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The KMC-3 XPP endstation of the synchrotron BESSY II is dedicated to time-resolved studies of structural dynamics of matter upon optical and/or electrical excitation using hard X-ray diffraction with an accessible time range from 17 ps to several microseconds., The time-resolved hard X-ray diffraction endstation KMC-3 XPP for optical pump/X-ray probe experiments at the electron storage ring BESSY II is dedicated to investigating the structural response of thin film samples and heterostructures after their excitation with ultrashort laser pulses and/or electric field pulses. It enables experiments with access to symmetric and asymmetric Bragg reflections via a four-circle diffractometer and it is possible to keep the sample in high vacuum and vary the sample temperature between ∼15 K and 350 K. The femtosecond laser system permanently installed at the beamline allows for optical excitation of the sample at 1028 nm. A non-linear optical setup enables the sample excitation also at 514 nm and 343 nm. A time-resolution of 17 ps is achieved with the ‘low-α’ operation mode of the storage ring and an electronic variation of the delay between optical pump and hard X-ray probe pulse conveniently accesses picosecond to microsecond timescales. Direct time-resolved detection of the diffracted hard X-ray synchrotron pulses use a gated area pixel detector or a fast point detector in single photon counting mode. The range of experiments that are reliably conducted at the endstation and that detect structural dynamics of samples excited by laser pulses or electric fields are presented.

Using ultrafast x-ray diffraction, we directly monitor the lattice dynamics induced by femtosecond laser pulses in nanoscale thin films of bismuth iron garnet in external magnetic fields ${H}_{\mathrm{ext}}$. We control the ultrafast laser-induced lattice strain amplitude by changing the laser pulse helicity. The strength of ${H}_{\mathrm{ext}}$ is used as an external parameter to switch the helicity dependence on and off, respectively. Based on magneto-optical spectroscopic measurements, we explain these phenomena by magnetic circular dichroism. Our findings highlight an important approach for ultrafast manipulation of lattice strain in magnetic materials, in particular insulators, and open exciting perspectives towards ultrafast control of lattice strain and heat-induced magnetization switching and spin waves in bismuth substituted iron garnets using the polarization of light.

International audience; In this paper, we investigate the magnetic, optical, and lattice responses of a Pt/Cu/Bi 1 Y 2 Fe 5 O 12 /Gd 3 Ga 5 O 12 heterostructure to femtosecond laser excitation of the opaque Pt/Cu metallic bilayer. The electronic excitation generates coherent and incoherent phonons, which trigger high-frequency standing spin waves (SWs) in the dielectric Bi 1 Y 2 Fe 5 O 12 layer via a phonon-induced change of magnetic anisotropy. We find that the incoherent phonons (heat) can induce a fast (1000 ps) decrease of the magnetic order by different spin-phonon interaction scenarios. These results open perspectives for generating high-frequency SWs in buried magnetic garnets.

The plasmon-driven dimerization of 4-nitrothiophenol (4NTP) to 4-4’-dimercaptoazobenzene (DMAB) has become a testbed for understanding bimolecular photoreactions enhanced by nanoscale metals, in particular, regarding the relevance of electron transfer and heat transfer from the metal to the molecule. By adding a methylene group between the thiol bond and the nitrophenyl, we add structural flexibility to the reactant molecule. Time-resolved surface-enhanced Raman-spectroscopy proves that this (4-nitrobenzyl)mercaptan (4NBM) molecule has a larger dimerization rate and dimerization yield than 4NTP and higher selectivity towards dimerization. X-ray photoelectron spectroscopy and density functional theory calculations show that the electron transfer would prefer activation of 4NTP over 4NBM. We conclude that the rate limiting step of this plasmonic reaction is the dimerization step, which is dramatically enhanced by the additional flexibility of the reactant. This study may serve as an example for using nanoscale metals to simultaneously provide charge carriers for bond activation and localized heat for driving bimolecular reaction steps. The molecular structure of reactants can be tuned to control the reaction kinetics.

International audience; When the spatial dimensions of metallic heterostructures shrink below the mean free path of its conduction electrons, the transport of electrons and hence the transport of thermal energy by electrons continuously changes from diffusive to ballistic. Electron-phonon coupling sets the mean free path to the nanoscale and the time for equilibration of electron and lattice temperatures to the picosecond range. A particularly intriguing situation occurs in trilayer heterostructures combining metals with very different electron-phonon coupling strength: Heat energy deposited in few atomic layers of Pt is transported into a nanometric Ni film, which is heated more than the Cu film through which the heat is released. Femtosecond pump-probe experiments with hard X-ray pulses provide a layer-specific probe of the heat energy. A purely diffusive two-temperature model with increased thermal conductivity of hot electrons excellently reproduces the observed signals from all three layers. At the time when the Ni lattice is maximally heated, no significant heat has entered the Cu lattice. This phenomenon would be enhanced in thinner layers where ballistic transport dominates. In this context it is shown that purely diffusive transport can lead to a linear time-to-length dependence that must not be misinterpreted as ballistic transport.

Two-pulse laser excitation of FePt nanolayers distinguishes ultrafast stresses of magnetic excitations from the Poisson effect., Invar-behavior occurring in many magnetic materials has long been of interest to materials science. Here, we show not only invar behavior of a continuous film of FePt but also even negative thermal expansion of FePt nanograins upon equilibrium heating. Yet, both samples exhibit pronounced transient expansion upon laser heating in femtosecond x-ray diffraction experiments. We show that the granular microstructure is essential to support the contractive out-of-plane stresses originating from in-plane expansion via the Poisson effect that add to the uniaxial contractive stress driven by spin disorder. We prove the spin contribution by saturating the magnetic excitations with a first laser pulse and then detecting the purely expansive response to a second pulse. The contractive spin stress is reestablished on the same 100-ps time scale that we observe for the recovery of the ferromagnetic order. Finite-element modeling of the mechanical response of FePt nanosystems confirms the morphology dependence of the dynamics.

This paper quantifies the lattice expansion of an insulator upon two photon excitation. The ultrafast x-ray diffraction experiments measure a clean quadratic dependence of the strain on the laser fluency and prove that the pulse intensity is the relevant quantity, as the signal is anti-proportional to the pulse duration. The investigated material Bi:YIG is the standard material for magnonics, where ultrashort laser-pulses can create spin-waves via various mechanisms, including strain modulation of the anisotropy

Owing to their ability of concentrating electromagnetic fields to subwavelength mode volumes, plasmonic nanoparticles foster extremely high light–matter coupling strengths reaching far into the strong-coupling regime of light–matter interaction. In this article, we present an experimental investigation on the dependence of coupling strength on the geometrical size of the nanoparticle. The coupling strength for differently sized hybrid plasmon–core exciton–shell nanorods was extracted from the typical resonance anticrossing of these systems, obtained by controlled modification of the environment permittivity using layer-by-layer deposition of polyelectrolytes. The observed size dependence of the coupling strength can be explained by a simple model approximating the electromagnetic mode volume by the geometrical volume of the particle. On the basis of this model, the coupling strength for particles of arbitrary size can be predicted, including the particle size necessary to support single-emitter strong cou...

We investigate the ultrafast magnetization dynamics of FePt in the L10 phase after an optical heating pulse, as used in heat assisted magnetic recording. We compare continuous and nanogranular thin films and emphasize the impact of the finite size on the remagnetization dynamics. The remagnetization speeds up significantly with increasing external magnetic field only for the continuous film, where domain wall motion governs the dynamics. The ultrafast remagnetization dynamics in the continuous film are only dominated by heat transport in the regime of high magnetic fields, whereas the timescale required for cooling is prevalent in the granular film for all magnetic field strengths. These findings highlight the necessary conditions for studying the intrinsic heat transport properties in magnetic materials., 7 pages, 4 Figures

International audience; We investigate spin-wave resonance modes and their damping in insulating thin films of bismuth-substituted yttrium iron garnet by performing femtosecond magneto-optical pump-probe experiments. For large magnetic fields in the range below the magnetization saturation, we find that the damping of high-order standing spin-wave (SSW) modes is about 40 times lower than that for the fundamental one. The observed phenomenon can be explained by considering different features of magnetic anisotropy and exchange fields that, respectively, define the precession frequency for fundamental and high-order SSWs. These results provide further insight into SSWs in iron garnets and may be exploited in many new photomagnonic devices.

The electric field-dependence of structural dynamics in a tetragonal ferroelectric lead zirconate titanate thin film is investigated under subcoercive and above-coercive fields using time-resolved X-ray diffraction. The domain nucleation and growth are monitored in real time during the application of an external field to the prepoled thin film capacitor. We propose the observed broadening of the in-plane peak width of the symmetric 002 Bragg reflection as an indicator of the domain disorder and discuss the processes that change the measured peak intensity. Subcoercive field switching results in remnant disordered domain configurations. Published under license by AIP Publishing.

International audience; We demonstrate that femtosecond laser pulses allow triggering high-frequency standing spin-wave modes in nanoscale thin films of a bismuth-substituted yttrium iron garnet. By varying the strength of the external magnetic field, we prove that two distinct branches of the dispersion relation are excited for all the modes. This is reflected in particular at a very weak magnetic field (∼33 mT) by a spin dynamics with a frequency up to 15 GHz, which is 15 times higher than the one associated with the ferromagnetic resonance mode. We argue that this phenomenon is triggered by ultrafast changes of the magnetic anisotropy via laser excitation of incoherent and coherent phonons. These findings open exciting prospects for ultrafast photo magnonics. The continuous demand for more energy efficient and faster data transport and processing devices has triggered intense research activity to carry information with other means than the electron charge, which is associated with an inevitable Joule heating in current semiconductor-based information technologies [1]. One of the most promising ways to achieve this goal is the use of the coherent collective excitation of spins in magnetic materials, commonly known as magnons or spin waves (SWs) [2-5]. These waves can propagate in both metallic and dielectric magnetic media without involving any charge transport, which avoids the Joule heating, and therefore reduces substantially the power consumption for data processing. Besides this energy efficiency, using SWs offers other important advantages for ultrafast nanoscale computation due to their broad high frequency range from GHz to THz and tunable wavelength down to the nanoscale [6]. From a fundamental point of view, SWs exhibit remarkably rich physics involving both dipolar and exchange interactions [6,7]. This is reflected by versatile dispersion relations containing magnetostatic and exchange modes, which can either be tuned by an external magnetic field (H ext) and/or the sample size [3,6]. In this context, intense research is being carried out to understand the generation, propagation, manipulation, and detection of SWs in a continuously growing field of modern magnetism called magnonics [2-5]. Because of its low magnetic damping constant, the yttrium iron garnet (YIG) has attracted a lot of attention in the field of magnonics [8]. Indeed, many important magnetostatic SWs based devices have been realized using YIG during the last decade [9-12]. However, due to the small saturation magnetization of YIG together with the restrictions imposed by the size of the microwave antennas on the excited SWs wavelength with the standard method of microwave magnetic fields, magnetostatic SWs frequencies in such devices did not exceed a few GHz at low field, which is a major limiting factor for ultrafast applications. On the other hand, due to the strong exchange interaction between spins, the exchange SWs mode can have higher frequencies compared to the magnetostatic one. The possibility of triggering such exchange modes requires a nonuniform dynamical field across the magnetic film thickness [13], which is very challenging to induce using microwave antennas [13-15]. Recently, femtosecond laser pulses have been used as an efficient stimulus to excite a coherent spin precession [16,17]. In particular, it was demonstrated that femtosecond laser pulses can excite exchange standing SWs (SSWs) in metallic [18,19] and semiconductor [20,21] ferromagnets via thermal processes. On the other hand, most studies on iron garnets have been dedicated to the excitation and control of the homogenous resonance mode (k ¼ 0, i.e., low frequency) via nonthermal excitation mechanisms [22-29]. An important question in this context concerns the possibility to take advantage of femtosecond laser pulses for triggering a high frequency SSW in dielectric thin films of iron garnets. In this Letter, we demonstrate femtosecond laser-excited high frequency even and odd SSWs in nanoscale films of Bi-substituted yttrium iron garnet (Bi-YIG). Bi-YIG materials have, in addition to a low damping [30], very large magneto-optical Faraday effects [31], which make them well adapted for new photo magnonics devices. By varying the strength of the external applied magnetic field H ext , we demonstrate two distinct branches of the dispersion relation PHYSICAL REVIEW LETTERS 123, 027202 (2019) 0031-9007=19=123(2)=027202(6) 027202-1

On the basis of the layer-by-layer deposition of polyelectrolytes, we have designed hybrid nanolayer composites for integrated optoacoustic experiments. The femtosecond-laser-excitation of an Azo-functionalized film launches nanoscale strain waves at GHz frequencies into a transparent polymer layer. Gold nanorods deposited on the surface sense the arrival of these hyper-sound-waves on the picosecond time scale via a modification of their longitudinal plasmon resonance. We simulated the strain waves using a simple linear masses-and-springs model, which yields good agreement with the observed time scales associated with the nanolayer thicknesses of the constituent materials. From systematic experiments with calibrated strain amplitudes we conclude that reversible viscoelastic deformations of the polyelectrolyte multilayers are triggered by ultrashort pressure transients of about 4 MPa. Our experiments show that strain-mediated interactions in nanoarchitectures composed of molecular photoswitches and plasmon...

Ultrafast X-ray diffraction experiments require careful adjustment of the spatial overlap between the optical excitation and the X-ray probe pulse. This is especially challenging at high laser repetition rates. Sample distortions caused by the large heat load on the sample and the relatively low optical energy per pulse lead to only tiny signal changes. In consequence, this results in small footprints of the optical excitation on the sample, which turns the adjustment of the overlap difficult. Here a method for reliable overlap adjustment based on reciprocal space mapping of a laser excited thin film is presented.

We measure the transient strain profile in a nanoscale multilayer system composed of yttrium, holmium, and niobium after laser excitation using ultrafast x-ray diffraction. The strain propagation through each layer is determined by transient changes in the material-specific Bragg angles. We experimentally derive the exponentially decreasing stress profile driving the strain wave and show that it closely matches the optical penetration depth. Below the N\'eel temperature of Ho, the optical excitation triggers negative thermal expansion, which is induced by a quasi-instantaneous contractive stress and a second contractive stress contribution increasing on a 12-ps timescale. These two timescales were recently measured for the spin disordering in Ho [Rettig et al., Phys. Rev. Lett. 116, 257202 (2016)]. As a consequence, we observe an unconventional bipolar strain pulse with an inverted sign traveling through the heterostructure.

Negatively charged ultraflat gold nanotriangles (AuNTs) stabilized by the anionic surfactant dioctyl sodium sulfosuccinate (AOT) were reloaded with the cationic surfactant benzylhexadecyldimethylammonium chloride (BDAC). Because of the spontaneous formation of a catanionic AOT micelle/BDAC bilayer onto the surface of the reloaded AuNTs, a reduction of Ag+ ions leads to the formation of spherical silver nanoparticles (AgNPs). With increasing concentration of AgNPs on the AuNTs, the localized surface plasmon resonance (LSPR) is shifted stepwise from 1300 to 800 nm. The tunable LSPR enables to shift the extinction maximum to the wavelength of the excitation laser of the Raman microscope at 785 nm. Surface-enhanced Raman scattering (SERS) experiments performed under resonance conditions show an SERS enhancement factor of the analyte molecule rhodamine RG6 of 5.1 X 10(5), which can be related to the silver hot spots at the periphery of the undulated gold nanoplatelets.

Catanionic vesicles spontaneously formed by mixing the anionic surfactant bis(2-ethylhexyl) sulfosuccinate sodium salt with the cationic surfactant cetyltrimethylammonium bromide were used as a reducing medium to produce gold clusters, which are embedded and well-ordered into the template phase. The gold clusters can be used as seeds in the growth process that follows by adding ascorbic acid as a mild reducing component. When the ascorbic acid was added very slowly in an ice bath round-edged gold nanoflowers were produced. When the same experiments were performed at room temperature in the presence of Ag+ ions, sharp-edged nanoflowers could be synthesized. The mechanism of nanoparticle formation can be understood to be a non-diffusion-limited Ostwald ripening process of preordered gold nanoparticles embedded in catanionic vesicle fragments. Surface-enhanced Raman scattering experiments show an excellent enhancement factor of 1.7 · 105 for the nanoflowers deposited on a silicon wafer. Deutsche Forschungsgemeinschaft https://doi.org/10.13039/501100001659

We study gadolinium thin films as a model system for ferromagnets with negative thermal expansion. Ultrashort laser pulses heat up the electronic subsystem and we follow the transient strain via ultrafast x-ray diffraction. In terms of a simple Grueneisen approach, the strain is decomposed into two contributions proportional to the thermal energy of spin and phonon subsystems. Our analysis reveals that upon femtosecond laser excitation, phonons and spins can be driven out of thermal equilibrium for several nanoseconds.

International audience; We investigate the heat transport through a rare earth multilayer system composed of yttrium (Y), dysprosium (Dy), and niobium (Nb) by ultrafast x-ray diffraction. This is an example of a complex heat flow problem on the nanoscale, where several different quasiparticles carry the heat and conserve a nonequilibrium for more than 10 ns. The Bragg peak positions of each layer represent layer-specific thermometers that measure the energy flow through the sample after excitation of the Y top layer with fs-laser pulses. In an experiment-based analytic solution to the nonequilibrium heat transport problem, we derive the individual contributions of the spins and the coupled electron-lattice system to the heat conduction. The full characterization of the spatiotemporal energy flow at different starting temperatures reveals that the spin excitations of antiferromagnetic Dy speed up the heat transport into the Dy layer at low temperatures, whereas the heat transport through this layer and further into the Y and Nb layers underneath is slowed down. The experimental findings are compared to the solution of the heat equation using macroscopic temperature-dependent material parameters without separation of spin and phonon contributions to the heat. We explain why the simulated energy density matches our experiment-based derivation of the heat transport, although the simulated thermoelastic strain in this simulation is not even in qualitative agreement.

Monitoring structural changes in ferroelectric thin films during electric field induced polarization switching is important for a full microscopic understanding of the coupled motion of charges, atoms, and domain walls in ferroelectric nanostructures. We combine standard ferroelectric test sequences of switching and nonswitching electrical pulses with time-resolved x-ray diffraction to investigate the structural response of a nanoscale $\mathrm{Pb}({\mathrm{Zr}}_{0.2}{\mathrm{Ti}}_{0.8}){\mathrm{O}}_{3}$ ferroelectric oxide capacitor upon charging, discharging, and polarization reversal. We observe that a nonlinear piezoelectric response of the ferroelectric layer develops on a much longer time scale than the $RC$ time constant of the device. The complex atomic motion during the ferroelectric polarization reversal starts with a contraction of the lattice, whereas the expansive piezoelectric response sets in after considerable charge flow due to the applied voltage pulses on the electrodes of the capacitor. Our simultaneous measurements on a working device elucidate and visualize the complex interplay of charge flow and structural motion and challenges theoretical modeling.

We present time-resolved x-ray reflectivity measurements on laser excited coherent and incoherent surface deformations of thin metallic films. Based on a kinematical diffraction model, we derive the surface amplitude from the diffracted x-ray intensity and resolve transient surface excursions with sub-Angstrom spatial precision and 70 ps temporal resolution. The novel analysis allows for decomposition of the surface amplitude into multiple coherent acoustic modes and a substantial contribution from incoherent phonons which constitute the sample heating., Comment: 4 pages, 3 figures

We investigate the structural and thermal nonequilibrium dynamics including the spin-reordering dynamics of an antiferromagnetic Dysprosium (Dy) nanolayer after excitation with fs-laser pulses by means of ultrafast structural and magnetic x-ray diffraction experiments.

The amplitude of surface distortions induced by transient grating excitation has been measured via time-dependent x-ray diffraction (XRD). Results show 4 times higher amplitude of the incoherent surface deformation compared to the propagating surface acoustic waves with a total amplitude of 4a.

We present an optically induced remanent photostriction in BiFeO3, resulting from the photovoltaic effect, which is used to modify the ferromagnetism of Ni film in a hybrid BiFeO3/Ni structure. The 75% change in coercivity in the Ni film is achieved via optical and nonvolatile control. This photoferromagnetic effect can be reversed by static or ac electric depolarization of BiFeO3. Hence, the strain dependent changes in magnetic properties are written optically, and erased electrically. Light-mediated straintronics is therefore a possible approach for low-power multistate control of magnetic elements relevant for memory and spintronic applications., Report on photopolarization effect in BiFeO3 used to write magnetic properties via the remanent photostriction

We introduce a method to analyze optical and viscoelastic properties of the surrounding medium of GNRs by using hyper-sound waves, generated by new, efficient, inexpensive optoacoustic soft-matter transducers.

We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain epsilon similar to 5 x 10(-4) is calibrated by ultrafast X-ray diffraction.

We present a nanostructured device that functions as photoacoustic hard x-ray switch. The device is triggered by femtosecond laser pulses and allows for temporal gating of hard x-rays on picosecond (ps) timescales. It may be used for pulse picking or even pulse shortening in 3rd generation synchrotron sources. Previous approaches mainly suffered from insufficient switching contrasts due to excitation-induced thermal distortions. We present a new approach where thermal distortions are spatially separated from the functional switching layers in the structure. Our measurements yield a switching contrast of 14, which is sufficient for efficient hard x-ray pulse shortening. The optimized structure also allows for utilizing the switch at high repetition rates of up to 208 kHz. Published by AIP Publishing.

We employ ultrafast X-ray diffraction to compare the lattice dynamics of laser-excited continuous and granular FePt films on MgO (100) substrates. Contrary to recent results on free-standing granular films, we observe in both cases a pronounced and long-lasting out-of-plane expansion. We attribute this discrepancy to the in-plane expansion, which is suppressed by symmetry in continuous films. Granular films on substrates are less constrained and already show a reduced out-of-plane contraction. Via the Poisson effect, out-of-plane contractions drive in-plane expansion and vice versa. Consistently, the granular film exhibits a short-lived out-of-plane contraction driven by ultrafast demagnetization which is followed by a reduced and delayed expansion. From the acoustic reflections of the observed strain waves at the film-substrate interface, we extract a 13% reduction of the elastic constants in thin 10 nm FePt films compared to bulk-like samples. (C) 2018 Author(s).

Femtosecond X-ray scattering offers the opportunity to investigate reversible lattice dynamics with unprecedented accuracy. We show in a prototype experiment how strain propagation modifies the functionality of a ferroelectric system on its intrinsic time scale.

We report on a versatile and accurate method for determining the time delay between femtosecond X-ray and optical pulses in an optical pump/X-ray diffraction probe experiment. Upon excitation with moderate pump fluences, Bragg peaks of thin SrTiO3 (STO)/SrRuO3 (SRO) superlattices display 50% changes in diffracted X-ray intensity, followed by a pronounced lineshift (Δθ/θ=0.03°) on a 10 ps time-scale. A parallel time-resolved measurement of the instantaneous all-optical reflectivity change allows for a precise temporal analysis of the fully reversible X-ray response and gives the time delay zero with an accuracy of ±100 fs.

The plasmon resonance of metal nanoparticles determines their optical response in the visible spectral range. Many details such as the electronic properties of gold near the particle surface and the local environment of the particles influence the spectra. We show how the cheap but highly precise fabrication of composite nanolayers by spin-assisted layer-by-layer deposition of polyelectrolytes can be used to investigate the spectral response of gold nanospheres (GNS) and gold nanorods (GNR) in a self-consistent way, using the established Maxwell–Garnett effective medium (MGEM) theory beyond the limit of homogeneous media. We show that the dielectric function of gold nanoparticles differs from the bulk value and experimentally characterize the shape and the surrounding of the particles thoroughly by SEM, AFM and ellipsometry. Averaging the dielectric functions of the layered surrounding by an appropriate weighting with the electric field intensity yields excellent agreement for the spectra of several nanoparticles and nanorods with various cover-layer thicknesses.

We review different approaches to measure the transport of F atoms and ions in rare-gas matrices and compare the experimental results to simulations. Static measurements on sandwich structures and co-doped matrices yield rather long travel ranges beyond 2 nm, in accord with early classical simulations which predict a channeling of the F atoms in rare gas matrices. Nonadiabatic simulations show a rapid energy loss, fast nonadiabatic dynamics, and only short travel ranges of typically 1 unit cell. The rapid energy loss, fast nonadiabatic transitions and the time scale for direct dissociation (∼250 fs) are verified by femtosecond pump–probe experiments. It remains a challenge to account for the long-range migration when nonadiabatic processes are allowed in simulations, and to measure the long-distance flights directly by ultrafast spectroscopy.

Here, we present an Au@Pt core-shell multibranched nanoparticle as a new substrate capable of in situ surface-enhanced Raman scattering (SERS), thereby enabling monitoring of the catalytic reaction on the active surface. By careful control of the amount of Pt deposited bimetallic Au@Pt, nanoparticles with moderate performance both for SERS and catalytic activity were obtained. The Pt-catalyzed reduction of 4-nitrothiophenol by borohydride was chosen as the model reaction. The intermediate during the reaction was captured and clearly identified via SERS spectroscopy. We established in situ SERS spectroscopy as a promising and powerful technique to investigate in situ reactions taking place in heterogeneous catalysis.

We apply ultrafast x-ray diffraction with femtosecond temporal resolution to monitor the lattice dynamics in a thin film of multiferroic BiFeO3 after above-band-gap photoexcitation. The sound-velocity limited evolution of the observed lattice strains indicates a quasi-instantaneous photoinduced stress which decays on a nanosecond time scale. This stress exhibits an inhomogeneous spatial profile evidenced by the broadening of the Bragg peak. These new data require substantial modification of existing models of photogenerated stresses in BiFeO3: the relevant excited charge carriers must remain localized to be consistent with the data.

We present time-resolved X-ray diffraction data on antiferromagnetic Holmium thin films after direct femtosecond laser excitation. The strong magnetostriction in Holmium allows to correlate the observed ultrafast lattice dynamics to the antiferromagnetic helical spin structure.

Herein, a facile method is presented to integrate large gold nanoflowers (similar to 80 nm) and small gold nanoparticles (2-4 nm) into a single entity, exhibiting both surface-enhanced Raman scattering (SERS) and catalytic activity. The as-prepared gold nanoflowers were coated by a gelatin layer, in which the gold precursor was adsorbed and in situ reduced into small gold nanoparticles. The thickness of the gelatin shell is controlled to less than 10 nm, ensuring that the small gold nanoparticles are still in a SERS-active range of the inner Au core. Therefore, the reaction catalyzed by these nanocomposites can be monitored in situ using label-free SERS spectroscopy. In addition, these bifunctional nanocomposites are also attractive candidates for application in SERS monitoring of bioreactions because of their excellent biocompatibility.

A new concept for shortening hard X-ray pulses emitted from a third-generation synchrotron source down to few picoseconds is presented. The device, called the PicoSwitch, exploits the dynamics of coherent acoustic phonons in a photo-excited thin film. A characterization of the structure demonstrates switching times of

We investigate coherent phonon propagation in a thin film of ferroelectric PbZr0.2Ti0.8O3 (PZT) by ultrafast x-ray diffraction (UXRD) experiments, which are analyzed as time-resolved reciprocal space mapping (RSM) in order to observe the in- and out-of-plane structural dynamics simultaneously. The mosaic structure of the PZT leads to a coupling of the excited out-of-plane expansion to in-plane lattice dynamics on a picosecond timescale, which is not observed for out-of-plane compression., 5 pages, 4 figures

We investigate the thermoelastic response of a nanolayered sample composed of a metallic SrRuO3 (SRO) electrode sandwiched between a ferroelectric Pb(Zr0.2Ti0.8)O3 (PZT) film with negative thermal expansion and a SrTiO3 substrate. SRO is rapidly heated by fs-laser pulses with 208 kHz repetition rate. Diffraction of x-ray pulses derived from a synchrotron measures the transient out-of-plane lattice constant c of all three materials simultaneously from 120 ps to 5 mus with a relative accuracy up to Delta c/c = 10^-6. The in-plane propagation of sound is essential for understanding the delayed out of plane expansion., Comment: 5 pages, 3 figures

Reversible structural changes of a nanostructure were measured nondestructively with subpicometer spatial and subpicosecond temporal resolution via x-ray diffraction (XRD). The spatially periodic femtosecond excitation of a gallium arsenide/aluminum gallium arsenide superlattice results in coherent lattice motions with a 3.5-picosecond period, which was directly monitored by femtosecond x-ray pulses at a 1-kilohertz repetition rate. Small changes (Δ R / R = 0.01) of weak Bragg reflexes ( R = 0.005) were detected. The phase and amplitude of the oscillatory XRD signal around a new equilibrium demonstrate that displacive excitation of the zone-folded acoustic phonons is the dominant mechanism for strong excitation.

Epitaxially grown metallic oxide transducers support the generation of ultrashort strain pulses in SrTiO${}_{3}$ (STO) with high amplitudes up to 0.5$%$. The strain amplitudes are calibrated by real-time measurements of the lattice deformation using ultrafast x-ray diffraction. We determine the speed at which the strain fronts propagate by broadband picosecond ultrasonics and conclude that, above a strain level of approx. 0.2$%$, the compressive and tensile strain components travel at considerably different sound velocities, indicating nonlinear wave behavior. Simulations based on an anharmonic linear-chain model are in excellent accord with the experimental findings and show how the spectrum of coherent phonon modes changes with time.

When gold nanoparticles are covered with nanometric layers of transparent polyelectrolytes, the plasmon absorption spectrum A(λ) increases by a factor of approximately three and shifts to the red. These modifications of dissipative experimental observables stop when the cover layer thickness approaches the particle diameter. Spectral modifications of dispersive parameters like the reflection R, however, keep changing with increasing cover layer thickness. The shift of the plasmon resonance caused by two interacting particle layers is studied as a function of the separating distance between the two layers. We discuss these observations in the context of an effective medium theory and conclude that it can only be applied for a layer thickness on the order of the particle diameter.

We show ultrafast all-optical reflectivity measurements on nonlinear propagating strain pulses for different fluences calibrated by ultrafast X-ray diffraction (UXRD) to the corresponding induced strain amplitudes.

We present first results on mosaicity changes in a ferroelectric PbZr0.2Ti0.8O3 thin film on a ps timescale utilizing a new ultrafast reciprocal space mapping technique.

We present ultrafast x-ray diffraction experiments on oxide nanostructures consisting of ferromagnetic and ferroelectric layers. We discuss how the strain couples to heat in electrons, phonons and magnons.

We determined experimentally the complex transient optical dielectric function of a well-characterized polyelectrolyte/gold-nanoparticle composite system over a broad spectral range upon short pulse laser excitation by simultaneously measuring the time-dependent reflectance and transmittance of white light pulses with femtosecond pump-probe spectroscopy. We extracted directly the ultrafast changes in the real and imaginary parts of the effective dielectric function, epsilon(eff)(r) (omega,t)and epsilon(eff)(i) (omega,t), from the experiment. This complete experimental set of information on the time-dependent complex dielectric function challenges theories modeling the transient dielectric function of gold particles and the effective medium.

Ultrafast X-ray diffraction yields material-specific information on transient strain in crystals, thin films and multilayers. Here we highlight ultrafast heat-driven processes in ferroelectric and ferromagnetic oxides.

We investigated the generation and propagation of coherent phonons in an oxide superlattice of SrRuO3and SrTiO3. The rich dynamics resulted in drastic modulations of various Bragg peaks on a 1-ps timescale.