Synthesis of nanoparticles by pulsed laser ablation of consolidated metal microparticles

This paper describes a novel process of nanoparticle synthesis by pulsed laser ablation of consolidated microparticles. Metal microparticles, including Cu, Al and Ag, are consolidated by a cold isobaric press with pressures up to a few hundred MPa before laser irradiation. Nanoparticles are then synthesized in air by high-power pulsed laser ablation of the microparticles using a Q-switched Nd:YAG laser. It is shown that the degree of compaction plays a significant role in determining the size of the produced nanoparticles. The effect of laser fluence and collector position on the distribution of particle size is examined. Photoacoustic deflection probing and nanosecond time-resolved visualization indicate that the novel process attains increased efficiency of laser-energy coupling with the target. PACS 81.07.-b; 81.07.Wx; 42.62.Cf     

Laser ablation of microparticles for nanostructure generation

The process of laser ablation of microparticles has been shown to generate nanoparticles from microparticles; but the generation of nanoparticle networks from microparticles has never been reported before. We report a unique approach for the generation of nanoparticle networks through ablation of microparticles. Using this approach, two samples containing microparticles of lead oxide (Pb₃O₄) and nickel oxide (NiO), respectively, were ablated under ambient conditions using a femtosecond laser operating in the MHz repetition rate regime. Nanoparticle networks with particle diameter ranging from 60 to 90 nm were obtained by ablation of microparticles without use of any specialized equipment, catalysts or external stimulants. The formation of finer nanoparticle networks has been explained by considering the low pressure region created by the shockwave, causing rapid condensation of microparticles into finer nanoparticles. A comparison between the nanostructures generated by ablating microparticle and those by ablating bulk substrate was carried out; and a considerable reduction in size and narrowed size distribution was observed. Our nanostructure fabrication technique will be a unique process for nanoparticle network generation from a vast array of materials.     

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     

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.     

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.     

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.     

Enhancement of the synthesis efficiency of carbon cluster ions by the irradiation of two laser pulses to polymers in vacuum

We investigated the effect of the pre-irradiation of a polymer target in vacuum, using a low-fluence laser pulse, on the synthesis efficiency of carbon cluster ions ejected by laser ablation. A polymer target was irradiated by two laser pulses. The first laser was used for the pre-irradiation, and the second laser was used for ablation. The masses of the ions in the ablation plume were analyzed by time-of-flight mass spectrometry. It was found that the synthesis efficiency of carbon cluster ions was enhanced by the pre-irradiation. The effects of the fluence of the pre-irradiation, the wavelengths of the lasers, and the interval between the oscillations of the two laser pulses on the enhancement of the cluster synthesis are reported. PACS 52.38.Mf; 81.07.-b; 36.40.-c; 61.46.+w     

Plasmonics properties of trimetallic Al@Al2O3@Ag@Au and Al@Al2O3@AuAg nanostructures

Bimetallic and trimetallic nanoparticles have attracted significant attention in recent times due to their enhanced electrochemical and catalytic properties compared to monometallic nanoparticles. The numerical calculations using Mie theory has been carried out for three-layered metal nanoshell dielectric–metal–metal (DMM) system consisting of a particle with a dielectric core (Al@Al₂O₃), a middle metal Ag (Au) layer and an outer metal Au (Ag) shell. The results have been interpreted using plasmon hybridization theory. We have also prepared Al@Al₂O₃@Ag@Au and Al@Al₂O₃@AgAu triple-layered core–shell or alloy nanostructure by two-step laser ablation method and compared with calculated results. The synthesis involves temporal separations of Al, Ag, and Au deposition for step-by-step formation of triple-layered core–shell structure. To form Al@Ag nanoparticles, we ablated silver for 40 min in aluminium nanoparticle colloidal solution. As aluminium oxidizes easily in water to form alumina, the resulting structure is core–shell Al@Al₂O₃. The Al@Al₂O₃ particle acts as a seed for the incoming energetic silver particles for multilayered Al@Al₂O₃@Ag nanoparticles is formed. The silver target was then replaced by gold target and ablation was carried out for different ablation time using different laser energy for generation of Al@Al₂O₃@Ag@Au core–shell or Al@Al₂O₃@AgAu alloy. The formation of core–shell and alloy nanostructure was confirmed by UV–visible spectroscopy. The absorption spectra show shift in plasmon resonance peak of silver to gold in the range 400–520 nm with increasing ablation time suggesting formation of Ag–Au alloy in the presence of alumina particles in the solution.     

Bimodal Nanoparticle Size Distributions Produced by Laser Ablation of Microparticles in Aerosols

Silver nanoparticles were produced by laser ablation of a continuously flowing aerosol of microparticles in nitrogen at varying laser fluences. Transmission electron micrographs were analyzed to determine the effect of laser fluence on the nanoparticle size distribution. These distributions exhibited bimodality with a large number of particles in a mode at small sizes (3–6-nm) and a second, less populated mode at larger sizes (11–16-nm). Both modes shifted to larger sizes with increasing laser fluence, with the small size mode shifting by 35% and the larger size mode by 25% over a fluence range of 0.3–4.2-J/cm². Size histograms for each mode were found to be well represented by log-normal distributions. The distribution of mass displayed a striking shift from the large to the small size mode with increasing laser fluence. These results are discussed in terms of a model of nanoparticle formation from two distinct laser–solid interactions. Initially, laser vaporization of material from the surface leads to condensation of nanoparticles in the ambient gas. Material evaporation occurs until the plasma breakdown threshold of the microparticles is reached, generating a shock wave that propagates through the remaining material. Rapid condensation of the vapor in the low-pressure region occurs behind the traveling shock wave. Measurement of particle size distributions versus gas pressure in the ablation region, as well as, versus microparticle feedstock size confirmed the assignment of the larger size mode to surface-vaporization and the smaller size mode to shock-formed nanoparticles.     

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.     

The effect of target size on α-Fe nanoparticle preparation by?pulsed laser ablation

Two methods of preparing Fe nanoparticles at atmospheric pressure were conducted using pulsed laser ablation of a 0.5-mm-diameter Fe wire and a bulk Fe target. Passivated α-Fe nanoparticles covered with a shell of γ-Fe₂O₃ were prepared at different process parameters. The influences of average laser power, repetition rate, pulse duration and carrier-gas pressure on the mean particle size for two laser ablation methods were investigated, respectively. The results show that the target size has a large effect on the nanoparticle preparation though we have the same range of laser process parameters. Except the carrier-gas pressure, the influence of the laser parameters on the mean particle size is almost opposite for the two laser ablation methods. Besides, the ablation mechanisms were discussed to understand the variation of mean particle sizes with target size.     

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利用时空分辨的测量技术,测定了XeCl紫外激光烧蚀金属Cu消融粒子的发射光谱随时间与空间的强度分布。通过在不同的氢气压强下拍摄到的XeCl308nm紫外激光烧蚀金属Cu消融粒子的发光羽照片,发现激光消融粒子发光羽的颜色在不同区域有不同的颜色,不同区域的发光羽颜色随环境气压的改变而变化。随环境气压的增大,发光羽不仅逐渐变小,而且逐渐变淡。对激光消融粒子发光羽的机理进行了探讨,激光消融粒子发光羽的发光动力学模式在不同区域有不同的发光模式,且随环境气压的变化而改变。定性地解释了所观察的实验现象。     

Hydrodynamic modeling of femtosecond laser ablation of metals in vacuum and in liquid

We numerically examine the mechanisms involved in nanoparticle formation by laser ablation of metallic targets in vacuum and in liquid. We consider the very early ablation stage providing initial conditions for much longer plume expansion processes. In the case of ultrashort laser ablation, the initial population of primary nanoparticles is formed at this stage. When a liquid is present, the dynamics of the laser plume expansion differs from that in vacuum. Low compressibility of the ambient liquid results in strong confinement conditions. As a result, ablation threshold rises drastically, the ablated material is compressed, part of it becomes supersaturated and the backscattered material additionally heats the target. The extension of a molten layer leads to the additional ablation at a later stage also favoring nanoparticle formation. The obtained results thus explain recent experimental findings and help to predict the role of the experimental parameters. The performed analysis indicates ways of a control over nanoparticle synthesis.     

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     

Subpicosecond excimer laser ablation of thick gold films of ultra-fine particles generated by a gas deposition technique

The results of UV laser ablation of gold nanoparticle films on glass substrates using femtosecond pulses are presented. Films of ultra-fine gold particles were prepared by an inert gas evaporation and deposition technique, resulting in a well-defined log-normal particle size distribution of (7ǃ) nm. The pulse length of the laser was 500 fs at a wavelength of 248 nm. Ablation thresholds, ablation rates at different fluxes, and the morphology of the ablated structures are presented. For the nanoparticle films studied an ablation rate five times higher than that of gold films prepared by the conventional evaporation technique was found. The ablation thresholds and rates are supposed to depend on the particle size and also on the evaporation pressure. These results are explained by taking into account the energy transport properties of nanocrystalline and conventionally evaporated gold films.     

New nanohybrid materials for biophotonics

Hybrid nanomaterials were prepared by one- and two-step procedures in the absence of water. Femtosecond laser ablation of a ZnO target in absolute ethanol afforded a colloidal ZnO solution. Dye molecules were grafted onto the ZnO nanoparticle surface by mixing the ZnO solution with an ethanol solution of tetramethylrhodamine B isothiocyanate or rhodamine B. Formation of strongly facetted nanohybrid particles with the average size of 21 nm was observed by HRTEM measurements. Ablation of ZnO in the presence of the dyes afforded nanohybrids with the average size of 12 nm. The occurrence of energy transfer from the ZnO nanoparticles towards the attached dye molecules was demonstrated by photoluminescence spectroscopy of the nanohybrids after single and multi-photon excitations. In particular, two-photon absorption of the nanohybrids ZnO core gave rise to emission of the grafted dyes. PACS 81.07.Bc; 81.07.Nb; 78.67.Bf; 78.55.Et; 81.15.Fg     

Nanoparticles by Laser Ablation

This review concerns nanoparticles collected in the form of nanopowder or a colloidal solution by laser ablating a solid target that lies in a gaseous or a liquid environment. The paper discusses the advantages of the method as compared with other methods for nanoparticle synthesis, outlines the factors on which the properties of the produced nanoparticles depend, explains the mechanisms and models involved in the generation of nanoparticles by laser ablation, clarifies the differences between nanoparticle generation in gaseous and liquid environments, presents some experimental desigins and equipment used by the several groups for nanoparticle generation by laser ablation, describes the techniques used for “tuning” the width of the nanoparticles size distribution, and finally presents a few interesting examples of nanoparticles generated by laser ablation.     

Gas and Pressure Dependence for the Mean Size of Nanoparticles Produced by Laser Ablation of Flowing Aerosols

Silver nanoparticles were produced by laser ablation of a continuously flowing aerosol of microparticles entrained in argon, nitrogen and helium at a variety of gas pressures. Nanoparticles produced in this new, high-volume nanoparticle production technique are compared with our earlier experiments using laser ablation of static microparticles. Transmission electron micrographs of the samples show the nanoparticles to be spherical and highly non-agglomerated under all conditions tested. These micrographs were analyzed to determine the effect of carrier gas type and pressure on size distributions. We conclude that mean diameters can be controlled from 4 to 20 nm by the choice of gas type and pressure. The smallest nanoparticles were produced in helium, with mean sizes increasing with increasing molecular weight of the carrier gas. These results are discussed in terms of a model based on cooling via collisional interaction of the nanoparticles, produced in the laser exploded microparticle, with the ambient gas.     

Room temperature synthesis of an optically and thermally responsive hybrid PNIPAM–gold nanoparticle

Composites of metal nanoparticles and environmentally sensitive polymers are useful as nanoactuators that can be triggered externally using light of a particular wavelength. We demonstrate a synthesis route that is easier than grafting techniques and allows for the in situ formation of individual gold nanoparticles encapsulated by an environmentally sensitive polymer, while also providing a strong interaction between the polymer and the metal particle. We present a one-pot, room-temperature synthesis route for gold metal nanoparticles that uses poly-N-isopropyl acrylamide as the capping and stabilizing agent and ascorbic acid as the reducing agent and achieves size control similar to the most common citric acid synthesis. We show that the composite can be precipitated reversibly by temperature or light using the non-radiative decay and conversion to heat of the surface plasmon resonance of the metal nanoparticle. The precipitation is induced by the collapse of the polymer cocoon surrounding each gold nanoparticle, as can be seen by surface plasmon spectroscopy. The experiments agree with theoretical models for the heat generation in a colloidal suspension that support fast switching with low laser power densities. The synthesized composite is a simple nanosized opto-thermal switch.     

Pulsed-laser generation of gold nanoparticles with on-line surface plasmon resonance detection

Size of nanoparticles is an important parameter for their applications. The real-time monitoring is required for reliable and reproducible production of nanoparticles with controllable size. We present results of our research on development of the system for the online nanoparticle characterization during their production by a laser. The laser ablation chamber which allows measurements of surface plasmon resonance spectra during the nanoparticle generation process has been designed and fabricated. The online characterization system was tested by producing and modification of gold nanoparticles. Nanoparticles were generated by nanosecond-laser (wavelength 1064 nm) ablation of gold target in deionized water, and optimal conditions for the highest nanoparticle productivity were estimated. The mean diameter of nanoparticles was determined using their absorption spectra measured in the real-time during the ablation experiments and from the TEM images analysis, and it varied from 20 to 45 nm. The mismatch between nanoparticle diameters, estimated using these two methods, is due to the polydispersity of the generated nanoparticles. The further experiments of laser-induced modification of colloidal gold nanoparticles were carried out using second harmonic (wavelength 532 nm) of nanosecond Nd:YAG laser and alteration in nanoparticle size were acquired by the online measurement system.