and the beginning formation of a nanoscale water network. This finding is supported by real-space imaging of the solvatomers and vibrational frequency shifts of the OH stretch and bending modes calculated for these specific interfaces.

physics.chem-ph

Spatio-Temporal Electron Propagation Dynamics in Au/Fe/MgO(001) in nonequilibrium: Revealing Single Scattering Events and the Ballistic Limit

Understanding the microscopic spatio-temporal dynamics of nonequilibrium charge carriers in heterosystems promises optimization of process and device design towards desired energy transfer. Hot electron transport is governed by scattering with other electrons, defects, and bosonic excitations. Analysis of the energy dependence of scattering pathways and identification of diffusive, super-diffusive, and ballistic transport regimes are current challenges. We determine in femtosecond time-resolved two-photon photoelectron emission spectroscopy the energy-dependent change of the electron propagation time through epitaxial Au/Fe(001) heteostructures as a function of Au layer thickness for energies of 0.5 to \unit[2.0]{eV} above the Fermi energy. We describe the laser-induced nonequilibrium electron excitation and injection across the Fe/Au interface using real-time time-dependent density functional theory and analyze the electron propagation through the Au layer by microscopic electron transport simulations. We identify ballistic transport of minority electrons at energies with a nascent, optically excited electron population which is determined by the combination of photon energy and the specific electronic structure of the material. At lower energy, super-diffusive transport with 1 to 4 scattering events dominates. The effective electron velocity accelerates from 0.3 to \unit[1]{nm/fs} with an increase in the Au layer thickness from 10 to 100~nm. This phenomenon is explained by electron transport that becomes preferentially aligned with the interface normal for thicker Au layers, which facilitates electron momentum / energy selection by choice of the propagation layer thickness.

cond-mat.mtrl-sci

A femtosecond time resolved view of vibrationally assisted electron transfer across the metal/aqueous interface

Understanding heterogeneous charge transfer is crucial if we are to build the best electrolyzers, fuel cells and photoelectrochemical water splitting devices that chemistry allows. Because the elementary processes involved have timescales ranging from femto- to milliseconds, direct simulation is not generally possible. Model Hamiltonian approaches thus have a crucial role in gaining mechanistic insight. Current generations of such theories describe a reactant(s) or product(s) that interacts with electrolyte via a single effective interaction. Such approaches thus obscure the extent to which particular solvent fluctuations influence charge transfer. Here we demonstrate experimentally that for a prototypical system, a ferrocene terminated alkane thiol self-assembled monolayer (SAM) on gold in contact with aqueous electrolyte, charge transfer from the Au to the ferrocene can be induced by vibrational excitation of the ferrocene aromatic CH. Intriguingly the energy of the aromatic CH vibration, 0.38 eV, is a large fraction of the effective solvent interaction strength inferred for the ferrocene/ferrocenium system in prior electrochemical studies: 0.85 eV. Our results thus demonstrate the coupling of charge transfer to a specific solvent motion and more generally imply that solvent may affect reduction/oxidation rates in electrocatalysis by coupling to a few distinct solvent motions. Identifying these motions is crucial in rationalizing trends in reactivity with change in electrolyte and thus in pursuing electrolyte engineering from first principles.

physics.chem-ph

Photon shot-noise limited transient absorption soft X-ray spectroscopy at the European XFEL

Femtosecond transient soft X-ray Absorption Spectroscopy (XAS) is a very promising technique that can be employed at X-ray Free Electron Lasers (FELs) to investigate out-of-equilibrium dynamics for material and energy research. Here we present a dedicated setup for soft X-rays available at the Spectroscopy & Coherent Scattering (SCS) instrument at the European X-ray Free Electron Laser (EuXFEL). It consists of a beam-splitting off-axis zone plate (BOZ) used in transmission to create three copies of the incoming beam, which are used to measure the transmitted intensity through the excited and unexcited sample, as well as to monitor the incoming intensity. Since these three intensity signals are detected shot-by-shot and simultaneously, this setup allows normalized shot-by-shot analysis of the transmission. For photon detection, the DSSC imaging detector, which is capable of recording up to 800 images at 4.5 MHz frame rate during the FEL burst, is employed and allows approaching the photon shot-noise limit. We review the setup and its capabilities, as well as the online and offline analysis tools provided to users.

physics.ins-det

Ultrafast electron dynamics in Au/Fe/MgO(001) analyzed by Au- and Fe-selective pumping in time-resolved two-photon photoemission spectroscopy: Separation of excitations in adjacent metallic layers

The transport of optically excited, hot electrons in heterostructures is analyzed by femtosecond, time-resolved two-photon photoelectron emission spectroscopy (2PPE) for epitaxial Au/Fe/MgO(001). We compare the temporal evolution of the 2PPE intensity upon optically pumping Fe or Au, while the probing occurs on the Au surface. In the case of Fe-side pumping, assuming independent relaxation in the Fe and Au layers, we determine the hot electron relaxation times in these individual layers by an analysis of the Au layer thickness dependence of the observed, effective electron lifetimes in the heterostructure. We show in addition that such a systematic analysis fails for the case of Au-side pumping due to the spatially distributed optical excitation density, which varies with the Au layer thickness. This work extends a previous study [Beyazit et al., Phys. Rev. Lett. 125, 076803 (2020)] by new data leading to reduced error bars in the determined lifetimes and by a non-linear term in the Au-thickness dependent data analysis which contributes for similar Fe and Au film thicknesses.

cond-mat.mtrl-sci

Electron Dynamics at High-Energy Densities in Nickel from Non-linear Resonant X-ray Absorption Spectra

The pulse intensity from X-ray free-electron lasers (FELs) can create extreme excitation densities in solids, entering the regime of non-linear X-ray-matter interactions. We show L3-edge absorption spectra of metallic nickel thin films with fluences entering a regime where several X-ray photons are incident per absorption cross-section. Main features of the observed non-linear spectral changes are described with a predictive rate model for electron population dynamics during the pulse, utilizing a fixed density of states and tabulated ground-state properties.

cond-mat.mtrl-sci

The interplay of local electron correlations and ultrafast spin dynamics in fcc Ni

The complex electronic structure of metallic ferromagnets is determined by a balance between exchange interaction, electron hopping leading to band formation, and local Coulomb repulsion. The interplay between the respective terms of the Hamiltonian is of fundamental interest, since it produces most, if not all, of the exotic phenomena observed in the solid state. By combining high energy and temporal resolution in femtosecond time-resolved X-ray absorption spectroscopy with ab initio time-dependent density functional theory we analyze the electronic structure in fcc Ni on the time scale of these interactions in a pump-probe experiment. We distinguish transient broadening and energy shifts in the absorption spectra, which we demonstrate to be caused by electron repopulation and correlation-induced modifications of the electronic structure, respectively. Importantly, the theoretical description of this experimental result hence requires to take the local Coulomb interaction into account, revealing a temporal interplay between band formation, exchange interaction, and Coulomb repulsion.

cond-mat.mtrl-sci

Hydration at highly crowded interfaces

Understanding the molecular and electronic structure of electrolytes at interfaces requires an analysis of the interactions between the electrode surface, the ions, and the solvent environment on equal footing. Here, we tackle this challenge by exploring the initial stages of Cs+ hydration on a Cu(111) surface by combining experiment and theory. Remarkably, we observe "inside out" solvation of Cs ions, i.e, their preferential location at the perimeter of the water clusters on the metal surface. In addition, water-Cs complexes containing multiple Cs+ ions are observed to form at these surfaces. Established models based on maximum ion-water coordination and the double layer notion cannot account for this situation and the complex interplay of microscopic interactions is the key to a fundamental understanding.

cond-mat.mes-hall

Relaxation of photo-excited hot carriers beyond multi-temperature models: General theory description verified by experiments on Pb/Si(111)

The equilibration of electronic carriers in metals after excitation by an ultra-short laser pulse provides an important class of non-equilibrium phenomena in metals and allows measuring the effective electron-phonon coupling parameter. Since the observed decay of the electronic distribution is governed by the interplay of both electron-electron and electron-phonon scattering, the interpretation of experimental data must rely on models that ideally should be easy to handle, yet accurate. In this work, an extended rate-equation model is proposed that explicitly includes non-thermal electronic carriers while at the same time incorporating data from first-principles calculations of the electron-phonon coupling via Eliashberg-Migdal theory. The model is verified against experimental data for thin Pb films grown on Si(111). Improved agreement between theory and experiment at short times (<0.3ps) due to non-thermal electron contributions is found. Moreover, the rate equations allow for widely different coupling strength to different phonon subsystems. Consequently, an indirect, electron-mediated energy transfer between strongly and weakly coupled groups of phonons can be observed in the simulations that leads to a retarded equilibration of the subsystems only after several picoseconds.

cond-mat.mtrl-sci

Ultrafast transport and energy relaxation of hot electrons in Au/Fe/MgO(001) heterostructures analyzed by linear time-resolved photoelectron spectroscopy

In condensed matter, scattering processes determine the transport of charge carriers. In case of heterostructures, interfaces determine many dynamic properties like charge transfer and transport and spin current dynamics. Here we discuss optically excited electron dynamics and their propagation across a lattice-matched, metal-metal interface of single crystal quality. Using femtosecond time-resolved linear photoelectron spectroscopy upon optically pumping different constituents of the heterostructure we establish a technique which probes the electron propagation and its energy relaxation simultaneously. In our approach a near-infrared pump pulse excites electrons directly either in the Au layer or in the Fe layer of epitaxial Au/Fe/MgO(001) heterostructures while the transient photoemission spectrum is measured by an ultraviolet probe pulse on the Au surface. Upon femtosecond laser excitation, we analyze the relative changes in the electron distribution close to the Fermi energy and assign characteristic features of the time-dependent electron distribution to transport of hot and non-thermalized electrons from the Fe layer to the Au surface and vice versa. From the measured transient electron distribution we determine the excess energy which we compare with a calculation based on the two-temperature model and takes diffusive electron transport into account. On this basis we identify a transition from a super-diffusive to a diffusive transport regime to occur for a Au layer thickness of 20-30~nm.

cond-mat.mtrl-sci