Effect of picosecond laser induced cavitation bubbles generated on Au targets in a nanoparticle production set-up

This work is aimed at an analysis of the influence on the efficiency of nanoparticle production of a cavitation bubble (CB), which forms during the laser ablation process in high-fluence regime. The CB is produced on an Au metal target immersed in water by 1064 nm ps Nd:YAG laser pulses at different fluences. Its time–space evolution is monitored by a shadowgraphic set-up, while the Au nanoparticles production rate is tagged by the growth of the plasmon resonance, which is detected by measuring shot-by-shot the UV-Vis absorbance. We analyze the dependence of bubble size on the experimental parameters. Our results appear of interest to enhance the nanoparticle production efficiency in a liquid medium.     

1064-nm laser fragmentation of thin Au and Ag flakes in acetone for highly productive pathway to stable metal nanoparticles

The laser-induced fragmentation of thin Au and Ag flakes in acetone by 1064-nm nanosecond laser (with the fluence typically ∼2 J/cm²) potentially offers a highly productive pathway to stable metal nanoparticles in liquid. Acetone serves as a superior liquid medium that keeps fine metal nanoparticles free from precipitation even in such concentrated nanoparticle solutions exceeding ∼0.1 M. Thin metal flakes have good capability to absorb the 1064-nm laser energy as efficiently as in the visible region. A part of the thus laser-heated molten flakes explosively split into submicroparticles, and some other significant part directly into fine nanoparticles. Both kinds of product particles have minor absorption cross-sections for subsequent laser pulses at 1064 nm, and thus no longer fragment further. One of the two kinds of Ag flakes studied in this work yielded fine Ag nanoparticles at a remarkable high production rate of 1.1 mg/min for the input laser power of only ∼0.65 W.     

In-situ study of Ag nanoparticle hydrosol optical spectra evolution during laser ablation/fragmentation

The results of in-situ monitoring of a laser fragmentation process of a largely polydisperse and morphologically heterogeneous citrate-reduced Ag hydrosol containing a fraction of Ag nanowires are presented. The laser fragmentation was performed using several wavelengths of the incident laser pulses (1064, 532 and 355 nm). Surface plasmon extinction spectra monitoring the nanoparticle fragmentation process were acquired pulse by pulse and related to transmission electron microscopy (TEM) images and statistical TEM image analysis of Ag nanoparticles collected in selected stages of the fragmentation. It was found that, due to different interactions of the laser pulses of various wavelengths with a specific fraction of the Ag nanoparticles in the hydrosol, the course of the fragmentation process depends on the wavelength, leading to different size distributions of the nanoparticles in the resulting hydrosol. The laser pulses of 532 nm wavelength are the most effective for the fragmentation process of the citrate-reduced Ag hydrosol, yielding the narrowest size distribution and the smallest mean radius of the Ag nanoparticles. PACS 81.07.-b; 73.21.-b; 81.16.-c     

Laser vaporisation of absorbing liquid under transparent cover

Vaporization of absorbing liquid (water) under a transparent solid cover upon exposure to nanosecond pulses of a holmium laser (λ = 2920 nm) is studied using acoustic and optical diagnostics. The features of the optical signal reflected from the liquid–cover interface suggest that a vapor cavity appears at a submicrometer distance from this interface and exists for about one hundred microseconds. An additional acoustic signal appearing after returning the light signal to the initial level is caused by known cavitation effects accompanying vapor cavity fracture and collapse in liquid.     

Excitation of high energy levels under laser exposure of suspensions of nanoparticles in liquids

Laser exposure of suspensions of nanoparticles in liquids leads to excitation of high energy levels in both liquid and nanoparticle material. The emission spectrum of the colloidal solution under exposure of a suspension metallic nanoparticles in water to radiation of a Nd:YAG laser of a picosecond range of pulse duration is discussed. Excitation of nuclear energy levels and neutron release is experimentally studied on the model system of transmutation of Hg into Au that occurs under exposure of Hg nanodrops suspended in D₂O. The proposed mechanism involves: (i) emission of X-ray photons by Hg nanoparticles upon laser exposure, leading to neutron release from D₂O, (ii) initiation of Hg → Au transmutation by the capture of neutrons. The effect of transmutation is more pronounced using ¹⁹⁶Hg isotope instead of Hg of natural isotope composition. The influence of laser pulse duration on the degree of transmutation (from fs through ns range) is discussed.     

Effect of submillisecond radiation of the erbium laser on absorbing liquid

Pressure pulses occurring in water under the effect of submillisecond radiation of the Er³⁺:YAG laser on the free and covered liquid surface were measured. The behavior of pressure pulses is caused by the photoacoustic effect, explosive boiling of the superheated liquid surface layer, and cavitation processes developing after laser exposure.     

Synthesis of nanoparticles and suspensions by pulsed laser ablation of microparticles in liquid

Recent studies demonstrated that the process to produce metal and oxide nanoparticles by laser ablation of consolidated microparticles is a convenient and energy-efficient way to prepare nanoparticles. In this work, the novel process is applied to nanoparticle synthesis in the liquid environment and the results are compared with those by the gas-phase process. Metal and oxide nanoparticles are synthesized by pulsed laser ablation of the compacted metal microparticles using a Q-switched Nd:YAG laser in water. It is shown that the process is effective for preparing nanoparticle suspensions having relatively uniform size distributions. While the laser fluence and the degree of compaction strongly influence the size of the produced nanoparticle in air, the sedimentation time is shown to be the most critical factor to determine the mean size of the suspended particles.     

Excimer laser-assisted annealing of silicate glass with ion-synthesized silver nanoparticles

The effect of KrF excimer laser radiation on a composite layer consisting of sodium-potassium silicate glass with silver nanoparticles is studied as a function of the number of laser nanosecond pulses. The silver nanoparticles are synthesized by ion implantation. The measured optical absorption of the composite layer demonstrates that the silver nanoparticle size decreases monotonically as the number of laser pulses increases. Rutherford backscattering shows that laser annealing is accompanied by silver diffusion into the bulk of the glass and partial metal evaporation from the sample surface. The detected decrease in the silver nanoparticle size is discussed in terms of simultaneous melting of silver nanoparticles and the glass matrix due to the absorption of laser radiation.     

Sound generation in the atmosphere upon exposure to high-power milli- and microsecond laser pulses

A review of works on generation of acoustic pulses in the atmosphere upon exposure to high-power laser pulses is presented in this paper. Characteristics of sound pulses in the atmosphere accompanying the propagation of high-power milli- and microsecond laser pulses, including the peak sound pressure level and the shape and spectrum of acoustic pulses, are discussed. The special features of acoustic pulses from individual liquid and solid aerosol particles and ensembles of monodisperse particles and polydisperse atmospheric aerosol are discussed. The characteristics of acoustic signals from long laser sparks and collective optical discharges are considered.     

Temporal and Spectral Characterization of Breakdown Plasma Induced by Laser Radiation in Colloidal Solutions of Gold Nanoparticles

Temporal and spectral characteristics of laser-induced breakdown plasma in colloidal solutions of gold nanoparticles were experimentally studied. Near-infrared laser sources of nanosecond pulses were used. It was shown that under certain experimental conditions nanosized plasma around nanoparticles might change to laser-induced breakdown plasma in liquid. The dependencies of the plasma temporal and spectral characteristics on laser pulse duration as well as resulting nanoparticles properties were studied. Laser-induced breakdown plasma lifetime was shown to be comparable with laser pulse duration. The efficiency of gold nanoparticles fragmentation was shown to depend on laser pulse duration. Similar experiments were carried out under reduced external pressure. It turned out to affect the properties of both plasma plume and nanoparticles. Transmission electron microscopy and disc measuring centrifuge were used for nanoparticle morphology and size analysis. Extinction spectra of colloidal solutions and emission spectra of plasma were studied by means of optical spectroscopy.     

Synthesis and investigation of stable copper nanoparticle colloids

The synthesis of stable nanoparticle colloids by laser ablation of the copper target in water and fragmentation of Cu + CuO nanopowder with pulsed fiber laser irradiation with a wavelength of 1064 nm and pulse duration of 100 ns has been investigated experimentally. The influence of the technological parameters on the nanoparticle size and stability of the colloid has been studied. It has been shown that the laser ablation creates the CuO spherical nanoparticles. Subsequent fragmentation makes it possible to reduce the nanoparticle size in a colloid and to produce a stable colloidal solution from an aqueous suspension of Cu + CuO nanopowder.     

In-situ bioconjugation in stationary media and in liquid flow by femtosecond laser ablation

In-situ functionalization of gold nanoparticles with fluorophore-tagged oligonucleotides is studied by comparing femtosecond laser ablation in stationary liquid and in biomolecule flow. Femtosecond laser pulses induce significant degradation to sensitive biomolecules when ablating gold in a stationary solution of oligonucleotides. Contrary, in-situ conjugation of nanoparticles in biomolecule flow considerably reduces the degree of degradation studied by gel electrophoresis and UV–Vis spectrometry. Ablating gold with 100 μJ femtosecond laser pulses DNA sequence does not degrade, while the degree of fluorophore tag degradation was 84% in stationary solution compared to 5% for 1 mL/min liquid flow. It is concluded that femtosecond laser-induced degradation of biomolecules is triggered by absorption of nanoparticle conjugates suspended in the colloid and not by ablation of the target. Quenching of nanoparticle size appears from 0.5 μM biomolecule concentration for 0.3 μg/s nanoparticle productivity indicating the successful surface functionalization. Finally, increasing the liquid flow rate from stationary to 450 mL/min enhances nanoparticle productivity from 0.2 μg/s to 1.5 μg/s, as increasing liquid flow allows removal of light absorbing nanoparticles from the ablation zone, avoiding attenuation of subsequent laser photons.     

Influence of processing time on nanoparticle generation during picosecond-pulsed fundamental and second harmonic laser ablation of metals in tetrahydrofuran

The influence of fundamental and second harmonic wavelength on ablation efficiency and nanoparticle properties is studied during picosecond laser ablation of silver, zinc, and magnesium in polymer-doped tetrahydrofuran. Laser ablation in stationary liquid involves simultaneously the fabrication of nanoparticles by ablation of the target material and fragmentation of dispersed nanoparticles by post irradiation. The ratio in which the laser pulse energy contributes to these processes depends on laser wavelength and colloidal properties. For plasmon absorbers (silver), using the second harmonic wavelength leads to a decrease of the nanoparticle productivity over process time along with exponential decrease in particle diameter, while using the fundamental wavelength results in a constant ablation rate and linear decrease in particle diameter. For colloids made of materials without plasmon absorption (zinc, magnesium), laser scattering is the colloidal property that limits nanoparticle productivity by Mie-scattering of dispersed nanoparticle clusters.     

AFM investigation of nanoparticles formed on silicon surface by femtosecond laser pulses

It is shown by atomic force microscopy that nanoparticles formed upon ablation of surface of single-crystal and porous silicon by femtosecond laser pulses have a lateral size from several tens to 200 nm and a height from 2 to 30 nm. Dependences of the nanoparticle sizes and surface concentrations on the residual pressure, which demonstrate the gas atmosphere influence on the nanoparticle formation, are obtained.     

Growth of ZnO nanoparticles and nanorods with ultrafast pulsed laser deposition

In this work, we study the application of ultrafast pulsed laser deposition (PLD) in ZnO nanomaterial synthesis, including nanoparticles and nanorods. PLD using long pulse (nanosecond) lasers has been widely used as a method for growing prototype materials. The recently-emerged ultrafast PLD is expected to be able to overcome the problem of large liquid droplet formation. Using near infrared and femtosecond laser pulses in ablation, we first characterize the ablation plume using a Langmuir probe and plasma optical emission spectroscopy. We then examine the structural properties of the nanoparticles generated during low-fluence ablation. Finally, we demonstrate that using nanoparticle aggregates as templates, assisted by plume-excited nitrogen radicals at a high fluence, high quality ZnO nanorods can be grown free of metal catalysts.     

Metal nanoparticle production by pulsed laser nanostructuring of thin metal films

The controllable nanostructuring of thin metal films by nanosecond UV laser pulses is introduced as a novel technique for the production of metal nanoparticles supported on a range of different oxide substrates, including indium tin oxide. This processing is performed at low macroscopic temperatures. The physical mechanisms underlying the nanostructuring are discussed and applications for these nanoparticle films, including as catalysts for nanotube/nanowire growth and in surface enhanced Raman spectroscopy measurements, are introduced.     

Numerical modeling of short pulse laser interaction with Au nanoparticle surrounded by water

Short pulse laser interaction with a metal nanoparticle surrounded by water is investigated with a hydrodynamic computational model that includes a realistic equation of state for water and accounts for thermoelastic behavior and the kinetics of electron-phonon equilibration in the nanoparticle. Computational results suggest that, at laser fluences close to the threshold for vapor bubble formation, the region of biological damage due to the laser-induced thermal spike and the interaction of the pressure wave with internal cell structures can be localized within short distances from the absorbing particle comparable to the particle diameter. This irradiation regime is suitable for targeted generation of thermal and mechanical damage at the sub-cellular level.     

Laser fragmentation of organic microparticles into colloidal nanoparticles in a free liquid jet

We present a novel approach for laser fragmentation of melamine cyanurate microcrystals suspended in liquid into colloidal nanoparticles. Laser fragmentation is done by irradiating a liquid jet of melamine cyanurate suspended in water with intense picosecond pulses. The free liquid jet is generated by a nozzle with small diameter and provides a thin liquid filament (d _fil<1 mm) perpendicular to the focused laser beam. This geometry allows tight focusing resulting in high intensities without the danger of damaging an optical element like windows necessary in conventional flow cells or cuvettes. It reduces losses of excitation light by avoiding scattering or absorption in front of the focus. We stabilized the nanoparticles electrosterically in-situ with neutral and polyelectrolytic polymers preventing agglomeration and precipitation. The threshold for sufficient stabilization of laser-fragmented nanoparticles (d _hydrodyn≈200 nm) is reached at a mass fraction of 0.25 wt% dextrin as a neutral polymer and 0.01 wt% polyacrylic acid as a polyelectrolytic polymer. Hydrodynamic size and zeta-potential of the nanoparticles can be controlled by mass fraction of the stabilization agent.     

Self-organization in a chromium thin film under laser irradiation

Self-organization of chromium on glass was observed during laser ablation of the metal film with partially overlapping laser pulses. The beam of a nanosecond pulse laser tightly focused to a line was applied to the back-side ablation of the chromium thin film on a glass substrate. While the line ablated with a single laser pulse had sharp edges on both sides with ridges of the melted metal, the use of partially overlapping pulses formed a complicated structure made of the metal remaining from the ridges. Regular structures of ripples were developed in a certain range of laser fluence and pulse overlap. The ripple period could be controlled from 2.5 to 4 μm by variation of the processing parameters. Various experimental techniques were applied to test the structures, and different models of the ripple formation in the thin metal film were considered. The initial quasi-periodical formation started because of dewetting of thin liquid metal films on the glass substrate after its melting. Similar to the evaporation of liquid films, the small perturbation in the ridge thickness was able to induce instability in evaporation of the thin melted metal film. Freezing of the nonequilibrium state between laser pulses was one of the stabilizing factors in self-organization of the metal.     

Physical fabrication of colloidal ZnO nanoparticles combining wet-grinding and laser fragmentation

Combination of wet-grinding and laser fragmentation is a promising approach to advance both methods: Laser fragmentation will be more efficient when combined with mechanical treatment and wet-grinding may take advance of the abrasion-free laser process to achieve fabrication of smaller particles. By mechanical pre-treatment of zinc oxide microparticles in a stirred-media mill, the starting material is activated by generation of crystallographic defects, which strongly enhance the efficiency of subsequent laser fragmentation. Picosecond-laser irradiation of mechanically treated and untreated microparticles suspended in water yielded in colloidal zinc oxide nanoparticles. Furthermore, nanoparticle productivity and properties can be controlled by variation of anionic surfactant concentration.