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.     

Synthesis of Si nanoparticles with narrow size distribution by pulsed laser ablation

We synthesized Si nanoparticles by pulsed nanosecond-laser ablation. We applied a positive voltage bias during laser irradiation and effectively reduced size distribution. Scanning electron micrographs of samples showed the nanoparticles to be highly non-agglomerated. Si nanoparticles have the average diameter of 4–5 nm, the geometrical standard deviation of 1.35, and the density of 1.6 × 10¹²/cm². A MOS device showed excellent charge trap behavior with a flat-band voltage shift over 7 V, which can be applied for memory device applications.     

Noble metal nanoparticles produced by nanosecond laser ablation

Silver and gold thin films were deposited by pulsed laser ablation in a controlled Ar atmosphere at pressures between 10 and 100 Pa. Different morphologies, ranging from isolated nanoparticle arrays up to nanostructured thin films were observed. Fast imaging of the plasma allowed deducing the expansion dynamics of the ablated plume. Plasma velocity and volume were used together with the measured average ablated mass per pulse as input parameters in a model to estimate the average size of nanoparticles grown in the plume. The nanoparticle size is expected to decrease from 4 nm down to 1 nm with decreasing Ar pressure between 100 and 10 Pa: this was confirmed by transmission electron micrographs which indicate a reduced dispersion of particle size over narrow size ranges. The production of substrates for surface enhanced Raman scattering whose performances critically depend on nanoparticle size, shape, and structure is discussed.     

Synthesis of silver nanoparticles and antimony oxide nanocrystals by pulsed laser ablation in liquid media

Pulsed laser ablation in liquid media (PLALM) is a prominent technique for the controlled fabrication of nanomaterials via rapid reactive quenching of ablated species at the interface between the plasma and liquid. Results on nanoparticles and nanocrystals formed by PLALM of silver (Ag) and antimony (Sb) solid targets in different liquid environments (Sodium Dodecyl Sulfate, distilled water) are presented. These experiments were done by irradiating solid targets of Ag and Sb with a nanosecond pulsed Nd:YAG laser output of wavelength 532 nm. Nanoparticles of silver and nanocrystals of antimony oxide (Sb₂O₃) obtained were characterized using UV-Vis spectrometry, Scanning Electron Microscopy (SEM), transmission electron microscopy (TEM), X-ray Energy Dispersion Analysis (EDAX) and X-ray diffractometry (XRD). The morphology of nanomaterials formed is studied as a function of surfactant environment. The silver nanoparticles obtained were spherical of size in the order of 10–35 nm in solution of SDS having different concentrations. In case of the Sb target, ablation was performed in two different molarities of SDS solution and distilled water. Nanocrystals of Sb₂O₃ in powder form having cubic and orthorhombic phases were formed in SDS solution and as fibers of nanocrystals of cubic Sb₂O₃ in distilled water.     

Plume dynamics during film and nanoparticles deposition by pulsed laser ablation

The gas dynamics of pulsed laser ablation of silicon target in the helium gas ambient is investigated via direct simulation Monte Carlo method with a real physical scale of target-substrate configuration. A shock driven process is clearly observed. It is shown that the interaction of the shock front with the target surface and the vapor front induce significant backward flux of ablated particles and oscillating behavior of vapor front. A confined layer mixed with high density Si and He atoms is formed around the contact front. Its behavior is important to the nanoparticle formation and deposition.     

Synthesis of cubic ruthenium nitride by reactive pulsed laser ablation

The recent synthesis of platinum nitride opens the possibility of novel platinum-group metal nitrides to exist. In this work we report the synthesis of ruthenium nitride by reactive pulsed laser ablation. Several plausible structures have been evaluated by ab initio calculations using the full potential linearized augmented plane wave method, in order to investigate the ruthenium nitride structural and electronic properties. In fact, the predicted symmetry of stoichiometric RuN matches the experimental diffraction data. RuN crystallizes with NaCl-type structure at room temperature with cell-parameter somewhat larger than predicted by calculations. However we found a marginal chemical strength in these nitrides. The material is destroyed by mild acid and basic solutions. Under annealing RuN decomposes abruptly for temperatures beyond 100 °C. Since the thermal stability correlates directly with the mechanical properties our finding cast doubts than the latter transition metal nitrides can be ultra-hard materials at ambient conditions.     

激光烧蚀金属Al诱导发光的动力学研究

利用时间分辨的光谱测量技术,测定了XeCl紫外激光在不同条件下烧蚀金属Al诱导产生光谱线及其强度随时间的分布.结果表明：等离子体辐射光谱线由原子光谱线、一价离子光谱线及连续辐射背景光组成.Al原子光谱线的辐射强度与持续时间为最大,一价离子光谱线次之,以连续辐射背景光为最小.对激光烧蚀金属诱导发光的机理进行了探讨.等离子体中连续辐射背景光来自高能电子的韧致辐射和电子与离子的复合,原子光谱线和一价离子光谱线主要来自等离子体中电子与离子的复合.用此机理定性地解释了所观察到的实验现象. 关键词： 激光烧蚀 时间分辨光谱 辐射机理 金属Al     

Investigation of Ag nanoparticles produced by nanosecond pulsed laser ablation in water

A study is presented of the properties of Ag nanoparticles produced by nanosecond pulsed laser ablation in twice-distilled water. An Ag target was immersed in the liquid and irradiated by the fundamental, second, third and fourth harmonics of a Nd:YAG laser system to create different colloids. Two specific boundary values of the laser fluence were applied for each wavelength. The properties of the nanoparticles at different wavelengths of the laser radiation were examined. The characterization of the colloids was performed immediately after their fabrication. Spherical and spherical-like shapes of the nanoparticles created were established. The formation of nanowires was observed when the second and the third harmonics of the laser were used. It is connected with self-absorption of the incident laser light from the already-created nanoparticles and depends also on the laser fluence. The size distribution of the nanoparticles is estimated by transmission electron microscopy. Generally, their mean size and standard deviation decreased as the wavelength of the incident laser light was increased and increased with the increase of the laser fluence. The substantial discrepancy between the results already commented on for both characteristics considered and others, obtained by dynamic light scattering, is discussed. The structure of the nanoparticles was established to be single and polycrystalline, and the phase composition in both cases is identified as consisting of cubic silver. The nanoparticles are slightly oxidized.     

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.     

Silver nanoparticles generated by pulsed laser ablation in supercritical CO2 medium

Pulsed laser ablation (PLA) has been widely employed in industrial and biological applications and in other fields. The environmental conditions in which PLA is conducted are important parameters that affect both the solid particle cloud and the deposition produced by the plume. In this work, the generation of nanoparticles (NPs) has been developed by performing PLA of silver (Ag) plates in a supercritical CO₂ medium. Ag NPs were successfully generated by allowing the selective generation of clusters. Laser ablation was performed with an excitation wavelength of 532 nm under various pressures and temperatures of CO₂ medium. On the basis of the experimental result, both surface of the irradiated Ag plate and structure of Ag NPs were significantly affected by the changes in supercritical CO₂ pressure and temperature. With increasing irradiation pressure, plume deposited in the surrounding crater created by the ablation was clearly observed. In Field Emission Scanning Electron Microscopy (FE-SEM) the image of the generated Ag NPs on the silicon wafer and the morphology of Ag particles were basically a sphere-like structure. Ag particles contain NPs with large-varied diameter ranging from 5 nm to 1.2 μm. The bigger Ag NPs melted during the ablation process and then ejected smaller spherical Ag NPs, which formed nanoclusters attached on the molten Ag NPs. The smaller Ag NPs were also formed around the bigger Ag NPs. Based on the results, this new method can also be used to obtain advanced nano-structured materials.     

CdSe &; ZnS core/shell nanoparticles generated by laser ablation of microparticles

Laser Ablation of Microparticles (LAM) is a process of nanoparticle formation in which microparticles in a flowing aerosol are continuously ablated by high-power laser pulses. For the first time, we have produced CdSe/ZnS core/shell nanoparticles using a double ablation apparatus, designed to undergo a two-step LAM process. This process can be inverted to produce ZnS/CdSe core/shell nanoparticles. The present work focuses on the range around ∼15 nm radius heterostructures and uses high-resolution transmission electron microscopy (HRTEM) to image core and shells. For smaller particles, core shell structures have been detected with energy dispersive spectroscopy (EDS) 5 nm spot size beam and fast Fourier transform (FFT) spectra. Differences in the ablation behavior were measured between the two IIB–VIA type semiconductors.     

Synthesis of silver nanoparticles by laser ablation in pure water

We have successfully produced silver nanoparticles by irradiating an Ag target with a 532-nm laser beam in pure water. By working with high laser power and small spot sizes, we were able to synthesize very small spherical particles with a typical size of 2–5 nm. The influence of the beam spot size, the laser power, and the ablation time were studied, and the possible mechanisms of particle formation are discussed. PACS 79.20.Ds; 81.07.-b     

Highly luminescent undoped and Mn-doped ZnS nanoparticles by liquid phase pulsed laser ablation

In this paper we report the synthesis of highly luminescent ZnS and Mn-doped ZnS nanoparticles with uniform particle size distribution by liquid phase pulsed laser ablation. The formation of nanosized ZnS crystallites was confirmed by high-resolution transmission electron microscopy (HRTEM) images. The optical properties of these nanoparticles were studied by room temperature photoluminescence (PL) spectra. The PL emission from the ZnS nanoparticles shows a sharp peak in the UV region (334 nm) corresponding to the band edge and a broad peak in the visible region which can be attributed to the sulphur vacancies, cation vacancies and surface states in the nanocrystals. The yellow emission from the Mn-doped ZnS nanoparticles can be attributed to the radiative transition between ⁴T₁ and ⁶A₁ levels within the 3d⁵ orbital of Mn²⁺.     

Investigation of metal nanoparticles produced by laser ablation and their catalytic activity

Polydiphenylsilylenemethylene (PDPhSM) thin films, which are difficult to fabricate by conventional methods because of their insolubility and high melting point, have been synthesized by using laser-ablated metal nanoparticles for the thermal ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (TPDC) in this paper. TPDC was first evaporated on silicon substrates and then exposed to metal (Pt, Cu and Ag) nanoparticles deposition by laser ablation prior to heat treatment. The catalytic activity of Pt, Cu and Ag nanoparticles has been studied. The results showed that the mean diameter of Pt nanoparticles was the smallest, Cu nanoparticles the moderate and Ag nanoparticles the biggest, while the polymerization efficiency for Pt nanoparticles was the highest, Cu nanoparticles the moderate and Ag nanoparticles the lowest. In addition, the penetration behaviours of Pt, Cu and Ag nanoparticles into the TPDC monomer films during laser ablation were different due to the particle size or the chemical interaction between metal nanoparticles and TPDC molecules.     

Size classification of Si nanoparticles formed by pulsed laser ablation in helium background gas

We have developed an integrated process system for the formation of nanoparticles by pulsed laser ablation (PLA) in helium background gas, size classification using a differential mobility analyzer (DMA), and deposition on a substrate. The DMA has been improved to operate at pressures of less than 10 Torr. The classification resolution of the low-pressure operating DMA (LP-DMA), transporting properties of nanoparticles under low pressure, have been investigated theoretically in order to evaluate the performance of the size classification for the integrated system. By operating the integrated system at less than 10 Torr, we have measured the size distribution of Si nanoparticles in the gas phase formation field by sweeping the applied voltage to the LP-DMA and counting the charged nanoparticle concentration with an electrometer. Moreover, we successfully deposited the classified Si nanoparticles on a substrate by fixing the voltage. We have verified that the integrated system can be applied to the clean physical vapor deposition process for accurately size-controlled nanoparticles.     

A simple model for high fluence ultra-short pulsed laser metal ablation

The ultra-short laser metal ablation is a very complex process, the complete simulation of which requires applications of complicated hydrodynamics or molecular dynamics models, which, however, are often time-consuming and difficult to apply. For many practical applications, where the laser ablation depth is the main concern, a simplified model that is easy to apply but at the same time can also provide reasonably accurate predictions of ablation depth is very desirable. Such a model has been developed and presented in this paper, which has been found to be applicable for laser pulse duration up to 10 ps based on comparisons of model predictions with experimental measurements.     

Effect of insitu annealing on physical properties of Si nanoparticles synthesized by pulsed laser ablation

Silicon nanocrystalline particles with a uniform size were successfully synthesized by a sequential system of pulsed-laser ablation, insitu annealing and a size classification using a differential mobility analyzer (DMA). Transmission electron microscopy (TEM) observations revealed that the insitu annealing was quite effective in improving morphological uniformity of the particles; most of the nanoparticles annealed above a temperature of 900 °C showed a spherical shape. The silicon nanoparticles classified after the annealing showed a very narrow size-distribution with a geometrical standard deviation of approximately 1.1. Raman scattering measurement and high-resolution TEM observation showed that the annealing was also effective in improving a crystallinity of the particles. The silicon nanoparticles showed photoluminescence (PL) in near-IR and visible region at room temperature, which depended on the insitu annealing condition; the full-width at half-maximum (FWHM) of the PL spectrum decreased with the increase in annealing temperature and reached as narrow as 190 meV corresponding to the sharp size distribution of the emitting particles. PACS 81.40.Pq; 81.07.Bc