Laser-assisted shape selective fragmentation of nanoparticles

Experimental results are presented on laser-assisted fragmentation of gold-containing nanoparticles suspended in liquids (either ethanol or water). Two kinds of nanoparticles are considered: (i) elongated Au nanorods synthesized by laser ablation of a gold target immersed in liquid phase; (ii) gold-covered NiCo nanorods with high aspect ratio (θ ∼ 10) synthesized by wet chemistry processes. The shape selectivity induced by laser fragmentation of these nanorods is gained via tuning the wavelength of laser radiation into different parts of the spectrum of their plasmon resonance corresponding to different aspect ratios θ. Fragmentation is performed using three laser wavelengths, involving a Cu vapour laser (510 and 578 nm) and a Nd:YAG (1064 nm). Nanoparticles are characterized by UV-vis spectrometry, Transmission Electron Microscopy (TEM). The effect of laser pulse duration (nanosecond against picosecond range) is also studied in the case of fragmentation with an IR laser radiation.     

Physical mechanism of silicon ablation with long nanosecond laser pulses at 1064 nm through time-resolved observation

Nanosecond (ns) laser ablation can provide a competitive solution for silicon micromachining in many applications. However, most of the previous studies focus on ns lasers at visible or ultraviolet (UV) wavelengths. The research is very limited for ns lasers at infrared (e.g., 1064 nm) wavelengths (which often have the advantage of much lower cost per unit average output power), and the research is even less if the ns laser also has a long pulse duration on the order of ∼100 ns. In this paper, time-resolved observation using an ICCD (intensified charge-coupled device) camera has been performed to understand the physical mechanism of silicon ablation by 200-ns and 1064-nm laser pulses. This kind of work has been rarely reported in the literature. The research shows that for the studied conditions, material removal in laser silicon ablation is realized through surface vaporization followed by liquid ejection that occurs at a delay time of around 200-300 ns. The propagation speed is on the order of ∼1000 m/s for laser-induced plasma (ionized vapor) front, while it is on the order of ∼100 m/s or smaller for the front of ejected liquid. It has also been found that the liquid ejection is very unlikely due to phase explosion, and its exact underlying physical mechanism requires further investigations.     

Generation of nanospikes via laser ablation of metals in liquid environment and their activity in surface-enhanced Raman scattering of organic molecules

The formation of dense arrays of nanospikes occurs under laser ablation of bulk targets (Ag, Au, Ta, Ti) immersed in liquids such as water or ethanol. The average height of spikes is 50 nm and their density on the target amounts to 10¹⁰ cm⁻². The effect is observed with sufficiently short laser pulses. In particular, either a 350 ps or a 90 ps Nd:YAG lasers are used in their fundamental harmonics. The nanospikes are characterized by UV-Visible reflection spectrometry and atomic force microscopy. The oscillations of electrons within nanospikes result in a permanent coloration of the surface and a modification of the optical reflection spectra of the metal. Scanning the laser beam along the metal surface allows its nanostructuring over extended areas (∼1 cm²). The nanostructured Ag surface shows enhanced Raman scattering of acridine molecules at a concentration of 10⁻⁵ M/l, whereas the initial Ag targets do not show any signal within the accuracy of measurements.     

Influence of oxygen post-treatment on laser-induced damage of antireflection coatings prepared by electron-beam evaporation and ion beam assisted deposition

Antireflection coatings at the center wavelength of 1053 nm were prepared on BK7 glasses by electron-beam evaporation deposition (EBD) and ion beam assisted deposition (IBAD). Parts of the two kinds of samples were post-treated with oxygen plasma at the environment temperature after deposition. Absorption at 1064 nm was characterized based on surface thermal lensing (STL) technique. The laser-induced damage threshold (LIDT) was measured by a 1064-nm Nd:YAG laser with a pulse width of 38 ps. Leica-DMRXE Microscope was applied to gain damage morphologies of samples. The results revealed that oxygen post-treatment could lower the absorption and increase the damage thresholds for both kinds of as-grown samples. However, the improving effects are not the same.     

Line patterning with large refractive index changes in the deep inside of glass by nanosecond pulsed YAG laser irradiation

Nanosecond (∼100 ns) pulsed (10 Hz) Nd:YAG laser operating at the wavelength (λ) of 1064 nm with pulse energies of 0.16-1.24 mJ/cm² has irradiated 10Sm₂O₃·40BaO·50B₂O₃ glass. It is demonstrated for the first time that the structural modification resulting the large decease (∼3.5%) in the refractive index is induced by the irradiation of YAG laser with λ=1064 nm. The lines with refractive index changes are written in the deep inside of 100-1000 μm depths by scanning laser. The line width is 1-13 μm, depending on laser pulse energy and focused beam position. It is proposed that the samarium atom heat processing is a novel technique for inducing structural modification (refractive index change) in the deep interior of glass.     

Evolution of surface morphology of NiO thin films under swift heavy ion irradiation

NiO nanoparticle thin films grown on Si substrates were irradiated by 107 MeV Ag⁸⁺ ions. The films were characterized by glancing angle X-ray diffraction and atomic force microscopy. Ag ion irradiation was found to influence the shape and size of the nanoparticles. The pristine NiO film consisted of uniform size (∼100 nm along major axis and ∼55 nm along minor axis) elliptical particles, which changed to also of uniform size (∼63 nm) circular shape particles on irradiation at a fluence of 3 × 10¹³ ions cm⁻². Comparison of XRD line width analysis and AFM data revealed that the particles in the pristine films are single crystalline, which turn to polycrystalline on irradiation with 107 MeV Ag ions.     

Ion implantation inducing nanovoids characterized by TEM and STEM

The evolution of nanoparticles in sequentially ion-implanted Ag and Ag/Cu into silica glasses has been studied. The doses for implantation (×10¹⁶ ions/cm²) were 5Ag, 5Ag/5Cu and 5Ag/15Cu. Ag nanoclusters have been formed in the implanted 5Ag specimen. In the implanted 5Ag/5Cu specimen, some formed nanoclusters have brighter center features. With an increase of Cu ions dose, the nanoclusters with brighter center features become prevalent. The microstructural properties of the nanoparticles are characterized by transmission electron microscopy. Scanning transmission electron microscope high-angle annular dark field and high-resolution transmission electron microscopy are also utilized to study the formed nanoparticles. The results show that nanovoids have been induced into metal nanoparticles during the ion implanting process, not the core-shell nanoparticles as other workers believed. The nanovoids can be the aggregation of vacancies induced by irradiation.     

Surface morphologic and structural analysis of IR irradiated silver

The microstructural morphological changes in laser irradiated targets are investigated. Nd:YAG laser (1064 nm, ∼12 ns nominal, 1.1 MW) is used to irradiate 4 N pure (99.99%) fine polished and annealed silver samples in ambient air and under vacuum ∼10⁻⁶ Torr. The laser spot size and power density at tight focus are 12 μm and 3×10¹¹ W/cm², respectively. SEM micrographs and X-ray diffractograms of the exposed and unexposed targets reveal the surface texture and structural changes, respectively. Amongst the ablation mechanisms involved, exfoliation and hydrodynamic sputtering are found to be dominant. Surface modifications appear in the form of craters and ripples formation. Heat is conducted non-uniformly through narrow channels at the surface. Thermal stresses induced by the laser do not disturb inter planar distance of the target. On the other hand irradiation causes significant variations in grain size and diffracted X-rays intensities.     

Synthesis and characterization of zinc oxide nanoparticles by laser ablation of zinc in liquid

We report formation of colloidal suspension of zinc oxide nanoparticles by pulsed laser ablation of a zinc metal target at room temperature in different liquid environment. We have used photoluminescence, atomic force microscopy and X-ray diffraction to characterize the nanoparticles. The sample ablated in deionized water showed the photoluminescence peak at 384 nm (3.23 eV), whereas peaks at 370 nm (3.35 eV) were observed for sample prepared in isopropanol. The use of water and isopropanol as a solvent yielded spherical nanoparticles of 14-20 nm while in acetone we found two types of particles, one spherical nanoparticles with sizes around 100 nm and another platelet-like structure of 1 μm in diameter and 40 nm in width. The absorption peak of samples prepared in deionized water and isopropanol are seen to be substantially blue shifted relative to that of the bulk zinc oxide due to the strong confinement effect. The technique offers an alternative for preparing the nanoparticles of active metal.     

Nano-graphene structures deposited by N-IR pulsed laser ablation of graphite on Si

Thin nano-structured carbon films have been deposited in vacuum by pulsed laser ablation, from a rotating polycrystalline graphite target, on Si 〈1 0 0〉 substrates, kept at temperatures ranging from RT to 800 °C. The laser ablation was performed by a Nd:YAG laser, operating in the near IR (λ = 1064 nm).X-ray diffraction analysis, performed at grazing incidence angle, both in-plane (ip-gid) and out-of-plane (op-gid), has shown the growth of oriented nano-sized graphene particles, characterised by high inter-planar stacking distance (d_? ∼ 0.39 nm), compared to graphite. The film structure and texturing are strongly related both to laser wavelength and substrate temperature: the low energy associated to the IR laser radiation (1.17 eV) generates activated carbon species of large dimensions that, also at low T (∼400 °C), easy evolve toward more stable sp² aromatic bonds, in the plume direction. Increasing temperature the nano-structure formation increases, causing a further aggregation of aromatic planes, voids formation, and a related density (by X-ray reflectivity) drop to very low values. SEM and STM show for these samples a strongly increased macroscopic roughness. The whole process, mainly at higher temperatures, is characterised by a fast kinetic mode, far from equilibrium and without any structural or spatial rearrangement.     

Optical features of the gold nanoparticles deposited on ITO substrates

We have performed firstly studies of the photoinduced second order susceptibilities in the Au nanoparticles (NP) A, B and C under simultaneous influence of the bicolor 1064 nm and bicolor laser treatment (1064 nm 10 ns pulsed laser with pulse power densities 532 nm 10 ns laser treatment and the cw 300 mW 532 nm SHG coherent laser beams. We have studied three types of samples possessing irregular and different dense parameters of the Au NP deposited on the ITO substrate. We have found that the maximal bicolor (1064 nm and 532 nm) stimulated optical second harmonic generation for the 10 ns pulse duration was observed for the samples possessing irregular Au NP deposited on the ITO. We have performed studies of the photoinduced second order susceptibilities in the Au NP under simultaneous influence of the bicolor 1064 nm and bicolor laser treatment (1064 nm 10 ns pulsed laser with pulse power densities 532 nm 10 ns laser treatment and the cw 300 mW 532 nm SHG coherent laser beams). We have found that during the 15-20 min of the cw treatment there occur the principal changes in the absorption maxima. These maxima indicate on the occurrence of the additional absorption nearby the 308 nm and 310 nm and 345 nm spectral bands. The later are caused by the occurrence of the trapping levels in the border between the ITO substrate and the Au nanoparticles.     

Laser ablation of silver and gold in liquid ammonia

Laser ablation of a silver (Ag) and/or gold (Au) target was performed in liquid ammonia (l-NH₃) at 233 K using nanosecond laser pulses of 1064, 532 and 355 nm wavelengths. An “in situ” monitoring of the ablation process by UV/vis/NIR spectroscopy has shown the evolution of the surface plasmon extinction band of silver or gold nanoparticles and thus confirmed their formation. While sols of Au nanoparticles in l-NH₃ are quite stable in air, those of Ag nanoparticles undergo oxidation to Ag(I) complexes with NH₃ ligands. On the other hand, formation of solvated electrons, namely of the (e⁻)NH₃ solvates, has not been unequivocally confirmed under the conditions of our laser ablation/nanoparticle fragmentation experiment, since only very weak vis/NIR spectral features of these solvates were observed with a low reproducibility. Reference experiments have shown that the well-known chemical production of these solvates is hindered by the presence of Ag and Au plates. Ag and Au targets can thus possibly act as electron scavengers in our ablation experiments.     

532 nm laser based on V-type doubly resonant intra-cavity frequency-doubling

LD side-pumped dual interconnected V-type quasi-continuous wave green laser has been demonstrated. The two Nd:YAG modules were placed in a plane-concave V-type resonator and a plane-concave straight cavity formed two stable operation beam of the 1064-nm fundamental frequency laser. Through acousto-optic Q-switched and frequency doubling crystal, two double-frequency laser beams arrived at the folded flat mirror, which were unidirectional output by the folded flat mirror at the end. As the pumped current was 50 A, the 532 nm green laser maximum average output power of 206 W at a repetition of 22.4 kHz was achieved with a pulse width of 201 ns and the largest single pulse energy of 9.2 mJ, corresponding to a peak power of 45.8 kW and a double frequency efficiency of 60.2%.     

Photoluminescence of ZnO nanoparticles generated by laser ablation in deionized water

Zinc oxide (ZnO) nanoparticles were synthesized using pulsed laser ablation of a Zn metal plate in deionized water without using surfactant. The beam of a Q-switched Nd:YAG laser of 1064-nm and 532-nm wavelengths at 6-ns pulse width and different fluences is employed to irradiate the solid target in water. Transmission electron microscopy images revealed that the size of the ZnO nanoparticles formed by the 532-nm wavelength laser beam is smaller than that of the nanoparticles generated by the 1064-nm wavelength laser beam. The room-temperature photoluminescence spectra of the ZnO nanoparticles show intense violet emission along with emission in blue and green bands. The excellent ultraviolet emission indicates that the ZnO nanostructures have a low defect concentration.     

High level compressive residual stresses produced in aluminum alloys by laser shock processing

Laser shock processing (LSP) has been proposed as a competitive alternative technology to classical treatments for improving fatigue and wear resistance of metals. We present a configuration and results for metal surface treatments in underwater laser irradiation at 1064 nm. A convergent lens is used to deliver 1.2 J/cm² in a 8 ns laser FWHM pulse produced by 10 Hz Q-switched Nd:YAG, two laser spot diameters were used: 0.8 and 1.5 mm.Results using pulse densities of 2500 pulses/cm² in 6061-T6 aluminum samples and 5000 pulses/cm² in 2024 aluminum samples are presented. High level of compressive residual stresses are produced −1600 MPa for 6061-T6 Al alloy, and −1400 MPa for 2024 Al alloy. It has been shown that surface residual stress level is higher than that achieved by conventional shot peening and with greater depths. This method can be applied to surface treatment of final metal products.     

Photoluminescence spectra of thin films containing CdSe/ZnS quantum dots irradiated by 532-nm laser radiation and gamma-rays

We have investigated temporal behavior of the photoluminescence (PL) spectra of thin films containing CdSe/ZnS quantum dots irradiated by 532 nm laser radiation and gamma-rays. Under ∼100 W/cm² laser radiation, the PL intensity (I_PL) increases with irradiation time upto about 500 s and thereafter declines linearly. The wavelength of the PL emission (λ_peak) exhibits a blue-shift with exposure time. Upon simultaneous irradiation by 100 W/cm² 532-nm laser, as well as 0.57 and 1.06 MeV gamma-rays, the temporal behaviors of both I_PL and λ_peak are significantly different; I_PL increases to a saturation level, and the magnitude of the blue-shift in λ_peak is reduced. We discuss possible mechanisms underlying these results.     

Phase transitions in femtosecond laser ablation

In this study we simulate an interaction of femtosecond laser pulses (100 fs, 800 nm, 0.1-10 J/cm²) with metal targets of Al, Au, Cu, and Ni. For analysis of laser-induced phase transitions, melting and shock waves propagation as well as material decomposition we use an Eulerian hydrocode in conjunction with a thermodynamically complete two-temperature equation of state with stable and metastable phases. Isochoric heating, material evaporation from the free surface of the target and fast propagation of the melting and shock waves are observed. On rarefaction the liquid phase becomes metastable and its lifetime is estimated using the theory of homogeneous nucleation. Mechanical spallation of the target material at high strain rates is also possible as a result of void growth and confluence. In our simulation several ablation mechanisms are taken into account but the main issue of the material is found to originate from the metastable liquid state. It can be decomposed either into a liquid-gas mixture in the vicinity of the critical point, or into droplets at high strain rates and negative pressure. The simulation results are in agreement with available experimental findings.     

Characterization of Ag and Au nanoparticles created by nanosecond pulsed laser ablation in double distilled water

Pulsed laser ablation of Ag and Au targets, immersed in double-distilled water is used to synthesize metallic nanoparticles (NPs). The targets are irradiated for 20 min by laser pulses at different wavelengths—the fundamental and the second harmonic (SHG) (λ = 1064 and 532 nm, respectively) of a Nd:YAG laser system. The ablation process is performed at a repetition rate of 10 Hz and with pulse duration of 15 ns. Two boundary values of the laser fluence for each wavelength under the experimental conditions chosen were used—it varied from several J/cm² to tens of J/cm². Only as-prepared samples were measured not later than two hours after fabrication. The NPs shape and size distribution were evaluated from transmission electron microscopy (TEM) images. The suspensions obtained were investigated by optical transmission spectroscopy in the near UV and in the visible region in order to get information about these parameters. Spherical shape of the NPs at the low laser fluence and appearance of aggregation and building of nanowires at the SHG and high laser fluence was seen. Dependence of the mean particle size at the SHG on the laser fluence was established. Comments on the results obtained have been also presented.     

Spontaneous organisation of ZnS nanoparticles into monocrystalline nanorods with highly enhanced dopant-related emission

A natural self-assembly process of semiconductor nanoparticles leading to the formation of doped, monocrystalline nanorods with highly enhanced dopant-related luminescence properties is reported. ∼4 nm sized, polycrystalline ZnS nanoparticles of zinc-blende (cubic) structure, doped with Cu⁺-Al³⁺ or Mn²⁺ have been aggregated in the aqueous solution and grown into nanorods of length ∼400 nm and aspect ratio ∼12. Transmission electron microscopic (TEM) images indicate crystal growth mechanisms involving both Ostwald-ripening and particle-to-particle oriented-attachment. Sulphur-sulphur catenation is proposed for the covalent-linkage between the attached particles. The nanorods exhibit self-assembly mediated quenching of the lattice defect-related emission accompanied by multifold enhancement in the dopant-related emission. This study demonstrates that the collective behavior of an ensemble of bare nanoparticles, under natural conditions, can lead to the formation of functionalized (doped) nanorods with enhanced luminescence properties.     

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.