Single Femtosecond Laser-Pulse-Induced Superficial Amorphization and Re-Crystallization of Silicon.

Superficial amorphization and re-crystallization of silicon in <111> and <100> orientation after irradiation by femtosecond laser pulses (790 nm, 30 fs) are studied using optical imaging and transmission electron microscopy. Spectroscopic imaging ellipsometry (SIE) allows fast data acquisition at multiple wavelengths and provides experimental data for calculating nanometric amorphous layer thickness profiles with micrometric lateral resolution based on a thin-film layer model. For a radially Gaussian laser beam and at moderate peak fluences above the melting and below the ablation thresholds, laterally parabolic amorphous layer profiles with maximum thicknesses of several tens of nanometers were quantitatively attained. The accuracy of the calculations is verified experimentally by high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (STEM-EDX). Along with topographic information obtained by atomic force microscopy (AFM), a comprehensive picture of the superficial re-solidification of silicon after local melting by femtosecond laser pulses is drawn.

Characterization of self-assembled metallodendrimers in solution, in the gas phase, and at air/solid interfaces.

It is found that 4,4'-bipyridines functionalized in their 3,3'-positions with Fréchet dendrons of 0th to 3rd generation self-assemble with (dppp)M(II) triflates (dppp: bis-(diphenylphosphino)propane; M = Pd, Pt) into metallo-supramolecular squares. They bear a nanometer-sized cavity inside an unpolar dendritic shell. A total of eight amide groups decorate the rims of the cavity connecting the dendrons to the square. Evidence for their formation up to the third generation comes from ESI-FTICR mass spectrometry and NMR experiments. Based on these results, the presence of significant amounts of other polygons or open-chain oligomers can be excluded. Exchange processes have been studied by variable-temperature NMR spectroscopy and by following the ligand exchanges between different squares by mass spectrometry. The ligand exchange is much slower for the Pt(II) squares as compared to their Pd(II) analogs. Visualization of films of these dendrimers using atomic force microscopy (AFM) provides information on their molecular dimensions. After deposition of a square monolayer on the surface, a slow reorganization within this layer is observed which leads to the formation of "tower-like" aggregates and multi-layer formation. The interplay of interactions between the dendrimers and the surface and interactions between different dendrimers are invoked to rationalize the observations.

Electrochemistry of nano-scale bacterial surface protein layers on gold.

The mechanism of the recrystallization of nano-scale bacterial surface protein layers (S-layers) on solid substrates is of fundamental interest in the understanding and engineering of biomembranes and e.g. biosensors. In this context, the influence of the charging state of the substrate had to be clarified. Therefore, the electrochemical behaviour of the S-layers on gold electrodes has been investigated by in-situ electrochemical quartz microbalance (EQMB) measurements, scanning force microscopy (SFM) and small-spot X-ray photoelectron spectroscopy (SS-XPS) of potentiostatically emersed substrates. It was shown that the negatively charged bonding sites of the S-layer units (e.g. carboxylates) can bond with positively charged Au surface atoms in the positively charged electrochemical double layer region positive of the point of zero charge ( approximately -0.8 V vs. saturated mercury-mercurous sulphate electrode). Surface conditions in other potential regions decelerated the recrystallization and fixation of S-layers. Time-resolved in-situ and ex-situ measurements demonstrated that two-dimensional S-layer crystal formation on gold electrodes can occur within few minutes in contrast to hours common in self-assembled monolayer (SAM) generation. These results proved that the recrystallization and fixation of 2D-crystalline S-layers on an electronic conductor can be influenced and controlled by direct electrochemical manipulation.