Melting is an everyday phase transition that is determined by thermodynamic parameters like temperature and pressure. In contrast, ultrafast melting is governed by the microscopic response to a rapid energy input and, thus, can reveal the strength and dynamics of atomic bonds as well as the energy flow rate to the lattice. Accurately describing these processes remains challenging and requires detailed insights into transient states encountered. Here, we present data from femtosecond electron diffraction measurements that capture the structural evolution of copper during the ultrafast solid to liquid phase transformations. At absorbed energy densities 2 to 4 times the melting threshold, melting begins at the surface slightly below the nominal melting point followed by rapid homogeneous melting throughout the volume. Molecular dynamics simulations reproduce these observations and reveal a weak electron lattice energy transfer rate for the given experimental conditions. Both simulations and experiments show no indications of rapid lattice collapse when its temperature surpasses proposed limits of superheating, providing evidence that inherent dynamics limits the speed of disordering in ultrafast melting of metals.

The ultrafast structural response of a thin iron film to sub-ps pulsed laser-induced heating has been investigated using time-resolved X-ray diffraction in the partial melting regime. A tetragonal distortion of the bcc-phase emerges at 6 ps. Its formation is delayed relative to the initial heating (1-2 ps) and partial melting (2-5 ps) of the material, and controlled by the stress release in the quasi-instantaneously pressurized film. The distortion persists for at least 60 ps indicating the formation of a metastable bct phase between the equilibrium bcc and fcc phases.

Irradiation of solid surfaces with intense ultrashort laser pulses represents a unique way of depositing energy into materials. It allows to realize states of extreme electronic excitation and/or very high temperature and pressure, and to drive materials close to and beyond fundamental stability limits. As a consequence, structural changes and phase transitions often occur along unusual pathways and under strongly non-equilibrium conditions. Due to the inherent multiscale nature - both temporally and spatially - of these irreversible processes their direct experimental observation requires techniques that combine high temporal resolution with the appropriate spatial resolution and the capability to obtain good quality data on a single pulse/event basis. In this respect fourth generation light sources, namely short wavelength, short pulse free electron lasers (FELs) are offering new and fascinating possibilities. As an example, this chapter will discuss the results of scattering experiments carried at the FLASH free electron laser at DESY (Hamburg, Germany), which allowed us to resolve laser-induced structure formation at surfaces on the nanometer to sub-micron length scale and in temporal regimes ranging from picoseconds to several nanoseconds with sub-picosecond resolution.

In this work we report on an ultrashort pulsed laser annealing-driven devitrification of thin film Cu67Zr33 metallic glass characterized by micro-beam X-ray diffraction and electron microscopy techniques. The essential feature of ultrashort pulsed laser annealing is ultrafast heating (10(14) K/s) by femtosecond optical excitation followed by extremely rapid cooling (10(10-12) K/s) due to heat dissipation into the film substrate. During repetitive optical excitation, we take X-ray diffraction snapshots of the intermediate, frozen-in stages of the glass-crystal transformation to study its kinetics. A quantitative analysis of the diffraction patterns supported by electron microscopy result shows that the glass-crystal transformation proceeds by a rapid formation of an energetically favourable layer of crystalline ZrO2 on the free surface of the glassy film accompanied by nucleation and growth of fcc-Cu in the residual amorphous matrix. We demonstrate that at low effective annealing temperatures the devitrification kinetics of both products is correlated, while at high temperatures they decouple and ZrO2 forms an order of magnitude faster than Cu. (C) 2021 The Authors. Published by Elsevier B.V.

Exploiting the element specificity of soft x-ray spectroscopy, we analyze the microscopic origin of ultrafast non-local dynamics induced by localized optical excitation in metal-insulator heterostructures. The performed ultraviolet pump - soft x-ray probe experiment is sensitive to all constituents of the [Fe/MgO]$_n$ heterostructures, and probes electronic as well as lattice excitations. Additional ultrafast electron diffraction experiments independently analyze the lattice dynamics of the Fe constituent, and provide in combination with the soft x-ray analysis and ab initio theory calculations comprehensive insight into the microscopic processes leading to local and non-local relaxation within one or among two constituents, respectively. Besides electronic excitations in Fe which relax within 1 ps by electron-phonon coupling, we identify a change at the oxygen K edge absorption at MgO sites which occurs already within 0.5 ps and is mediated by lattice excitations in Fe. This selective phonon transfer across the interface excites non-thermal, hot phonons in MgO. In addition a second, slower timescale is identified at the oxygen K pre-edge and the Fe L$_3$ edge. It represents heat transfer and thermalization of the heterostructure as a whole. Noteworthy, our experiments lack signatures of charge transfer across the interface and it is concluded that phononic processes dominate the competition of electronic and lattice excitations in these non-local dynamics.

The element specificity of soft X-ray spectroscopy makes it an ideal tool for analyzing the microscopic origin of ultrafast dynamics induced by localized optical excitation in metal-insulator heterostructures. Using [Fe/MgO]_n as a model system, we perform ultraviolet pump/soft X-ray probe experiments, which are sensitive to all constituents of these heterostructures, to probe both electronic and lattice excitations. Complementary ultrafast electron diffraction experiments independently analyze the lattice dynamics of the Fe constituent, and together with ab initio calculations yield comprehensive insight into the microscopic processes leading to local relaxation within a single constituent or non-local relaxation between two constituents. Besides electronic excitations in Fe, which are monitored at the Fe L_3 absorption edge and relax within 1 ps by electron-phonon coupling, soft X-ray analysis identifies a change at the oxygen K absorption edge of the MgO layers which occurs within 0.5 ps. This ultrafast energy transfer across the Fe-MgO interface is mediated by high-frequency, interface vibrational modes, which are excited by hot electrons in Fe and couple to vibrations in MgO in a mode-selective, non-thermal manner. A second, slower timescale is identified at the oxygen K pre-edge and the Fe L_3 edge. The slower process represents energy transfer by acoustic phonons and contributes to thermalization of the entire heterostructure. We thus find that the interfacial energy transfer is associated with non-equilibrium behavior in the phonon system. Because our experiments lack signatures of charge transfer across the interface, we conclude that phonon-mediated processes dominate the competition of electronic and lattice excitations in these non-local, non-equilibrium dynamics.

The ultrafast laser excitation of matters leads to nonequilibrium states with complex solid-liquid phase-transition dynamics. We used electron diffraction at mega-electron volt energies to visualize the ultrafast melting of gold on the atomic scale length. For energy densities approaching the irreversible melting regime, we first observed heterogeneous melting on time scales of 100 to 1000 picoseconds, transitioning to homogeneous melting that occurs catastrophically within 10 to 20 picoseconds at higher energy densities. We showed evidence for the heterogeneous coexistence of solid and liquid. We determined the ion and electron temperature evolution and found superheated conditions. Our results constrain the electron-ion coupling rate, determine the Debye temperature, and reveal the melting sensitivity to nucleation seeds.

The nanosize effect on electron-phonon interactions in free-electron noble metals has been a subject of intense discussion because of their important applications in physics, chemistry, and biomedicine. However, the interference from supports of dispersive nanoparticulate metals has led to controversial observations. We utilize freestanding, bicontinuous nanoporous gold (NPG) films to investigate electron-phonon interaction dynamics using ultrafast MeV electron diffraction. Compared to solid gold films, NPG shows faster electron phonon interaction and thus noticeably higher electron-phonon coupling constant. The results demonstrate that surface states of electrons and phonons play an important role in electron-phonon coupling of nanostructured materials.

Electron–phonon coupling processes determine electronic transport properties of materials and are responsible for the transfer of electronic excess energy to the lattice. With decreasing device dimensions an understanding of these processes in nanoscale materials is becoming increasingly important. Here we use time-resolved electron diffraction to directly study energy relaxation in thin bismuth films after optical excitation. Precise measurements of the transient Debye–Waller-effect for various film thicknesses and over an extended range of excitation fluences allow to separate different contributions to the incoherent lattice response. While phonon softening in the electronically excited state is responsible for an immediate increase of the r.m.s. atomic displacement within a few hundred fs, 'ordinary' electron–phonon coupling leads to subsequent heating of the material on a few ps time-scale. The data reveal distinct changes in the energy transfer dynamics which becomes faster for stronger excitation and smaller film thickness, respectively. The latter effect is attributed to a cross-interfacial coupling of excited electrons to phonons in the substrate.

Femtosecond pulses from X-ray free-electron lasers offer a powerful method for observing the coherent dynamic of phonons in crystalline materials, it is now shown. This time-resolved spectroscopic tool could provide insight into low-energy collective excitations in solids and how they interact at a microscopic level to determine the material’s macroscopic properties. The macroscopic characteristics of a material are determined by its elementary excitations, which dictate the response of the system to external stimuli. The spectrum of excitations is related to fluctuations in the density–density correlations and is typically measured through frequency-domain neutron1 or X-ray2,3,4 scattering. Time-domain measurements of these correlations could yield a more direct way to investigate the excitations of solids and their couplings both near to and far from equilibrium. Here we show that we can access large portions of the phonon dispersion of germanium by measuring the diffuse scattering from femtosecond X-ray free-electron laser pulses. A femtosecond optical laser pulse slightly quenches the vibrational frequencies, producing pairs of high-wavevector phonons with opposite momenta. These phonons manifest themselves as time-dependent coherences in the displacement correlations5 probed by the X-ray scattering. As the coherences are preferentially created in regions of strong electron–phonon coupling, the time-resolved approach is a natural spectroscopic tool for probing low-energy collective excitations in solids, and their microscopic interactions.

The macroscopic characteristics of a solid, such as its thermal, optical or transport properties are determined by the available microscopic states above its lowest energy level. These slightly higher quantum states are described by elementary excitations and dictate the response of the system under external stimuli. The spectrum of these excitations, obtained typically from inelastic neutron and x-ray scattering, is the spatial and temporal Fourier transform of the density-density correlation function of the system, which dictates how a perturbation propagates in space and time. As frequency-domain measurements do not generally contain phase information, time-domain measurements of these fluctuations could yield a more direct method for investigating the excitations of solids and their interactions both in equilibrium and far-from equilibrium. Here we show that the diffuse scattering of femtosecond x-ray pulses produced by a free electron laser (FEL) can directly measure these density-density correlations due to lattice vibrations in the time domain. We obtain spectroscopic information of the lattice excitations with unprecedented momentum- and frequency- resolution, without resolving the energy of the outgoing photon. Correlations are created via an acoustic analog of the dynamical Casimir effect, where a femtosecond laser pulse slightly quenches the phonon frequencies, producing pairs of squeezed phonons at momenta +q and -q. These pairs of phonons manifest as macroscopic, time-dependent coherences in the displacement correlations that are then probed directly by x-ray scattering. Since the time-dependent correlations are preferentially created in regions of strong electron-phonon coupling, the time-resolved approach is natural as a spectroscopic tool of low energy collective excitations in solids, and their microscopic interactions, both in linear response and beyond.

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We used photon pulses from an x-ray free-electron laser to study ultrafast x-ray-induced transitions of graphite from solid to liquid and plasma states. This was accomplished by isochoric heating of graphite samples and simultaneous probing via Bragg and diffuse scattering at high time resolution. We observe that disintegration of the crystal lattice and ion heating of up to 5 eV occur within tens of femtoseconds. The threshold fluence for Bragg-peak degradation is smaller and the ion-heating rate is faster than current x-ray-matter interaction models predict.

Time-resolved X-ray diffraction with ultrashort X-ray pulses from a laser-produced plasma is used to study the lattice response of a thin FeRh-film during a fs laser-driven anti-ferromagnetic to ferromagnetic phase transition.

1 Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32/46, PL-02-668 Warsaw, Poland 2 Institute of Physics, Czech Academy of Sciences, Na Slovance 2, 182 21 Prague 8, Czech Republic 3 Czech Technical University in Prague, Brehova 7, 115 19 Praha 1, Czech Republic 4 Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, D-22603 Hamburg, Germany 5 Lawrence Livermore National Laboratory, 7000 East Avenue, CA 94550 Livermore, USA 6 University of Duisburg-Essen, D-45117 Essen, Germany 7 Uppsala University, SE-75124 Uppsala, Sweden 8 FOM-Institute for Plasma Physics Rijnhuizen, P.O. Box 1207, 3430 BE Nieuwegein, The Netherlands 9 CCRLC Daresbury Laboratory, Warrington, Cheshire, WA4 4AD, UK 10 Andrzej Soltan Institute for Nuclear Studies, PL-05-400 Świerk/Otwock, Poland

We investigated single shot damage of Mo/Si multilayer coatings exposed to the intense fs XUV radiation at the Free-electron LASer facility in Hamburg - FLASH. The interaction process was studied in situ by XUV reflectometry, time resolved optical microscopy, and "post-mortem" by interference-polarizing optical microscopy (with Nomarski contrast), atomic force microscopy, and scanning transmission electron microcopy. An ultrafast molybdenum silicide formation due to enhanced atomic diffusion in melted silicon has been determined to be the key process in the damage mechanism. The influence of the energy diffusion on the damage process was estimated. The results are of significance for the design of multilayer optics for a new generation of pulsed (from atto- to nanosecond) XUV sources.

High-resolution ultrafast coherent diffractive imaging has been carried out at the FLASH FEL. Reconstructed images show no effect of sample destruction. Time resolved imaging was achieved by time-delay holography and with a synchronized optical laser.