Laser induced synthesis of nanoparticles in liquids

The review of results on nanoparticles formation is presented under laser ablation of Ag, Au, and Cu-containing solid targets in liquid environments (H₂O, C₂H₅OH, C₂H₄Cl₂, etc.). X-ray diffractometry (XRD), UV-vis optical transmission spectrometry, and high resolution transmission electron microscopy (HRTEM) characterize the nanoparticles. The morphology of nanoparticles is studied as the function of both laser fluence and nature of the liquid. The possibility to control the shape of nanoparticles by ablation of an Au target by an interference pattern of two laser beams is demonstrated. Formation of alloyed Au-Ag and Ag-Cu nanoparticles is reported under laser exposure of a mixture of individual nanoparticles. The effect of internal segregation of brass nanoparticles is discussed due to their small lateral dimensions. The factors are discussed that determine the distribution function of particles size under laser ablation. The influence of laser parameters as well as the nature on the liquid on the properties of nanoparticles is elucidated.     

Femtosecond laser ablation characteristics of nickel-based superalloy C263

Femtosecond laser (180 fs, 775 nm, 1 kHz) ablation characteristics of the nickel-based superalloy C263 are investigated. The single pulse ablation threshold is measured to be 0.26±0.03 J/cm² and the incubation parameter ξ=0.72±0.03 by also measuring the dependence of ablation threshold on the number of laser pulses. The ablation rate exhibits two logarithmic dependencies on fluence corresponding to ablation determined by the optical penetration depth at fluences below ∼5 J/cm² (for single pulse) and by the electron thermal diffusion length above that fluence. The central surface morphology of ablated craters (dimples) with laser fluence and number of laser pulses shows the development of several kinds of periodic structures (ripples) with different periodicities as well as the formation of resolidified material and holes at the centre of the ablated crater at high fluences. The debris produced during ablation consists of crystalline C263 oxidized nanoparticles with diameters of ∼2–20 nm (for F=9.6 J/cm²). The mechanisms involved in femtosecond laser microprocessing of the superalloy C263 as well as in the synthesis of C263 nanoparticles are elucidated and discussed in terms of the properties of the material.     

Pulsed laser induced synthesis of scheelite-type colloidal nanoparticles in liquid and the size distribution by nanoparticle tracking analysis

Pulsed laser ablation (PLA) of ceramic target in liquid phase was successfully employed to prepare calcium tungstate (CaWO₄) and calcium molybdate (CaMoO₄) colloidal nanoparticles. The crystalline phase, particle morphology and optical property of the colloidal nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy. The produced stable colloidal suspensions consisted of the well-dispersed nanoparticles showing a spherical shape. The mechanism for the laser ablation and nanoparticle forming was discussed under consideration of photo-ablation process. Nanoparticle tracking analysis using optical microscope combined with image analysis was proposed to determine the size distribution function of the prepared colloidal nanoparticles. The mean size of the CaWO₄ and CaMoO₄ colloidal nanoparticles were 16 and 29 nm, with a standard deviations of 2.1 and 5.2 nm, respectively.     

Tailored ablation processing of advanced biomedical hydroxyapatite by femtosecond laser pulses

The micromachining of hydroxyapatite (HAp) is highly important for orthopedics and dentistry, since human bone and teeth consist mainly of HAp. We demonstrate ultrashort Ti:sapphire laser ablation of HAp, using pulse-widths of 50 fs, 500 fs, and 2 ps at a wavelength of 820 nm and at 1 kpps. The crucial medical issue is to preserve the chemical properties of the machined (ablated) surface. If the chemical properties of HAp change, the human bone or tooth cannot re-grow after laser processing. Using X-ray photoelectron spectroscopy, we observe chemical properties of HAp ablated in air. The HAp is ablated at laser fluences of 3.2 J/cm² (6.4×10¹³ W/cm² at 50 fs), 3.3 J/cm² (6.6×10¹² W/cm² at 500 fs), and 9.6 J/cm² (4.8×10¹² W/cm² at 2 ps), respectively. As a result it is found that the ablated surface is unchanged after laser ablation over the pulse-width range used in this experiment. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-45/566-1533, E-mail: obara@obara.elec.keio.ac.jp     

Thin films of silver nanoparticles deposited in vacuum by pulsed laser ablation using a YAG:Nd laser

We report the deposition of thin films of silver (Ag) nanoparticles by pulsed laser ablation in vacuum using the third line (355 nm) of a YAG:Nd laser. The nanostructure and/or morphology of the films was investigated as a function of the number of ablation pulses, by means of transmission electron microscopy and atomic force microscopy. Our results show that films deposited with a small number of ablation pulses (500 or less), are not continuous, but formed of isolated nearly spherical Ag nanoparticles with diameters in the range from 1 nm to 8 nm. The effect of increasing the number of pulses by one order of magnitude (5000) is to increase the mean diameter of the globular nanoparticles and also the Ag areal density. Further increase of the number of pulses, up to 10,000, produces the formation of larger and anisotropic nanoparticles, and for 15,000 pulses, quasi-percolated Ag films are obtained. The presence of Ag nanoparticles in the films was also evidenced from the appearance of a strong optical absorption band associated with surface plasmon resonance. This band was widened and its peak shifted from 425 nm to 700 nm as the number of laser pulses was increased from 500 to 15,000.     

High-quality hydroxyapatite coating on biocompatible materials by laser-assisted laser ablation method

A new method for high-quality hydroxyapatite (HAp) coating is developed, the laser-assisted laser ablation method. In this method, two lasers are used. One is used for ablation of a HAp target. The other, the assist laser, is used to irradiate a Ti substrate surface. The effects of the assist laser irradiation are to anneal the HAp coating and to improve its adhesive strength to the Ti substrate. The quality of the HAp coating depends on the delay time of the assist-laser irradiation. HAp coatings obtained at a delay time of 10 microseconds or more are more amorphous. It was confirmed that the amorphous part of a coating dissolves in simulated body fluid, while the crystalline part does not. The value of the Ca/P ratio in a coating obtained at a delay time of a few microseconds is close to the stoichiometric value. PACS 81.16.Mk     

Synthesis of CaWO<Subscript>4</Subscript> nanocolloidal suspension via pulsed laser ablation and its optical properties

Pulsed laser ablation (PLA) in the liquid phase was successfully employed to synthesize calcium tungstate (CaWO₄) nanocolloidal suspension. The crystalline phase, particle morphology and laser ablation mechanism for the colloidal nanoparticles were investigated using XRD, TEM and SEM. The obtained colloidal suspension consisted of well-dispersed CaWO₄ nanoparticles which showed a spherical shape with sizes ranging from 5 to 30 nm. The laser ablation and the nanoparticle forming process were discussed under consideration of the photo-ablation mechanism, where the nanoparticles were generated by rapid condensation of the plume in high pressured ethanol vapor. The optical properties of the prepared CaWO₄ colloidal nanoparticles were analyzed in detail using XPS, Raman spectroscopy, UV-Vis spectroscopy and PL spectrophotometry. The optical band gap was estimated by Tauc and Menths law. PACS 42.62.-b; 82.70.Dd; 78.55.Hx; 81.07.Wx     

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.     

Effect of deposition parameters on morphology and size of FeCo nanoparticles synthesized by pulsed laser ablation deposition

The experimental parameters that control the surface morphology and size of iron cobalt nanoparticles synthesized at room temperature by pulsed laser ablation deposition (PLAD) technique have been systematically investigated. The nanoparticle synthesis has been achieved at higher operating gas pressures of argon. It was found that nanoparticles upon deposition formed small clusters, the size of which increases with decreasing pressure, increasing laser-energy density, and decreasing target-to-substrate distance. This trend could be attributed to change in the kinetic energy of deposited nanoparticles with varying argon pressure, laser-energy, and target-to-substrate distance. The nanoparticles size and size distribution showed strong dependence on argon pressure and weak dependence on laser-energy density and target-to-substrate distance.     

Structural,optical, and nonlinear optical properties of indium nanoparticles prepared by laser ablation

A study of indium nanoparticles prepared by two laser ablation techniques is reported. The suspensions of indium nanoparticles were prepared using the laser ablation of bulk indium in liquids. The prepared suspensions of indium nanoparticles were analyzed by the X-ray fluorescence spectroscopy and absorption spectroscopy. The position of the surface plasmon resonance of In-containing suspensions (350 nm) was consistent with the estimations taking into account the average size of In nanoparticles (43 nm) measured using the X-ray fluorescence spectroscopy. The nonlinear optical parameters of indium nanoparticles-containing liquids were studied by the z-scan technique using a picosecond Nd:YAG laser. We compare the laser ablation in liquids with the laser ablation of indium in vacuum at the tight and weak focusing conditions of a Ti:sapphire laser and analyze the 60 nm indium nanoparticles synthesized in the latter case. PACS 42.65.An; 42.65.Hw; 42.65.Jx; 61.46.Df; 78.67.Bf     

Catalyst-free synthesis of vertically-aligned ZnO nanowires by?nanoparticle-assisted pulsed laser deposition

Vertically aligned ZnO nanowires have been successfully synthesized on c-cut sapphire substrates by a catalyst-free nanoparticle-assisted pulsed-laser ablation deposition (NAPLD) in Ar and N₂ background gases. In NAPLD, the nanoparticles formed in the background gas by laser ablation are used for the growth of the nanowires. The surface density of the nanowires can be controlled by varying the density of nanoparticles, which is in turn achieved by varying ablation laser parameters such as the energy and the repetition rate. When single ZnO nanowire synthesized in a N₂ background gas was excited by 355 nm laser-pulse with a pulse-width of 8 ns, stimulated emission was clearly observed, indicating high quality of the nanowire.     

Generation of higher harmonics of femtosecond radiation in clusters

The frequency conversion of laser radiation in cluster media is studied by the method of laser ablation of surfaces containing different nanoparticles (Cr₂O₃, In₂O₃, Ag, Sn, Au, and Cu). Using plasma that contains In₂O₃ nanoparticles as an example, it is shown that the resonant amplification of certain harmonics in the plateau-like distribution of harmonics, which is characteristic of the ablation of certain solid targets, is considerably modified in the case of targets that contain cluster formations. An increase in the conversion efficiency to harmonics in nanoparticle-containing media is discussed. In order to determine optimal characteristics of laser plasma with nanoparticles, their morphology is studied before and after laser ablation.     

II–VI semiconductor nanoparticles synthesized by laser ablation

Nanoparticles of the II–VI semiconductors CdTe, CdSe and ZnTe were synthesized by laser ablation (387 nm, 180 fs, 1 kHz, pulse energy of 7 μJ (fluence of 2 J/cm²)) of the target materials in methanol, de-ionized water and acetone. The nanoparticles size distributions follow log-normal functions with median diameters between about 6 and 11 nm for the several materials. The nanoparticles have the same crystalline structure as that of the corresponding bulk material and under the present conditions of ablation are rich in the higher volatility element of the two in the binary alloy and oxidized. Photoluminescence emission in the green-yellow (∼570 nm) was detected from CdSe nanoparticles.     

Nanoparticle formation during laser ablation of solids in liquids

The experimental data on the generation of metal and semiconductor nanoparticles during their laser ablation in liquids is reviewed. The dependence of the morphology of noble metal nanoparticles on the liquid type and laser parameters is discussed. The data on the kinetics of the formation of alloyed Au-Ag nanoparticles under laser irradiation of a mixture of colloid solutions of individual nanoparticles are presented. The effect of femtosecond laser beam self-action during metal ablation in liquids via the second harmonic generation at Ag nanoclusters is discussed. The data on the generation of core-shell nanoparticles during laser ablation of alloys and in the presence of the chemical interaction of formed nanoparticles with surrounding liquid are presented. It was shown that laser ablation of CdS and ZnSe crystals leads to the formation of quantum dots of these semiconductors in solution. The parameters controlling the properties of nanoparticles during ablation in liquids and possible applications of the method are discussed.     

Nanosecond pulsed laser ablation of silicon in liquids

Laser fluence and laser shot number are important parameters for pulse laser based micromachining of silicon in liquids. This paper presents laser-induced ablation of silicon in liquids of the dimethyl sulfoxide (DMSO) and the water at different applied laser fluence levels and laser shot numbers. The experimental results are conducted using 15 ns pulsed laser irradiation at 532 nm. The silicon surface morphology of the irradiated spots has an appearance as one can see in porous formation. The surface morphology exhibits a large number of cavities which indicates as bubble nucleation sites. The observed surface morphology shows that the explosive melt expulsion could be a dominant process for the laser ablation of silicon in liquids using nanosecond pulsed laser irradiation at 532 nm. Silicon surface’s ablated diameter growth was measured at different applied laser fluences and shot numbers in both liquid interfaces. A theoretical analysis suggested investigating silicon surface etching in liquid by intense multiple nanosecond laser pulses. It has been assumed that the nanosecond pulsed laser-induced silicon surface modification is due to the process of explosive melt expulsion under the action of the confined plasma-induced pressure or shock wave trapped between the silicon target and the overlying liquid. This analysis allows us to determine the effective lateral interaction zone of ablated solid target related to nanosecond pulsed laser illumination. The theoretical analysis is found in excellent agreement with the experimental measurements of silicon ablated diameter growth in the DMSO and the water interfaces. Multiple-shot laser ablation threshold of silicon is determined. Pulsed energy accumulation model is used to obtain the single-shot ablation threshold of silicon. The smaller ablation threshold value is found in the DMSO, and the incubation effect is also found to be absent.     

Fabrication and characterization of a granular film consisting of size-selected silver nanoparticles: application to a SERS substrate

Uniform-sized silver nanoparticles with average diameter of 13.7 nm have been prepared in the gas-phase by combining a pulsed laser ablation method with a low pressure-differential mobility analyzer (LP-DMA). By depositing the silver nanoparticles onto a silicon substrate, a granular film consisting of size-selected silver nanoparticles has been fabricated and its morphology and electronic properties have been examined using transmission electron microscopy (TEM) and UV-visible absorption spectroscopy. This granular silver film serves as a highly active substrate for surface-enhanced Raman scattering (SERS).     

Characterization of gaseous phase and nanoparticles produced in ultra-short pulsed laser ablation of transition metal borides

The plasma produced by ultra-short laser ablation of ZrB₂ and ReB₂ has been studied by ICCD imaging and time and space resolved optical emission spectroscopy. The aim was to clarify the mechanism of deposition leading to the morphology and composition found in the deposited films. The results indicate that for all systems the film characteristics are compatible with a deposition mechanism involving a growth from nanoparticles, ejected directly from the target, whose composition can be interpreted in terms of equilibrium vaporization during the flight from the target to the substrate.     

From polymer films to organic nanoparticles suspensions by means of excimer laser ablation in water

This study highlights the preparation of organic nanoparticles (NP) by laser ablation (LA) of polymeric materials in water. Experiments focused on poly(ethylene terephtalate) (PET) were carried out with the KrF laser pulse (248 nm). Size distribution and concentration of nanoparticles were deduced from suspensions turbidity measurements with the aid of Mie model, by Atomic Force Microscopy (AFM) on the basis of a statistical study and Scanning Electron Microscopy (SEM). The obtained results show that assemblies of spherical NP with a mean diameter 50 nm were synthesised. Composition and surface chemistry of NP were investigated using the Confocal Micro-Raman Spectroscopy (CMRS) and X-ray Photoelectron Spectroscopy (XPS). It indicates that NP are graphitic carbon rich and have a polymeric structure like polyacetylene. The possible mechanisms responsible of NP synthesis by under water LA of polymers was briefly discussed by investigating other polymers targets.     

Nanoparticles produced by laser ablation of solids in liquid environment

A review of results on nanoparticles formation is presented under laser ablation of Ag, Au, and Ti solids targets in liquid environments (H₂O, C₂H₅OH, C₂H₄Cl₂, etc.). X-ray diffractometry (XRD), UV-Vis optical transmission spectrometry, and high-resolution transmission electron microscopy (HRTEM) characterise the nanoparticles. The morphology of nanoparticles is studied as a function of both laser fluence and nature of the liquid. The evidence of an intermediate phase of Au-Ag alloy is presented under exposure of a mixture of individual nanoparticles to laser radiation. Self-influence of the beam of a femtosecond laser is discussed under the ablation of the Ag target in liquids under Ti:sapphire laser. The factors are discussed that determine the distribution function of particle size under laser ablation. The influence of laser parameters as well as the nature on the liquid on the properties of nanoparticles is elucidated. PACS 42.62.-b; 61.46.+w; 78.66.-w     

Production of nanoparticles of different materials by means of ultrashort laser pulses

Ultrashort pulsed laser ablation in vacuum of different targets was performed in order to investigate the possibility of producing nanoparticles with controlled size and shape. A systematic morphology characterization of deposited products was performed for nickel and silicon as a function of laser pulse intensity and wavelength, at a fixed pulse repetition rate. The nanoparticles were investigated by atomic force microscopy, and clear trends for their size and shape anisotropy were evidenced. The best conditions to obtain nanosized particles of oblate ellipsoidal shape, with the minor axis below 10 nm, were determined in the case of nickel targets. Our results show that ultrashort pulse laser deposition can be considered as an interesting technique for the tailoring of nanogranular films with the desired particles dimension and shape, according to the peculiar properties required in specific applications. Moreover, the preliminary features are very promising from the point of view of the production of magnetoresistive films with specific anisotropy.