CdSe quantum dots-poly(3-hexylthiophene) nanocomposite sensors for selective chloroform vapor detection at room temperature Appl. Phys. Lett. 101, 173108 (2012) An "edge to edge" jigsaw-puzzle two-dimensional vapor-phase transport growth of high-quality large-area wurtzite-type ZnO (0001) nanohexagons Appl. Phys. Lett. 101, 173105 (2012) Ti-doped hematite nanostructures for solar water splitting with high efficiency J. Appl. Phys. 112, 084312 (2012) Near-infrared enhanced carbon nanodots by thermally assisted growth
The formation of nanoparticles within the laser-induced cavitation bubble is studied in situ using small angle X-ray scattering with high spatiotemporal resolution. Directly after laser ablation, two different particle fractions consisting of compact primary particles of 8-10 nm size and agglomerates of 40-60 nm size are formed. The abundance of these species is strongly influenced by the dynamics of the oscillating cavitation bubble. Primary particle mass is most abundant during maximal expansion of the first bubble and reappears a little weaker in the rebound. In contrast to this, the mass abundance of agglomerates is relatively low in the first bubble but strongly increases during first bubble collapse and following rebound. Although most of the ablated material is trapped inside the bubble and follows its oscillation, a minor fraction of both species could be detected outside the cavitation bubble even before its final collapse.
Although the first nanoseconds to microseconds rule the resulting process yield of laser ablation in liquid, a comprehensive view involving combination of time-resolved measurement techniques is still lacking. In this paper, fundamental aspects of laser ablation of metals in water during the production of nanoparticles are discussed. Three fast diagnostic methods have been applied simultaneously. These are Optical Emission Spectroscopy for the plasma characterization, fast shadowgraph for plasma and cavitation bubble dynamics and laser scattering for the mechanisms of delivery of the produced materials in the liquid. Moreover, in order to validate the discussion, the effect on cavitation dynamics of the ablation of bulk and wire-shaped targets has been investigated together with the relative nanoparticles production yield. Unusual arrow-bow ejection phenomena between the cavitation bubble and the wire result in suppressed material back-deposition, causing efficient ejection of ablated matter into the liquid. The presented nanosecond and microsecond-resolved analysis allows estimating the timescale and role of the basic mechanisms involved in laser ablation in liquids as well as the thermodynamic characteristics of the processes.
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.
Residual ligands from colloidal synthesis of nanoparticles influence adsorption of nanoparticles to supports and may complicate fabrication of nanoparticle-decorated microparticles. In this work, we studied the adsorption of completely ligand-free metal nanoparticles and controlled ligand-functionalized nanoparticles to chemically inert microparticle supports. Adsorption of ligand-free silver nanoparticles to barium sulfate microparticle supports is a quantitative, nonreversible process following Freundlich adsorption isotherm. However, adsorption efficiency is very sensitive to ligand concentration applied during laser-based synthesis of silver nanoparticles: exceeding a specific threshold concentration of 50 μmol/L citrate equal to a nanoparticle ligand surface coverage of about 50%, results in an almost complete prevention of nanoparticle adsorption because of electrosteric repulsion by ligand shell. Laser-based synthesis of nanoparticle-decorated microparticles is demonstrated with a variety of metal nanoparticles (Ag, Au, Pt, Fe) and supporting microparticles (calcium phosphate, titanium dioxide, barium sulfate) with application potential in heterogeneous catalysis or biomedicine where ligand control offers extra value, like enhanced catalytic activity or biocompatibility.
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