Shyjumon Ibrahimkutty

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.

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.

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.

Pulsed laser ablation in liquids: Impact of the bubble dynamics on particle formation

Pulsed laser ablation in liquids (PLAL) is a multiscale process, involving multiple mutually interacting phenomena. In order to synthesize nanoparticles with well-defined properties it is important to understand the dynamics of the underlying structure evolution. We use visible-light stroboscopic imaging and X-ray radiography to investigate the dynamics occurring during PLAL of silver and gold on a macroscopic scale, whilst X-ray small angle scattering is utilized to deepen the understanding on particle genesis. By comparing our results with earlier reports we can elucidate the role of the cavitation bubble. We find that symmetry breaking at the liquid-solid interface is a critical factor for bubble motion and that the bubble motion acts on the particle distribution as confinement and retraction force to create secondary agglomerates.

A portable ultrahigh-vacuum system for advanced synchrotron radiation studies of thin films and nanostructures: EuSi2 nano-islands

A portable ultrahigh-vacuum system optimized for in situ variable-temperature X-ray scattering and spectroscopy experiments at synchrotron radiation beamlines was constructed and brought into operation at the synchrotron radiation facility ANKA of the Karlsruhe Institute of Technology, Germany. Here the main features of the new instrument are described and its capabilities demonstrated. The surface morphology, structure and stoichiometry of EuSi2 nano-islands are determined by in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy. A size reduction of about a factor of two of the nano-islands due to silicide decomposition and Eu desorption is observed after sample annealing at 1270 K for 30 min.

Asynchronous sampling for ultrafast experiments with low momentum compaction at the ANKA ring.

A high-repetition-rate pump-probe experiment is presented, based on the asynchronous sampling approach. The low-α mode at the synchrotron ANKA can be used for a time resolution down to the picosecond limit for the time-domain sampling of the coherent THz emission as well as for hard X-ray pump-probe experiments, which probe structural dynamics in the condensed phase. It is shown that a synchronization of better than 1 ps is achieved, and examples of phonon dynamics of semiconductors are presented.

Structural study of near-field ablation close to plasmon-resonant nanotriangles

The optical near fields in close vicinity to plasmonic nanoscale objects show a considerable enhancement of the electrical field and are localized to dimensions much less than the wavelength of light. The authors show that an ablation process caused by the near-field enhancement of femtosecond laser pulses pattern the substrate below gold nanotriangles is a way to image the near-field distribution with a resolution below 20 nm. The mechanism of ablation studied by pulsed x-ray scattering reveals the nonthermal nature of the process.

Direct Observation of the Thickness-Induced Crystallization and Stress Build-Up during Sputter-Deposition of Nanoscale Silicide Films

The kinetics of phase transitions during formation of small-scale systems are essential for many applications. However, their experimental observation remains challenging, making it difficult to elucidate the underlying fundamental mechanisms. Here, we combine in situ and real-time synchrotron X-ray diffraction (XRD) and X-ray reflectivity (XRR) experiments with substrate curvature measurements during deposition of nanoscale Mo and Mo1-xSix films on amorphous Si (a-Si). The simultaneous measurements provide direct evidence of a spontaneous, thickness-dependent amorphous-to-crystalline (a-c) phase transition, associated with tensile stress build-up and surface roughening. This phase transformation is thermodynamically driven, the metastable amorphous layer being initially stabilized by the contributions of surface and interface energies. A quantitative analysis of the XRD data, complemented by simulations of the transformation kinetics, unveils an interface-controlled crystallization process. This a-c phase transition is also dominating the stress evolution. While stress build-up can significantly limit the performance of devices based on nanostructures and thin films, it can also trigger the formation of these structures. The simultaneous in situ access to the stress signal itself, and to its microstructural origins during structure formation, opens new design routes for tailoring nanoscale devices.

Ultrafast laser pump X-ray probe experiments by means of asynchronous sampling

A high time resolution in the picosecond range is required for the time-domain investigation of phonon dynamics in crystalline systems. Following a recently developed scheme in the visible spectrum, this resolution can be achieved by a method called asynchronous optical x-ray sampling (ASOXS). A pulsed femtosecond laser with high repetition rate is synchronized to the electron bunches in a storage ring. A slight frequency detuning changes the mutual delay continuously, resulting in a time-domain x-ray sampling of the laser-excited system. At the synchrotron radiation source ANKA a machine mode with low momentum compaction factor αc is available, which delivers ultra-short x-ray pulses in the picosecond range.

Ultrafast X-ray scattering on nanoparticle dynamics

Pulsed X-ray scattering is used for the determination of structural dynamics of laser-irradiated gold particles. By combining several scattering methods such as powder scattering, small angle scattering and diffuse wide angle scattering it is possible to reconstruct the kinetics of structure evolution on several lengths scales and derive complementary information on the particles and their local environment. A generic structural phase diagram for the reaction as function of delay time after laser excitation and laser fluence can be constructed.