W. Wurth

Direct observation of electron dynamics in the attosecond domain

Dynamical processes are commonly investigated using laser pump–probe experiments, with a pump pulse exciting the system of interest and a second probe pulse tracking its temporal evolution as a function of the delay between the pulses. Because the time resolution attainable in such experiments depends on the temporal definition of the laser pulses, pulse compression to 200 attoseconds (1 as = 10-18 s) is a promising recent development. These ultrafast pulses have been fully characterized, and used to directly measure light waves and electronic relaxation in free atoms. But attosecond pulses can only be realized in the extreme ultraviolet and X-ray regime; in contrast, the optical laser pulses typically used for experiments on complex systems last several femtoseconds (1 fs = 10-15 s). Here we monitor the dynamics of ultrafast electron transfer—a process important in photo- and electrochemistry and used in solid-state solar cells, molecular electronics and single-electron devices—on attosecond timescales using core-hole spectroscopy. We push the method, which uses the lifetime of a core electron hole as an internal reference clock for following dynamic processes, into the attosecond regime by focusing on short-lived holes with initial and final states in the same electronic shell. This allows us to show that electron transfer from an adsorbed sulphur atom to a ruthenium surface proceeds in about 320 as.

Excitation, deexcitation, and fragmentation in the core region of condensed and adsorbed water

Using synchrotron radiation, Auger electron, and H+/D+‐ion yields have been studied at and above the O 1s excitation energies for condensed H2O/D2O layers of varying thickness, and for two reproducible adsorbate layers (so‐called bilayers and monolayers) on Ru(001). Decay electron spectra as well as polarization dependences, angular distributions, and energy distributions of desorbing ions have been investigated. For polarizations with sufficient E component perpendicular to the surface, a sharp peak in the H+ NEXAFS spectrum is seen for all layers which has no direct counterpart in the Auger NEXAFS spectra, and whose intensity maximizes for E oriented in the detection direction. This observation is interpreted as due to the 1a1→4a1 core‐to‐bound transition of the surface molecules whose final state decays electronically and dissociates on comparable time scales. This appears to have the consequence that the symmetry of the coupled excitation is different from that expected for the primary photoabsorption...

The liquid-liquid phase transition in silicon revealed by snapshots of valence electrons

The basis for the anomalies of water is still mysterious. Quite generally tetrahedrally coordinated systems, also silicon, show similar thermodynamic behavior but lack—like water—a thorough explanation. Proposed models—controversially discussed—explain the anomalies as a remainder of a first-order phase transition between high and low density liquid phases, buried deeply in the “no man’s land”—a part of the supercooled liquid region where rapid crystallization prohibits any experimental access. Other explanations doubt the existence of the phase transition and its first-order nature. Here, we provide experimental evidence for the first-order-phase transition in silicon. With ultrashort optical pulses of femtosecond duration we instantaneously heat the electronic system of silicon while the atomic structure as defined by the much heavier nuclear system remains initially unchanged. Only on a picosecond time scale the energy is transferred into the atomic lattice providing the energy to drive the phase transitions. With femtosecond X-ray pulses from FLASH, the free-electron laser at Hamburg, we follow the evolution of the valence electronic structure during this process. As the relevant phases are easily distinguishable in their electronic structure, we track how silicon melts into the low-density-liquid phase while a second phase transition into the high-density-liquid phase only occurs after the latent heat for the first-order phase transition has been transferred to the atomic structure. Proving the existence of the liquid-liquid phase transition in silicon, the hypothesized liquid-liquid scenario for water is strongly supported.

Ultrafast electron dynamics at surfaces probed by resonant Auger spectroscopy

Abstract Ultrafast charge transfer processes from adsorbates to substrates are believed to occur on the timescale of (sub)-femtoseconds. In this paper we present experimental evidence for resonant tunneling of electrons at surfaces in the time regime ranging from

Towards time resolved core level photoelectron spectroscopy with femtosecond x-ray free-electron lasers

We have performed core level photoelectron spectroscopy on a W(110) single crystal with femtosecond XUV pulses from the free-electron laser at Hamburg (FLASH). We demonstrate experimentally and through theoretical modelling that for a suitable range of photon fluences per pulse, time-resolved photoemission experiments on solid surfaces are possible. Using FLASH pulses in combination with a synchronized optical laser, we have performed femtosecond time-resolved core-level photoelectron spectroscopy and observed sideband formation on the W 4f lines indicating a cross correlation between femtosecond optical and XUV pulses.

Orientation and bonding of thiophene and 2,2′-bithiophene on Ag(111): a combined near edge extended X-ray absorption fine structure and Xα scattered-wave study

Abstract The adsorption of thiophene and 2,2′-bithiophene on Ag(111) was studied using temperature programmed desorption and near-edge X-ray-absorption fine-structure (NEXAFS). The assignment of the NEXAFS resonances is supported by Xα scattered-wave calculations. For thiophene we identify a compressed and a relaxed monolayer species. Whereas the molecules in the latter state are adsorbed parallel to the surface, they are adsorbed in an inclined geometry in the compressed monolayer. For 2,2′-bithiophene, in contrast, we find a mono- and a bi-layer species, which are both adsorbed in a flat-lying geometry on the Ag(111) surface. All adsorption species are weakly bound to the surface and comprise of undissociated molecules. In addition we demonstrate an X-ray-induced partial polymerization of thiophene multilayers.

Single-shot timing measurement of extreme-ultraviolet free-electron laser pulses

Arrival time fluctuations of extreme-ultraviolet (EUV) pulses from the free-electron laser in Hamburg (FLASH) are measured single-pulse resolved at the experimental end-station. To this end, they are non-collinearly superimposed in space and time with visible femtosecond laser pulses on a GaAs substrate. The EUV irradiation induces changes of the reflectivity for the visible pulse. The temporal delay between the two light pulses is directly encoded in the spatial position of the reflectivity change which is captured with a CCD camera. For each single shot, the relative EUV/visible arrival-time can be measured with about 40 fs rms accuracy. The method constitutes a novel route for an improvement of future pump–probe experiments at short-wavelength free-electron lasers (FELs) by a pulse-wise correction with simultaneously measured arrival times of individual EUV pulses.

Surface core level shifts of clean and oxygen covered Ru(0001)

We present the results of high resolution core level photoelectron spectroscopy employed to investigate the electronic structure of clean and oxygen covered Ir(111) surface. Ir 4f7/2 core level spectra are shown to be very sensitive to the local atomic environment. For the clean surface we detected two distinct components shifted by 550meV, originated by surface and bulk atoms. The larger Gaussian width of the bulk component is explained as due to experimentally unresolved subsurface components. In order to determine the relevance of the phonon contribution we examined the thermal behaviour of the core level lineshape using the Hedin-Rosengren theory. From the phonon- induced spectral broadening we found the Debye temperature of bulk and surface atoms to be 298 and 181K, respectively, which confirms the softening of the vibrational modes at the surface. Oxygen adsorption leads to the appearance of new surface core level components at 200meV and +230meV, which are interpreted as due to first-layer Ir atoms differently coordinated with oxygen. The coverage dependence of these components demonstrates that the oxygen saturation corresponds to 0.38ML, in good agreement with recent density functional theory calculations.

The soft x-ray instrument for materials studies at the linac coherent light source x-ray free-electron laser.

The soft x-ray materials science instrument is the second operational beamline at the linac coherent light source x-ray free electron laser. The instrument operates with a photon energy range of 480-2000 eV and features a grating monochromator as well as bendable refocusing mirrors. A broad range of experimental stations may be installed to study diverse scientific topics such as: ultrafast chemistry, surface science, highly correlated electron systems, matter under extreme conditions, and laboratory astrophysics. Preliminary commissioning results are presented including the first soft x-ray single-shot energy spectrum from a free electron laser.

Monochromator beamline for FLASH

The design of a high resolution monochromator for the vacuum ultraviolet free electron laser at Hamburg (FLASH), DESY, is described. The monochromator is constructed as a plane grating monochromator using collimated light. Modifications have been made to take into account the free electron laser (FEL) beam characteristics, in particular, the extremely high peak power density of the radiation. Ray tracing simulations yield a resolving power in the range of 10 000–70 000 depending on the photon energy and the grating in use. Our monochromator is equipped with a 200line∕mm grating for the energy range of 20–200eV—the operation regime of FLASH—and a high resolution 1200line∕mm grating for the energy range of 100–600eV, covering the higher harmonic radiation of the FEL.