Gold nanoparticles fabricated by pulsed laser ablation in supercritical CO2

Nanosecond pulsed laser ablation (PLA) of gold plate with an excitation wavelength of 532?nm was carried out in supercritical CO₂ (scCO₂) to fabricate gold nanoparticles. Surface morphology of the gold plate after irradiation and the crater depth after PLA were observed by scanning electron microscopy and laser scanning microscopy, while extinction spectra of gold nanoparticles collected in the glass slide was measured by UV?CVis spectrophotometer. The gold plate was ablated at various scCO₂ densities and irradiation times at constant temperature of 40??C. The ablation was also conducted at atmospheric condition with air to evaluate the environmental dependence of ablation. Both surface morphology of the irradiated gold plate and crater depth formation were significantly affected by the changes in scCO₂ density, the surrounding environment, and irradiation time. As expected, the increasing scCO₂ density resulted in a deeper ablation crater, however, the deepest crater was obtained at a density of 0.63?g/cm³ or pressure of 10?MPa. Gold nanoparticles generated by PLA in scCO₂ have been confirmed at the spectra band near 530?nm.     

Rhenium/rhenium oxide nanoparticles production using femtosecond pulsed laser ablation in liquid

In this study, rhenium/rhenium oxide nanoparticles (Re / ReO₃ NPs) have been produced for the first time in ultrapure water by using Femtosecond Pulsed Laser Ablation in Liquid (fsPLAL) method. X-Ray Diffraction (XRD) measurements and results obtained for NPs show the existence of well-crystallized peaks and preferred phases. Re NPs have hexagonal structure while ReO₃ NPs have the perovskite-like cubic crystal structures. The Re / ReO₃ ratio is also determined to be 53 / 47 with ~ 20 nm crystallite size, while pure ReO₃ crystallite sizes were measured to be ~ 25 nm. The TEM results have shown that the produced particles have a spherical shape, and particle sizes changes between ~ 20 nm and ~ 60 nm. The crystallite size is similar due to XRD results. Obtained nanoparticles exhibit promising applications for photonic devices with broad bandgap values which have measured to be 4.71 eV for Re / ReO₃ NPs mixture and 4.36 eV for pure ReO₃ NPs.     

Fluorine-supported flames ignited by a pulsed CO2 laser

The chemistry accompanying pulsed CO₂ laser irradiation of fuel—SF₆ mixtures was examined using time-integrated visible emission spectroscopy and analysis of the IR absorption spectra of end products. Under suitable conditions of laser energy, gas pressure, mixture ratio and cell geometry, the visible luminescence exhibits characteristics of fluorine-supported flames. Similar emission has been observed in irradiated fuel—S₂F₁₀ mixtures. An analysis of ignition delay versus absorbed laser energy is presented for CH₄SF₆ mixtures; it accounts for fluence-dependent absorption by these mixtures and models the effects of hydrodynamic motion on the initial pressure, density and temperature profiles in the samples using a computer code for two-dimensional wave propagation. Many of the IR absorption data are consistent with a reaction mechanism involving the formation of small hydrocarbon intermediates followed by efficient hydrogen abstraction to generate end products such as CS₂, CF₄ and C₂F₄. Mechanisms for reaction initiation are discussed.     

Comparison of structures of gold nanoparticles synthesized by pulsed laser ablation and magnetron sputtering

We present the results of studying the structure of gold nanoparticles synthesized on the silicon surface by two techniques: pulsed laser ablation and magnetron sputtering. The surface morphology is examined by scanning electron microscopy. The structure of the obtained gold nanoparticles is analyzed by transmission electron microscopy and electron diffraction. It is shown that nanoparticle sizes and crystal structures can be controlled by their thermal annealing. Mechanisms occurring during annealing of thin gold films and also their effect on the formation of nanoparticles with different structures are investigated.     

The influence of laser wavelength and fluence on palladium nanoparticles produced by pulsed laser ablation in deionized water

Homogeneous spherical palladium (Pd) nanoparticles were synthesized by pulsed laser ablation of a solid Pd foil target submerged in deionized water, without the addition of any external chemical surfactant. The influence of laser wavelength (355, 532, and 1064 nm) and fluence (8.92, 12.74, and 19.90 J/cm²) on nucleation, growth, and aggregation of Pd nanoparticles were systematically studied. Microstructural and optical properties of the obtained nanoparticles were studied by field emission transmission electron microscopy (FETEM), energy dispersive X-ray spectroscopy, and UV–vis spectroscopy. FETEM micrographs indicate that the average nanocrystallite sizes are relatively low (3–6 nm) and homogeneous for the particles synthesized at the laser wavelengths of 355 and 532 nm. However, at a laser wavelength of 1064 nm, the average nanocrystallite size is relatively large and inhomogeneous in nature. Moreover, we observe that the mean diameter and production rate of particles increases with an increase in laser fluence. The selected area electron diffraction patterns obtained from isolated Pd nanoparticles show the characteristic diffused electron diffraction rings of polycrystalline materials with a face-centered cubic structure. Absorbance spectrum of the synthesized nanoparticle solution shows a broad absorption band, which corresponds to a typical inter-band transition of a metallic system, indicating the production of pure palladium nanoparticles. The present work provides new insights into the effect of laser wavelength and fluence on the control of size and aggregation of palladium nanoparticles in the liquid medium.     

Silicon nanoclusters selectively generated by laser ablation in supercritical fluid

A novel method for generating nanomaterials is developed by performing laser ablation of silicon crystals in supercritical fluid. The method is shown to successfully generate silicon nanoclusters, and to allow for the selective generation of clusters having different electronic structures. This selective fabrication enables us to obtain the nanoclusters via a dry process, by changing only the fluid density and/or temperature when ablation is performed. The experimental procedures are not highly specialized, and a variety of researchers unfamiliar with wet chemical processes are able to obtain nanoclusters with different properties in only a few minutes. This new method can also be used to selectively obtain other semiconductor or metal nanomaterials with different properties.     

Preparation of copper oxide nanosheets by pulsed laser ablation in liquid for anticancer,antioxidant, and antibacterial activities

In this work, the preparation of copper oxide (CuO) nanosheets by laser ablation in water was demonstrated. The optical, structural, stability, and morphological properties of CuO nanosheets were investigated using UV–Vis spectrophotometer, X-ray diffraction (XRD), scanning electron microscope (SEM), and zeta potential (ZP). The XRD results confirm the formation of crystalline (CuO) with a monoclinic phase. The optical energy gap of CuO nanosheets was found to be 2.2 eV at 300 k. The average thickness of the synthesized copper oxide nanosheets is 25 nm. Energy dispersive X-ray result confirms the formation of stoichiometric CuO. The zeta potential result confirms the synthesized CuO colloid is stable. Gram-positive bacteria are found to be more susceptible to CuO nanosheets than Gram-negative bacteria. The synthesized copper oxidenanosheets are tested for antibacterial activity against Gram (+ve) and Gram (-ve) bacteria stains. The results suggest that CuO NPS can give hydrogen atoms and remove the unstable electron from DPPH at a rate of 200 μg/ml than 12.50 μg/ml. The results demonstrate that the copper oxide nanosheets have an effective antioxidant. Furthermore, according to a cytotoxicity assay, when cancer cells are incubated with copper oxide nanosheets, they are unable to grow well. copper oxide nanosheets can induce apoptosis and suppress pancreatic cell proliferation.     

Photofragmentation of phase-transferred gold nanoparticles by intense pulsed laser light

Gold nanoparticles with an average diameter of approximately 20 nm were prepared in an aqueous solution by a wet chemistry method. The parent gold nanoparticles were then capped with a 4-aminothiophenol protecting layer and transferred into toluene by tuning the surface charge of the modified nanoparticles. Gold nanoparticles before and after phase transfer were subjected to photofragmentation by a pulsed 532 nm laser. The effects of solvent properties and surface chemistry on the photofragmentation of the gold nanoparticles have been investigated. Fast photofragmentation has been observed in the organic solvent in which the dielectric constant, heat capacity, and thermal conductivity are lower. The results suggest new approaches for the preparation of very small gold clusters from gold nanoparticles.     

Bare phosphorus and binary phosphide cluster ions generated by laser ablation

Both positive and negative phosphorus cluster ions were generated from the laser ablation of a red phosphorus sample. The mass distribution of phosphorus cluster ions was found to be very sensitive to the power density of the ablation laser. The P ₇ ⁺ species exhibits the highest signal intensity in the recorded mass spectra of bare phosphorus cluster cations, as does P ₅ ^- among the anions. Their special structural stability can be attributed to their planar configuration and their aromatic character. As the phosphorus cluster size increases, the odd/even alternation of the signal intensity becomes more pronounced. For the P _n ⁺ species with n > 24, the relative abundance varies in the order of 8 and P _n ⁺ with n = 8k + 1 (k = 3–11) are more intense than their neighbors. For comparison, some binary phosphide cluster ions, including C_nP _m ^- , Si_nP _m ^- , B_nP _m ⁺ and Al_nP _m ⁺ , were produced as well. The mass distribution of binary phosphide cluster ions changes with different components. From analysis of the recorded mass spectra of the phosphide cluster ions, the larger clusters may be in a polyhedral configuration and tend to have all valence electrons paired.     

Composition/structural evolution and optical properties of ZnO/Zn nanoparticles by laser ablation in liquid media

We present composition-controlled synthesis of ZnO-Zn composite nanoparticles by laser ablation of a zinc metal target in pure water or in aqueous solution of sodium dodecyl sulfate (SDS). By SDS concentration, composition and size of the nanoparticles can be controlled in a wide range. Relative amounts of the components Zn and ZnO, the particle size, and the microstructure can evolve with SDS concentration in solution. High SDS concentration corresponds to high relative amount of Zn nanoparticles existing as the core in the core/shell nanostructures, whereas low SDS concentration leads to high ZnO amount. This was explained by a dynamic mechanism on the basis of the competition between aqueous oxidation and SDS capping protection. Correspondingly, optical absorption spectra evolve from the excitonic peak of ZnO (about 350 nm) to the Zn surface plasmon resonance (about 242 nm) with rise of SDS concentration. A blue (about 450 nm) photoluminescence was observed in the obtained ZnO nanoparticles, which was attributed to existence of interstitial zinc in ZnO lattices. This study has revealed that laser ablation of active metal in liquid media is an appropriate method to synthesize a series of metal oxide semiconductor-metal composite nanoparticles with controlled composition and size.     

Hollow nanoparticles of metal oxides and sulfides: fast preparation via laser ablation in liquid

In this work, diverse hollow nanoparticles of metal oxides and sulfides were prepared by simply laser ablating metal targets in properly chosen liquids. The Kirkendall voiding and the selective heating with an infrared laser were shown to work as two independent mechanisms for the formation of such hollow nanoparticles in only one- or two-step synthesis approaches. One of the prepared materials, ZnS hollow nanoparticles, showed high performance in gas sensing. The simple, fast, inexpensive technique that is proposed demonstrates very promising perspectives.     

Postpolymerization effect on molecular weight distribution generated by pulsed laser radical polymerization

The postpolymerization effect on molecular weight distribution (MWDs) and on the Pulsed Laser Polymerization (PLP) technique for evaluation of kinetic constants is investigated. General expressions for moments are derived for a polymerization scheme that contains the reactions of chain initiation, propagation, and termination by recombination or disproportionation, under polymerization initiation by an arbitrary sequence of radiation pulses. The results of calculation of MWDs and of the weight-average degree of polymerization (P _w) for methyl methacrylate are presented. It is shown that the P _w value strongly depends on postpolymerization. A new method for determining the rate constants of chain propagation and chain termination from a single experiment by polymerization with packets of laser pulses is presented.     

Optical transient absorption spectroscopy of LaO produced by pulsed laser ablation of La2O3

Temporally and spatially resolved absorption spectrometry has been used to study molecular LaO absorption in laser ablated plume from an La2O3 target The absorption time-of-flight (TOF) spectra of ground-state LaO molecules were measured The TOF spectra indicate that only one component is observed in vacuum and in an Ar ambient, while there are two component, a fast and a broad slow component, observed at higher O2 pressure. The absorbance of LaO molecules decreases gradually with increasing ambient gas pressure. The dependence of the absorbance of LaO on the detection distance can be fitted by an exponential decay equation. The shock wave model is used to describe the behavior of ground state LaO molecules in high O2 pressure region.     

A facile method of producing femtoliter metal cups by pulsed laser ablation

Cuplike structures of Au, Ag, Cu, Zn, Nb, Cd, Al, In, and Sn in the size range of 300 nm to a few micrometers with an internal volume of a few femtoliters have been produced by the laser ablation of metal targets in a vacuum, by optimizing, in each case, the laser fluence and the substrate temperature. The metal droplets impinging on the substrate seem to undergo a hydraulic jump driven by the surface tension forces before solidifying into cups. The cups are robust and can be functionalized with biomarkers, filled with nanoparticle sols, oxidized to crucibles, or detached from the substrate without causing any deformation. We envisage their potential applications as femtoliter metal containers.     

Photoluminescence of ZnO nanoparticles prepared by laser ablation in different surfactant solutions

ZnO nanoparticles were prepared by laser ablation of a zinc metal plate in a liquid environment using different surfactant (cationic, anionic, amphoteric, and nonionic) solutions. The nanoparticles were obtained in deionized water and in all surfactant solutions except the anionic surfactant solution. The average particle size and the standard deviation of particle size decreased with increasing amphoteric and nonionic surfactant concentrations. With the increase of the amphoteric surfactant concentration, the intensity of the defect emission caused by oxygen vacancies of ZnO rapidly decreased, while the exciton emission intensity increased. This indicates that anionic oxygen in the amphoteric surfactant molecules effectively occupied the oxygen vacancy sites at the ZnO nanoparticle surface due to charge matching with the positively charged ZnO nanoparticles.     

Photoacoustic monitoring of the mass removed in pulsed laser ablation

The mass Δm removed per pulse in laser ablation was shown to correlate with the acoustic signal A and the beam diameter ?. The functional forms of Δm(A, ?) were deduced for aluminum and polyvinyl chloride, for fluence ranging from 1.5 through 88 J cm^{− 2}. Δm so computed agreed with empirical values within experimental error. For samples whose mass is sensitive to environmental factors, off-line measurement of Δm was shown to be unreliable and real-time measurements such as acoustic monitoring became essential.     

Production of Au-Ag alloy nanoparticles by laser ablation of bulk alloys

Gold-silver alloy nanoparticles can be produced by pulsed laser irradiation of bulk alloy metals in water, preserving the stoichiometry of the target metals.     

Degradation of protein in nanoplasma generated around gold nanoparticles in solution by laser irradiation

We developed a method of protein degradation in an aqueous solution containing gold nanoparticles by irradiation of a pulse laser. In the present study, lysozyme was used as an example. Lysozyme degradation proceeded most efficiently when a pH of the solution was adjusted so that it was at the isoelectric point. The scheme of the lysozyme degradation is as follows: (1) Lysozyme molecules in the solution are neutralized and adsorbed on the gold nanoparticles with its pH value adjusted at the isoelectric point, (2) nanoplasma is generated in the close vicinity of a gold nanoparticle which is excited by an intense 532-nm laser, (3) lysozyme molecules in the nanoplasma are degraded into small fragments. Lysozyme degradation does not proceed efficiently at a pH value deviated from the isoelectric point because the lysozyme molecules are dissolved uniformly so that only a small portion of the lysozyme molecules are located in the vicinity of gold nanoparticles which create the nanoplasma.     

The dynamics of the SiF4 - sensitized processes initiated by a pulsed CO2 laser

A model enabling the examination of the dynamics of the SiF₄ - sensitized processes initiated by a pulsed CO₂ laser is outlined, taking into account three effects : energy absorption, energeticity of chemical reactions and expansion of hot gas created upon interaction of molecules with the infrared photon field. This approach was used to elucidate some aspects regarding the decomposition of PH₃ and GeH₄.     

Visualization of aerosol particles generated by near infrared nano- and femtosecond laser ablation

The expansion of aerosols generated by near infrared (NIR) nanosecond (ns) and femtosecond (fs) laser ablation (LA) of metals at atmospheric pressures was explored by laser-induced scattering. In order to achieve adequate temporal and spatial resolution a pulsed laser source was utilized for illuminating a 0.5 mm-wide cross section of the expanding aerosol. It could, for instance, be shown that NIR-ns-LA under quiescent argon atmosphere provokes the formation of a dense aerosol confined within a radially propagating vortex ring. The expansion dynamics achieved under these conditions were found to be fairly slow whereas the degree of aerosol dispersion for NIR-ns-LA using helium drastically increased due to its lower viscosity. As a consequence, the maximum diameter of expansion differed by a factor of approximately four. The trajectories of aerosol particles generated by NIR-ns-LA using argon could, furthermore, be simulated on the basis of computational fluid dynamics (CFD). For this purpose, a model inspired by the thermal character of NIR-ns-LA taking into account a sudden temperature build-up of 10,000 K at the position of the laser focus was implemented.