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Femtosecond carrier dynamics in layered 2H-MoTe2 semiconductor crystals have been investigated using soft x-ray transient absorption spectroscopy at the x-ray free-electron laser (XFEL) of the Pohang Accelerator Laboratory. Following above-bandgap optical excitation of 2H-MoTe2, the photoexcited hole distribution is directly probed via short-lived transitions from the Te 3d 5/2 core level (M5-edge, 572-577 eV) to transiently unoccupied states in the valence band. The optically excited electrons are separately probed via the reduced absorption probability at the Te M5-edge involving partially occupied states of the conduction band. A 400 ± 110 fs delay is observed between this transient electron signal near the conduction band minimum compared to higher-lying states within the conduction band, which we assign to hot electron relaxation. Additionally, the transient absorption signals below and above the Te M5 edge, assigned to photoexcited holes and electrons, respectively, are observed to decay concomitantly on a 1-2 ps timescale, which is interpreted as electron-hole recombination. The present work provides a benchmark for applications of XFELs for soft x-ray absorption studies of carrier-specific dynamics in semiconductors, and future opportunities enabled by this method are discussed.

In the last ten years, x-ray free-electron lasers (XFELs) have been successfully employed to characterize metalloproteins at room temperature using various techniques including x-ray diffraction, scattering, and spectroscopy. The approach has been to outrun the radiation damage by using femtosecond (fs) x-ray pulses. An example of an important and damage sensitive active metal center is the Mn4CaO5 cluster in photosystem II (PS II), the catalytic site of photosynthetic water oxidation. The combination of serial femtosecond x-ray crystallography and K beta x-ray emission spectroscopy (XES) has proven to be a powerful multimodal approach for simultaneously probing the overall protein structure and the electronic state of the Mn4CaO5 cluster throughout the catalytic (Kok) cycle. As the observed spectral changes in the Mn4CaO5 cluster are very subtle, it is critical to consider the potential effects of the intense XFEL pulses on the K beta XES signal. We report here a systematic study of the effects of XFEL peak power, beam focus, and dose on the Mn K beta(1,3) XES spectra in PS II over a wide range of pulse parameters collected over seven different experimental runs using both microcrystal and solution PS II samples. Our findings show that for beam intensities ranging from & SIM;5 x 10(15) to 5 x 10(17) W/cm(2) at a pulse length of & SIM;35 fs, the spectral effects are small compared to those observed between S-states in the Kok cycle. Our results provide a benchmark for other XFEL-based XES studies on metalloproteins, confirming the viability of this approach.

Femtosecond-resolved Extended X-ray Absorption Fine Structure (EXAFS) measurements of solvated transition metal complexes are successfully implemented at the X-ray Free Electron Laser LCLS. Benchmark experiments on [Fe(terpy)2]2+ in solution show a signal-to-noise ratio on the order of 500, comparable to typical 100 ps-resolution synchrotron measurements. In the few femtoseconds after photoexcitation, we observe the EXAFS fingerprints of a short-lived (∼100 fs) intermediate as well as those of a vibrationally hot long-lived (∼ns) excited state.

The laser-induced nonsequential double ionization (NSDI) of rare gas atoms in the near and mid-IR laser fields is studied experimentally and theoretically. We investigate electron-electron correlation at high recollision energies, experimentally achieving ponderomotive energies (Up) above 80 eV. The contribution of the two dominant channels of NSDI in the photoelectron momentum distribution, impact, and excitation ionization, are both shown to scale with ponderomotive energy and are well reproduced by theory. Surprisingly, for a large Up in mid-IR fields, a noticeable electron-electron anticorrelation signal emerges at low photoelectron momenta, which cannot be explained by these mechanisms within state-of-the-art theoretical approaches.

With the rising cost and insufficient supply of cobalt, the thrust for cobalt-free cathode materials with the high specific capacity to build Li-ion batteries has increased significantly. Using nickel as the prime electrochemical active species, we have synthesized a new-class of materials with the combination of ordered and disordered phases. To obtain high capacity and electrical charge neutrality, stoichiometry of cations designed in a way that it forms Li/Ni rich Ni-Ti-Mo oxide materials. In addition to conventional capacity from redox activity of transition metals, partially reversible oxygen redox reaction also contributes to electrochemical activity and thus results in unusual high capacity. The resultant cathode materials of LiNi0.5Ti0.5O2-(Li4MoO5)0.8 and LiNiO2 mixture phases reach the specific capacity of 240 mAh/g. Detailed soft X-ray absorption spectroscopy and electron microscopy are used to reveal the crystal phases in this system and trace changes in the Ni2+/Ni4+ redox couple during charge-discharge processes. Such comprehensive analysis of ordered-disordered oxides suggesting potentiality to develop high-capacity cobalt-free cathodes.

The Femtosecond X-ray Experiments scientific instrument is a versatile instrument for ultrafast pump–probe X-ray absorption, emission and scattering experiments at the European XFEL; the instrumentation, commissioning results and operation performance status are presented., The European X-ray Free-Electron Laser (EuXFEL) delivers extremely intense (>1012 photons pulse−1 and up to 27000 pulses s−1), ultrashort (

The technical implementation of a multi-MHz data acquisition scheme for laser–X-ray pump–probe experiments with pulse limited temporal resolution (100 ps) is presented. Such techniques are very attractive to benefit from the high-repetition rates of X-ray pulses delivered from advanced synchrotron radiation sources. Exploiting a synchronized 3.9 MHz laser excitation source, experiments in 60-bunch mode (7.8 MHz) at beamline P01 of the PETRA III storage ring are performed. Hereby molecular systems in liquid solutions are excited by the pulsed laser source and the total X-ray fluorescence yield (TFY) from the sample is recorded using silicon avalanche photodiode detectors (APDs). The subsequent digitizer card samples the APD signal traces in 0.5 ns steps with 12-bit resolution. These traces are then processed to deliver an integrated value for each recorded single X-ray pulse intensity and sorted into bins according to whether the laser excited the sample or not. For each subgroup the recorded single-shot values are averaged over ∼107 pulses to deliver a mean TFY value with its standard error for each data point,e.g.at a given X-ray probe energy. The sensitivity reaches down to the shot-noise limit, and signal-to-noise ratios approaching 1000 are achievable in only a few seconds collection time per data point. The dynamic range covers 100 photons pulse−1and is only technically limited by the utilized APD.

Ultrafast X-ray techniques serve as a direct probe of a long-lived pseudo-octahedral high-valent iron(V) complex. Its photo-induced formation from an azido-iron(III) precursor is observed in real-time with sub-picosecond resolution at SACLA XFEL.

We report about the development and implementation of a new setup for time-resolved X-ray absorption fine structure spectroscopy at beamline P11 utilizing the outstanding source properties of the low-emittance PETRA III synchrotron storage ring in Hamburg. Using a high intensitymicrometer-sized X-ray beam in combination with two positional feedback systems, measurements were performed on the transition metal complex fac-Tris[2-phenylpyridinato-C2,N]iridium(III) alsoreferred to as fac-Ir(ppy)$_3$. This compound is a representative of the phosphorescent iridium(III) complexes, which play an important role in organic light emitting diode (OLED) technology. The experiment could directly prove the anticipated photoinduced charge transfer reaction. Our results further reveal that the temporal resolution of the experiment is limited by the PETRA III X-ray bunch length of ∼ 103 ps full width at half maximum (FWHM).

Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.

Strong-field ionisation surprises with richness beyond current understanding despite decade long investigations. Ionisation with mid-IR light has promptly revealed unexpected kinetic energy structures that seem related to unanticipated quantum trajectories of the electrons. We measure first 3D momentum distributions in the deep tunneling regime (γ = 0.3) and observe surprising new electron dynamics of near-zero momentum electrons and extremely low momentum structures, below the eV, despite very high quiver energies of 95 eV. Such level of high-precision measurements at only 1 meV above the threshold, despite 5 orders higher ponderomotive energies, has now become possible with a specifically developed ultrafast mid-IR light source in combination with a reaction microscope, thereby permitting a new level of investigations into mid-IR recollision physics.

We present a novel nuclear activation-based method for the investigation of high-energy photons and electron dynamics within the laser-plasma interaction zone. This method is based on high density activation targets which are a pseudoalloy of several selected isotopes with different photo-neutron disintegration reaction thresholds. The gamma decay spectrum emitted by the activated target is used for the reconstruction of the bremsstrahlung spectrum generated by the electrons. This allows for the reconstruction of the spectrum of bremsstrahlung photons without any anticipated fit procedures. Furthermore, the characterization of the electrons in the interaction zone is accessible immediately. The consolidated findings about the interaction mechanisms could be used to realize, control and characterize laser driven particle generation, such as a pulsed neutron source for nuclear and material sciences using special target designs and materials in a pseudoalloic compound of isotopes. An additional application is the laser assisted nuclear transmutation to produce short-lived isotopes with activities suitable for medical diagnostics and therapy.

In recent years, the development of high power laser systems led to focussed intensities of more than 1022 W/cm2 at high pulse energies. Furthermore, both, the advanced high power lasers and the development of sophisticated laser particle acceleration mechanisms facilitate the generation of high energetic particle beams at high fluxes. The challenge of imaging detector systems is to acquire the properties of the high flux beam spatially and spectrally resolved. The limitations of most detector systems are saturation effects. These conventional detectors are based on scintillators, semiconductors, or radiation sensitive films.We present a nuclear activation-based imaging spectroscopy method, which is called NAIS, for the characterization of laser accelerated proton beams. The offline detector system is a combination of stacked metal foils and imaging plates (IP). After the irradiation of the stacked foils they become activated by nuclear reactions, emitting gamma decay radiation. In the next step, an autoradiography of the activated foils using IPs and an analysis routine lead to a spectrally and spatially resolved beam profile. In addition, we present an absolute calibration method for IPs.

The advent of mid-IR laser sources (λ ≥ 3.0 μm) permits scrutinizing strong-field photoionization of atoms and molecules deep into the tunnelling regime and unexpected features are being revealed [1]. A low kinetic energy structure (LES) was observed in the experimental photoelectron energy distribution and it was conspicuously absent in semi-classical and Keldysh-Faisal-Reiss (KFR) calculations. Further measurements are required revealing a full 3D momentum picture of the before-mentioned effects.