2017, Holtz, Marcel, Hauf, Christoph, Weisshaupt, Jannick, Salvador, Antonio-Andres Hernandez, Woerner, Michael, Elsaesser, Thomas

Table-top laser-driven hard x-ray sources with kilohertz repetition rates are an attractive alternative to large-scale accelerator-based systems and have found widespread applications in x-ray studies of ultrafast structural dynamics. Hard x-ray pulses of 100 fs duration have been generated at the Cu Kα wavelength with a photon flux of up to 109 photons per pulse into the full solid angle, perfectly synchronized to the sub- 100-fs optical pulses from the driving laser system. Based on spontaneous x-ray emission, such sources display a particular noise behavior which impacts the sensitivity of x-ray diffraction experiments. We present a detailed analysis of the photon statistics and temporal fluctuations of the x-ray flux, together with experimental strategies to optimize the sensitivity of optical pump/x-ray probe experiments. We demonstrate measurements close to the shot-noise limit of the x-ray source.

2015, Buchner, Franziska, Nakayama, Akira, Yamazaki, Shohei, Ritze, Hans-Hermann, Lübcke, Andrea

Time-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys.2013, 139, 214304). The temporal evolution of ionization energies for the excited ππ* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the ππ* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the nπ* state is possible at the given photon energies, but we have not found any experimental indication for signal from the nπ* state. In contrast to currently accepted relaxation mechanisms, we suggest that the nπ* state is not involved in the relaxation process of thymine in aqueous solution.

2014, Stodolna, A., Huismans, Y., Rouzée, A., Lépine, F., Vrakking, M.J.J.

The application of velocity map imaging for the detection of photoelectrons resulting from atomic or molecular ionization allows the observation of interferometric, and in some cases holographic structures that contain detailed information on the target from which the photoelecrons are extracted. In this contribution we present three recent examples of the use of photoelectron velocity map imaging in experiments where atoms are exposed to strong optical and dc electric fields. We discuss (i) observations of the nodal structure of Stark states of hydrogen measured in a dc electric field, (ii) mid-infrared strong-field ionization of metastable Xe atoms and (iii) the reconstruction of helium electronic wavepackets in an attosecond pump-probe experiment. In each case, the interference between direct and indirect electron pathways, reminiscent of the reference and signal waves in holography, is seen to play an important role.

2021, Schneidewind, Jacob, Argüello Cordero, Miguel A., Junge, Henrik, Lochbrunner, Stefan, Beller, Matthias

Water splitting to give molecular oxygen and hydrogen or the corresponding protons and electrons is a fundamental four-electron redox process, which forms the basis of photosynthesis and is a promising approach to convert solar into chemical energy. Artificial water splitting systems have struggled with orchestrating the kinetically complex absorption of four photons as well as the difficult utilization of visible light. Based on a detailed kinetic, spectroscopic and computational study of Milstein's ruthenium complex, we report a new mechanistic paradigm for water splitting, which requires only two photons and offers a new method to extend the range of usable wavelengths far into the visible region. We show that two-photon water splitting is enabled by absorption of the first, shorter wavelength photon, which produces an intermediate capable of absorbing the second, longer wavelength photon (up to 630 nm). The second absorption then causes O–O bond formation and liberation of O2. Theoretical modelling shows that two-photon water splitting can be used to achieve a maximum solar-to-hydrogen efficiency of 18.8%, which could be increased further to 28.6% through photochemical instead of thermal H2 release. It is therefore possible to exceed the maximum efficiency of dual absorber systems while only requiring a single catalyst. Due to the lower kinetic complexity, intrinsic utilization of a wide wavelength range and high-performance potential, we believe that this mechanism will inspire the development of a new class of water splitting systems that go beyond the reaction blueprint of photosynthesis.

2014, Burghoorn, M., Kniknie, B., van Deelen, J., Xu, M., Vroon, Z., van Ee, R., van de Belt, R., Buskens, P.

Textured transparent conductors are widely used in thin-film silicon solar cells. They lower the reflectivity at interfaces between different layers in the cell and/or cause an increase in the path length of photons in the Si absorber layer, which both result in an increase in the number of absorbed photons and, consequently, an increase in short-circuit current density (Jsc) and cell efficiency. Through optical simulations, we recently obtained strong indications that texturing of the transparent conductor in copper indium gallium (di-)selenide (CIGS) solar cells is also optically advantageous. Here, we experimentally demonstrate that the Jsc and efficiency of CIGS solar cells with an absorber layer thickness (dCIGS) of 0.85 μm, 1.00 μm and 2.00 μm increase through application of a moth-eye textured resist with a refractive index that is sufficiently similar to AZO (nresist = 1.792 vs. nAZO = 1.913-at 633 nm) to avoid large optical losses at the resist-AZO interface. On average, Jsc increases by 7.2%, which matches the average reduction in reflection of 7.0%. The average relative increase in efficiency is slightly lower (6.0%). No trend towards a larger relative increase in Jsc with decreasing dCIGS was observed. Ergo, the increase in Jsc can be fully explained by the reduction in reflection, and we did not observe any increase in Jsc based on an increased photon path length. © 2014 Author(s).

2014, Huang, Y., Fang, Y., Zhang, Z., Zhu, L., Sun, M.

Due to its amazing ability to manipulate light at the nanoscale, plasmonics has become one of the most interesting topics in the field of light-matter interaction. As a promising application of plasmonics, surface-enhanced Raman scattering (SERS) has been widely used in scientific investigations and material analysis. The large enhanced Raman signals are mainly caused by the extremely enhanced electromagnetic field that results from localized surface plasmon polaritons. Recently, a novel SERS technology called remote SERS has been reported, combining both localized surface plasmon polaritons and propagating surface plasmon polaritons (PSPPs, or called plasmonic waveguide), which may be found in prominent applications in special circumstances compared to traditional local SERS. In this article, we review the mechanism of remote SERS and its development since it was first reported in 2009. Various remote metal systems based on plasmonic waveguides, such as nanoparticle-nanowire systems, single nanowire systems, crossed nanowire systems and nanowire dimer systems, are introduced, and recent novel applications, such as sensors, plasmon-driven surface-catalyzed reactions and Raman optical activity, are also presented. Furthermore, studies of remote SERS in dielectric and organic systems based on dielectric waveguides remind us that this useful technology has additional, tremendous application prospects that have not been realized in metal systems.

2013, Legall, H., Stiel, H., Blobel, G., Seim, C., Baumann, J., Yulin, S., Esser, D., Hoefer, M., Wiesemann, U., Wirtz, M., Schneider, G., Rehbein, S., Hertz, H.M.

In the water window (2.2-4.4 nm) the attenuation of radiation in water is significantly smaller than in organic material. Therefore, intact biological specimen (e.g. cells) can be investigated in their natural environment. In order to make this technique accessible to users in a laboratory environment a Full-Field Laboratory Transmission X-ray Microscope (L-TXM) has been developed. The L-TXM is operated with a nitrogen laser plasma source employing an InnoSlab high power laser system for plasma generation. For microscopy the Ly α emission of highly ionized nitrogen at 2.48 nm is used. A laser plasma brightness of 5 × 1011 photons/(s × sr × μm2 in line at 2.48 nm) at a laser power of 70 W is demonstrated. In combination with a state-of-the-art Cr/V multilayer condenser mirror the sample is illuminated with 106 photons/(μm2 × s). Using objective zone plates 35-40 nm lines can be resolved with exposure times < 60 s. The exposure time can be further reduced to 20 s by the use of new multilayer condenser optics and operating the laser at its full power of 130 W. These exposure times enable cryo tomography in a laboratory environment.

2021, Zalibera, Michal, Ziegs, Frank, Schiemenz, Sandra, Dubrovin, Vasilii, Lubitz, Wolfgang, Savitsky, Anton, Deng, Shihu H.M., Wang, Xue-Bin, Advoshenko, Stanislav M., Popov, Alexey A.

We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of YxSc3−xN@C80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1–T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.

2020, Bredtmann, T., Patchkovskii, S.

Initial-state symmetry has been under-appreciated in strong-field spectroscopies, where laser fields dominate the dynamics. We demonstrate numerically that the transverse photoelectron phase structure, arising from the initial-state symmetry, is robust in strong-field rescattering, and has pronounced effects on strong-field photoelectron spectra. Interpretation of rescattering experiments need to take these symmetry effects into account. In turn, robust transverse photoelectron phase structures may enable attosecond sub-Ångström super-resolution imaging with structured electron beams.

2018, Lazić, S., Chernysheva, E., Hernández-Mínguez, A., Santos, P.V., van der Meulen, H.P.

On-chip quantum information processing requires controllable quantum light sources that can be operated on-demand at high-speeds and with the possibility of in-situ control of the photon emission wavelength and its optical polarization properties. Here, we report on the dynamic control of the optical emission from core-shell GaN/InGaN nanowire (NW) heterostructures using radio frequency surface acoustic waves (SAWs). The SAWs are excited on the surface of a piezoelectric lithium niobate crystal equipped with a SAW delay line onto which the NWs were mechanically transferred. Luminescent quantum dot (QD)-like exciton localization centers induced by compositional fluctuations within the InGaN nanoshell were identified using stroboscopic micro-photoluminescence (micro-PL) spectroscopy. They exhibit narrow and almost fully linearly polarized emission lines in the micro-PL spectra and a pronounced anti-bunching signature of single photon emission in the photon correlation experiments. When the nanowire is perturbed by the propagating SAW, the embedded QD is periodically strained and its excitonic transitions are modulated by the acousto-mechanical coupling, giving rise to a spectral fine-tuning within a ~1.5 meV bandwidth at the acoustic frequency of ~330 MHz. This outcome can be further combined with spectral detection filtering for temporal control of the emitted photons. The effect of the SAW piezoelectric field on the QD charge population and on the optical polarization degree is also observed. The advantage of the acousto-optoelectric over other control schemes is that it allows in-situ manipulation of the optical emission properties over a wide frequency range (up to GHz frequencies).