Anton Plech

Excitation of nanoscale vapor bubbles at the surface of gold nanoparticles in water

Intense nonequilibrium femtosecond laser excitation of gold nanoparticles in water leads to a transient heating of the nanoparticles, which decays via heat transfer to the water phase. It is shown that the water temperature rises to near the critical temperature and the water undergoes an explosive evaporation in the subnanosecond range. The formation of vapor bubbles shows a threshold dependence on laser fluence. The nascent nanoscale vapor bubbles change the heat dissipation drastically. The nanoscale structure is resolved directly with a combination of x-ray scattering methods sensitive to the particle lattice expansion and the change in the water structure factor.

Cavitation dynamics on the nanoscale

The ultrafast excitation of gold nanoparticle sols causes a strong nonequilibrium heating of the particle lattice and subsequently of the water shell close to the particle surface. Above a threshold in laser fluence, which is defined by the onset of homogeneous nucleation, nanoscale vapor bubbles develop around the particles, expand and collapse again within the first nanosecond after excitation. We show the existence of cavitation on the nanometer and subnanosecond time scale, described within the framework of continuum thermodynamics.

Nanoparticle formation in a cavitation bubble after pulsed laser ablation in liquid studied with high time resolution small angle x-ray scattering

We investigated nanoparticle formation after pulsed laser ablation in liquid using time-resolved small angle x-ray scattering. Laser ablation of a gold target in water induces a cavitation bubble in which two different particle species could be identified at maximum bubble extension: (i) primary particles of about 8–10 nm diameter, which show a smooth concentration gradient starting from the target and can also be found outside the cavitation bubble in the free liquid and (ii) secondary particles in the range of 45 nm diameter which have highest concentration in the upper part of the cavitation bubble but do not penetrate into the liquid.

Thermodynamics of nanosecond nanobubble formation at laser-excited metal nanoparticles

The nonlinear thermal behavior of laser-heated gold nanoparticles in aqueous suspension is determined by time-resolved optical spectroscopy and x-ray scattering. The nanoparticles can be excited transiently to high lattice temperatures owing to their large absorption cross-section and slow heat dissipation to the surrounding. A consequence is the observation of lattice expansion, changed optical transmission, vapor bubble formation or particle melting. The heat transfer equations are solved for two limiting cases of heat pulses shorter and longer than the characteristic cooling time. The results of pulsed excitation with femtosecond and nanosecond lasers are explained by the theoretical prediction, and the bubble formation is interpreted by a spinodal decomposition at the particle–liquid interface. It is shown that both the laser spectroscopy and x-ray scattering results agree qualitatively and quantitatively, underlining the validity of the comprehensive model.

Chopper system for time resolved experiments with synchrotron radiation

A chopper system for time resolved pump-probe experiments with x-ray beams from a synchrotron is described. The system has three parts: a water-cooled heatload chopper, a high-speed chopper, and a millisecond shutter. The chopper system, which is installed in beamline ID09B at the European Synchrotron Radiation Facility, provides short x-ray pulses for pump-probe experiments with ultrafast lasers. The chopper system can produce x-ray pulses as short as 200 ns in a continuous beam and repeat at frequencies from 0 to 3 kHz. For bunch filling patterns of the synchrotron with pulse separations greater than 100 ns, the high-speed chopper can isolate single 100 ps x-ray pulses that are used for the highest time resolution. A new rotor in the high-speed chopper is presented with a single pulse (100 ps) and long pulse (10 micros) option. In white beam experiments, the heatload of the (noncooled) high-speed chopper is lowered by a heatload chopper, which absorbs 95% of the incoming power without affecting the pulses selected by the high speed chopper.

A hierarchical view on material formation during pulsed-laser synthesis of nanoparticles in liquid.

Pulsed-laser assisted nanoparticle synthesis in liquids (PLAL) is a versatile tool for nanoparticle synthesis. However, fundamental aspects of structure formation during PLAL are presently poorly understood. We analyse the spatio-temporal kinetics during PLAL by means of fast X-ray radiography (XR) and scanning small-angle X-ray scattering (SAXS), which permits us to probe the process on length scales from nanometers to millimeters with microsecond temporal resolution. We find that the global structural evolution, such as the dynamics of the vapor bubble can be correlated to the locus and evolution of silver nanoparticles. The bubble plays an important role in particle formation, as it confines the primary particles and redeposits them to the substrate. Agglomeration takes place for the confined particles in the second bubble. Additionally, upon the collapse of the second bubble a jet of confined material is ejected perpendicularly to the surface. We hypothesize that these kinetics influence the final particle size distribution and determine the quality of the resulting colloids, such as polydispersity and modality through the interplay between particle cloud compression and particle release into the liquid.

The realization of sub-nanosecond pump and probe experiments at the ESRF

We present beamline ID09B that is designed for pump and probe experiments to 50 ps time-resolution. The beamline has been refurbished with a narrow-bandwidth undulator for Laue diffraction and diffraction from liquids. The new undulator has 235 poles, a 17 mm magnetic period and is operated at 6.5 mm gap. It produces a spectral flux of 2.0 x 10(8) photon/0.1% bw/pulse (10 mA) at the fundamental at 15.5 keV and an integral flux of 1.1 x 10(10) photon pulse(-1) in a 2.5% bandwidth. The optics has been renewed with a high-precision toroidal mirror and a cryogenic monochromator. The X-ray chopper used for single pulse selection is also described together with the femtosecond laser. Finally the diffraction from excited iodine molecules in CCl4 is investigated on the nanosecond time-scale. It turns out that the high-angle scattering is insensitive to the thermal chock from the laser: these oscillations are therefore readily used for structure determination. Conversely, the low-angle scattering probes the hydrodynamics of the liquid over longer length scales and the oscillations are believed to originate from thermal stress and expansion of the solvent.

Ultrafast X-Ray Solution Scattering Reveals an Unknown Reaction Intermediate in the Photolysis of [Ru3(CO)12]†

With the exception ofultrafastinfraredspectroscopy,whichhasbeenmostefficientin identifying intermediates based on the detection ofbridgingCOligands,mosttechniqueshavefailedtocharac-terize the structure of the intermediates. Recent ultrafastinfraredspectroscopicmeasurementshaveshownthatwhensolutions of [Ru

Ultrafast structural dynamics of the photocleavage of protein hybrid nanoparticles.

Protein-coated gold nanoparticles in suspension are excited by intense laser pulses to mimic the light-induced effect on biomolecules that occur in photothermal laser therapy with nanoparticles as photosensitizer. Ultrafast X-ray scattering employed to access the nanoscale structural modifications of the protein-nanoparticle hybrid reveals that the protein shell is expelled as a whole without denaturation at a laser fluence that coincides with the bubble formation threshold. In this ultrafast heating mediated by the nanoparticles, time-resolved scattering data show that proteins are not denatured in terms of secondary structure even at much higher temperatures than the static thermal denaturation temperature, probably because time is too short for the proteins to unfold and the temperature stimulus has vanished before this motion sets in. Consequently the laser pulse length has a strong influence on whether the end result is the ligand detachment (for example drug delivery) or biomaterial degradation.

Ultrashort laser pulse induced nanogratings in borosilicate glass

We report on nanogratings inscribed by repetitive femtosecond laser pulses into the bulk of borosilicate glass. The irradiation produces small nanopores (10–20 nm thick) which start to self-organize in gratings as well as elongated sheets of up to 400 nm length. A quantitative description of the grating structure and its development are obtained by a combination of focused ion beam milling, scanning electron microscopy, and small angle X-ray scattering (SAXS). The SAXS partial invariant of the thin sheets is found to correlate well with the measured optical retardance. Compared to fused silica nanogratings borosilicate glass shows a much smaller retardance due to re-annealing of pores. In addition, the nanograting period strongly deviates from the well-known λ/2n prediction. We could observe periods down to 60 nm (at an inscribing wavelength of 800 nm). This has not been observed yet in other glasses.