Synthesis of nanosized particles during laser ablation of gold in water

In this paper we report the formation of gold nanoparticles during laser ablation of gold target in water in the absence of any additives. The experiments were carried out by using the radiation of the pulsed Nd:YAG laser, operating at the second (532 nm, 10 ns, 10 Hz), or the fourth harmonic (266 nm) wavelengths. The properties of the nanoparticles were found to be susceptible to the additional 532 and 266 nm laser irradiation. It has been established that both the mean size of the nanoparticles and their stability could be varied by proper selection of the parameters of laser ablation and postirradiation such as laser fluence and wavelength combinations.     

Non-thermal laser-induced desorption of metal atoms with bimodal kinetic energy distribution

Laser-induced desorption of metal atoms at low rate has been studied for pulsed excitation with wavelengths of = 266, 355, 532 and 1064 nm. For this purpose sodium adsorbed on quartz served as a model system. The detached Na atoms were photo-ionized with the light of a second laser operating at = 193 nm and their kinetic energy distribution was determined by time-of-flight measurements. For = 1064 nm a distribution typical of thermal bond breaking is observed. If desorption, however, is stimulated with light of = 266 or 532 nm, the kinetic energy distribution is non-thermal with a single maximum atE _kin = 0.16 ± 0.02 eV. For = 355 nm the non-thermal distribution is even bimodal with maxima appearing atE _kin = 0.16 ± 0.02 and 0.33 ± 0.02 eV. These values of the kinetic energies actually remain constant under variation of all experimental parameters. They appear to reflect the electronic and geometric properties of different binding sites from which the atoms are detached and thus constitute fingerprints of the metal surface. The non-thermal desorption mechanism is discussed in the framework of the Menzel-Gomer-Redhead scenario. The transition from non-thermal to thermal desorption at large fluentes of the laser light could also be identified.     

Small size TiO2 nanoparticles prepared by laser ablation in water

Titanium dioxide nanoparticles in distilled H₂O solvent were prepared by laser ablation. The experiments were performed irradiating a Ti target with a second harmonic (532 nm) output of a Nd:YAG laser varying the operative fluence between 1 and 10 J cm⁻² and for an ablation time ranging from 10 to 30 min. Electron microscopy measurements have evidenced the predominant presence of nanoparticles with diameter smaller than 10 nm together with agglomerations of 100-200 nm whose content increases with the laser fluence. At low laser fluence the particles’ size distribution shows that more than 85% of the nanoparticles have a size smaller than 5 nm while at mid and high fluences the presence of 5-7 nm nanoparticles is predominant. XPS analysis has revealed the presence of different titanium suboxide phases with the prevalence of Ti-O bonds from TiO₂ species. The optical bandgap values, determined by UV-vis absorption measurements, are compatible with the anatase phase.     

Application of the laser ablation for conservation of historical paper documents

Laser ablation was applied for surface cleaning and spectroscopic diagnostics of historical paper documents and model samples in the framework of the conservation projects. During cleaning the spectra of ablation products were recorded by means of the LIBS technique which allowed for nearly non-destructive identification of surface layers such as contaminants, substrate and pigments. For consecutive laser pulses a strong decrease of band intensities of the emission lines of Ca, Na, K, Al and Fe ascribed to contaminants were observed. The effect was used for monitoring of the cleaning progress of stained paper. For surface cleaning and spectra excitation the Q-switched Nd:YAG laser of 6 ns pulsewidth operating at wavelengths of 266, 355, 532, and 1064 nm and of fluence selected from the range 0.3-0.9 J/cm² was applied. The ablation parameters were optimized in agreement with the literature and the results were confirmed by surface studies and testing of the mechanical and chemical properties, and also by the response to the ageing process of the paper substrate. In case of the model paper irradiated in the UV range at 266 and 355 nm a visual inspection revealed local damages of the cellulose fibers accompanied by a decrease of the mechanical strength of the substrate. The effect was more pronounced after artificial ageing. The best results were obtained for samples irradiated at 532 nm and at laser fluence below the damage threshold of 0.6 J/cm², which is in agreement with literature.     

Laser ablation synthesis of indium oxide nanoparticles in water

Colloidal solutions of Indium oxide nanoparticles have been produced by means of laser ablation in liquids (LALs) technique by simply irradiating with a second harmonic (532 nm) Nd:YAG laser beam a metallic indium target immersed in distilled water and varying the laser fluence up to 10 J cm⁻² and the ablation time up to 120 min. At all the investigated fluences the vaporization process of the indium target is the dominant one. It produces a majority (>80%) of small size (<6 nm) nanoparticles, with a very limited content of larger ones (size between 10 and 20 nm). The amount of particles increases regularly with the ablation time, supporting the scalability of the production technique. The deposited nanoparticles stoichiometry has been verified by both X-ray photoelectron spectroscopy (XPS) and Energy Dispersive X-ray (EDX) analysis. Optical bandgap values of 3.70 eV were determined by UV-vis absorption measurements. All these results confirm the complete oxidation of the ablated material.     

Characterization of the laser ablation plasma used for the deposition of amorphous carbon

The plasma produced by laser ablation of a graphite target was studied by means of optical emission spectroscopy and a Langmuir planar probe. Laser ablation was performed using a Nd:YAG laser with emission at the fundamental line with pulse length of 28 ns. In this work, we report the behavior of the mean kinetic energy of plasma ions and the plasma density, as a function of the laser fluence (J/cm²), and the target to probe (substrate) distance. The characterized regimes were employed to deposit amorphous carbon at different values of kinetic energy of the ions and plasma density. The mean kinetic energy of the ions could be changed from 40 to 300 eV, and the plasma density could be varied from 1 × 10¹² to 7 × 10¹³ cm⁻³. The main emitting species were C⁺ (283.66, 290.6, 299.2 and 426.65 nm) and C⁺⁺ (406.89 and 418.66 nm) with the C⁺ (426.65 nm) being the most intense and that which persisted for the longest times. Different combinations of the plasma parameters yield amorphous carbon with different structures. Low levels (about 40 eV) of ion energy produce graphitic materials, while medium levels (about 200 eV) required the highest plasma densities in order to increase the CC sp³ bonding content and therefore the hardness of the films. The structure of the material was studied by means of Raman spectroscopy, and the hardness and elastic modulus by depth sensitive nanoindentation.     

Generation of CdS clusters using laser ablation: the role of wavelength and fluence

The formation of cationic clusters in the laser ablation of CdS targets has been investigated as a function of wavelength and fluence by mass spectrometric analysis of the plume. Ablation was carried out at the laser wavelengths of 1064, 532, 355, and 266 nm in order to scan the interaction regimes below and above the energy band gap of the material. In all cases, the mass spectra showed stoichiometric Cd _n S _n ⁺ and nonstoichiometric Cd _n S _n−1⁺, Cd _n S _n+1⁺, and Cd _n S _n+2⁺ clusters up to 4900 amu. Cluster size distributions were well represented by a log-normal function, although larger relative abundance for clusters with n=13, 16, 19, 34 was observed (magic numbers). The laser threshold fluence for cluster observation was strongly dependent on wavelength, ranging from around 16 mJ/cm² at 266 nm to more than 300 mJ/cm² at 532 and 1064 nm. According to the behavior of the detected species as a function of fluence, two distinct families were identified: the “light” family containing S₂⁺ and Cd⁺ and the “heavy” clusterized family grouping Cd₂⁺ and Cd _n S _m ⁺. In terms of fluence, it has been determined that the best ratio for clusterization is achieved close to the threshold of appearance of clusters at all wavelengths. At 1064, 532, and 355 nm, the production of “heavy” cations as a function of fluence showed a maximum, indicating the participation of competitive effects, whereas saturation is observed at 266 nm. In terms of relative production, the contribution of the “heavy” family to the total cation signal was significantly lower for 266 nm than for the longer wavelengths. Irradiation at 355 nm in the fluence region of 200 mJ/cm² has been identified as the optimum for the generation of large clusters in CdS.     

Dual mode emission and harmonic generation in ZnO-CaO-Al2O3: Er nano-composite

Er³⁺ doped ZnO-CaO-Al₂O₃ nano-composite phosphor has been synthesized through combustion method and its emission and harmonic generation properties have been studied. The X-ray diffraction and thermal analysis techniques have been used to prove the dual phase (ZnO and CaO-Al₂O₃) nature of the phosphor. The phosphor has shown up-conversion emission on near-infra-red (976 nm) excitation and down-conversion emission on 355 nm excitation in presence of Er³⁺ and thus behaves as a dual mode phosphor. On excitation with 976 nm diode laser, material shows color tunability (calcination of composite material at different temperatures). Formation of ZnO nanocrystals on heat treatment of as-synthesized sample has shown its characteristic emission at 388 nm and also the energy transfer from ZnO to Er³⁺ ions. The low temperature emission measurements have been carried out and the results have been discussed. Phosphor has shown strong second harmonic generation (SHG) at 532 nm on 1064 nm and at 266 nm on 532 nm excitation.     

Optical and nonlinear optical characteristics of the Ge and GaAs nanoparticle suspensions prepared by laser ablation

The laser ablation of Ge and GaAs targets placed in water and ethanol was carried out using the fundamental radiation of nanosecond Nd:YLF laser. The results of preparation and the optical and nonlinear optical characterization of the Ge and GaAs nanoparticle suspensions are presented. The considerable shift of the band gap energy of the nanoparticles compared to the bulk semiconductors was observed. The distribution of nanoparticle sizes was estimated in the range of 1.5-10 nm on the basis of the TEM and spectral measurements. The nonlinear refractive indices and nonlinear absorption coefficients of Ge and GaAs nanoparticles were defined by the z-scan technique using second harmonic radiation of picosecond Nd:YAG laser (λ = 532 nm).     

Patterning of indium-tin oxide on glass with picosecond lasers

The results of patterning of the indium-tin oxide (ITO) film on the glass substrate with high repetition rate picosecond lasers at various wavelengths are presented. Laser radiation initiated the ablation of the material, forming grooves in ITO. Profile of the grooves was analyzed with a phase contrast optical microscope, a stylus type profiler, scanning electron microscope (SEM) and atomic force microscope (AFM). Clean removal of the ITO film was achieved with the 266 nm radiation when laser fluence was above the threshold at 0.20 J/cm², while for the 355 nm radiation, the threshold was higher, above 0.46 J/cm². The glass substrate was damaged in the area where the fluence was higher than 1.55 J/cm². The 532 nm radiation allowed getting well defined grooves, but a lot of residues in the form of dust were generated on the surface. UV radiation with the 266 nm wavelength provided the widest working window for ITO ablation without damage of the substrate. Use of UV laser radiation with fluences close to the ablation threshold made it possible to minimize surface contamination and the recast ridge formation during the process.     

Submicron foaming in gelatine by nanosecond and femtosecond pulsed laser irradiation

We compare the foaming characteristics induced by irradiation with single ns and fs laser pulses of UV, VIS and IR wavelengths on gelatines differing in gel strength (bloom values 75 and 225) and in crosslinking degree. We have observed that while laser irradiation with nanoseconds leads to the formation of a microfoam layer at 266 nm, and melting and crater formation at longer wavelengths (532 and 1064 nm), fs pulse irradiation leads to submicron foaming at all wavelengths studied (266, 400 and 800 nm). These results show the possibility of controlling the submicrometric foam structure in this biomaterial and can shed light into the working mechanisms of fs laser nanoprocessing in biomaterials, where increase of temperature, thermoelastic stress generation, and stress-induced bubble formation are mediated by the generated plasma.     

Surface modifications of AISI 1045 steel created by high intensity 1064 and 532 nm picosecond Nd:YAG laser pulses

Interaction of Nd:YAG laser, operating at 1064 or 532 nm wavelength and a pulse duration of 40 ps, with AISI 1045 steel was studied. Surface damage thresholds were estimated to be 0.30 and 0.16 J/cm² at the wavelengths of 1064 and 532 nm, respectively. The steel surface modification was studied at the laser energy density of 10.3 J/cm² (at 1064 nm) and 5.4 J/cm² (at 532 nm). The energy absorbed from Nd:YAG laser beam is partially converted to thermal energy, which generates a series of effects, such as melting, vaporization of the molten material, shock waves, etc. The following AISI 1045 steel surface morphological changes and processes were observed: (i) both laser wavelengths cause damage of the steel in the central zone of irradiated area; (ii) appearance of a hydrodynamic feature in the form of resolidified droplets of the material in the surrounding outer zone with 1064 nm laser wavelength; (iii) appearance of periodic surface structures, at micro- and nano-level, with the 532 nm wavelength and, (iv) development of plasma in front of the target. Generally, interaction of laser beam with the AISI 1045 steel (at 1064 and 532 nm) results in a near-instantaneous creation of damage, meaning that large steel surfaces can be processed in short time.     

Comparison of the laser ablation process on Zn and Ti using pulsed digital holographic interferometry

Pulsed digital holographic interferometry has been used to compare the laser ablation process of a Q-switched Nd-YAG laser pulse (wavelength 1064 nm, pulse duration 12 ns) on two different metals (Zn and Ti) under atmospheric air pressure. Digital holograms were recorded for different time delays using collimated laser light (532 nm) passed through the volume along the target. Numerical data of the integrated refractive index field were calculated and presented as phase maps. Intensity maps were calculated from the recorded digital holograms and are used to calculate the attenuation of the probing laser beam by the ablated plume. The different structures of the plume, namely streaks normal to the surface for Zn in contrast to absorbing regions for Ti, indicates that different mechanisms of laser ablation could happen for different metals for the same laser settings and surrounding gas. At a laser fluence of 5 J/cm², phase explosion appears to be the ablation mechanism in case of Zn, while for Ti normal vaporization seems to be the dominant mechanism.     

Fine structure in the time of flight distribution of C2 in laser produced plasma from graphite

Time resolved optical emission spectroscopy is employed to study the expansion dynamics of C₂ species in a graphite plasma produced during the Nd : YAG ablation. At low laser fluences a single peak distribution with low kinetic energy is observed. At higher fluences a twin peak distribution is found. It has been noted that these double peak time of flight distribution splits into a triple peak structure at distances ≥17mm from the target surface. The reason for the occurrence of multiple peak is due to different formation mechanisms of C₂ species.     

真空条件下不同波长固体激光烧蚀单晶硅的实验研究

通过倍频Nd：YAG固体激光的基波得到波长分别为532、355和266 nm的激光,研究了单晶硅（Si）对不同波长固体激光的吸收规律和3种不同波长激光在真空条件下烧蚀单晶Si的烧蚀特征。结果表明,单晶Si对波长为100~370 nm的紫外激光具有很好的吸收效果;在其他条件相同时,532 nm波长激光烧蚀单晶Si所需最低单脉冲能量（Ep=30 μJ）是355和266 nm波长激光烧蚀单晶Si所需最低单脉冲能量（Ep=15 μJ）的2倍;532、355和266 nm的激光烧蚀单晶Si的烧蚀阈值随着波长的变短而变小。     

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.     

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.     

Surface modifications of a titanium implant by a picosecond Nd:YAG laser operating at 1064 and 532 nm

Interaction of an Nd:YAG laser, operating at 1064 or 532 nm wavelength and pulse duration of 40 ps, with titanium implant was studied. Surface damage thresholds were estimated to 0.9 and 0.6 J/cm² at wavelengths 1064 and 532 nm, respectively. The titanium implant surface modification was studied by the laser beam of energy density of 4.0 and 23.8 J/cm² (at 1064 nm) and 13.6 J/cm² (at 532 nm). The energy absorbed from the Nd:YAG laser beam is partially converted to thermal energy, which generates a series of effects, such as melting, vaporization of the molten material, shock waves, etc. The following titanium/implant surface morphological changes were observed: (i) both laser wavelengths cause damage of the titanium in the central zone of the irradiated area, (ii) appearance of a hydrodynamic feature in the form of resolidified droplets of the material in the surrounding outer zone with the 1064 nm laser wavelength and (iii) appearance of wave-like microstructures with the 532 nm wavelength. Generally, both laser wavelengths and the corresponding laser energy densities can efficiently enhance the titanium/implant roughness. This implant roughness is expected to improve its bio-integration. The process of the laser interaction with titanium implant was accompanied by formation of plasma.     

High-quality and high-efficiency machining of glass materials by laser-induced plasma-assisted ablation using conventional nanosecond UV, visible, and infrared lasers

This paper reports the micromachining of fused quartz and Pyrex glass by laser-induced plasma-assisted ablation (LIPAA) using a conventional nanosecond laser at wavelengths 266 nm, 532 nm, and 1064 nm, respectively. High-quality surface structuring can be achieved at each of these wavelengths. The micrograting formed has periods of 14 7m at 266 nm, 20 7m at 532 nm, and 30 7m at 1064 nm, respectively. The ablation rate using a 266 nm laser is much larger than that at longer wavelengths. The ablation thresholds of laser fluence are 0.7 J/cm² for 266 nm, 1.5 J/cm² for 532 nm and 3.7 J/cm² for 1064 nm, respectively. The 532 nm and 1064 nm lasers enable hole drilling in 0.5 and 2.0-mm thick fused quartz and Pyrex glass substrates of about 0.7-0.8 mm in diameter. However, the less destructive through channel can be only formed in Pyrex glass by using a 532 nm laser.     

Laser ablation and deposition of wide bandgap semiconductors: plasma and nanostructure of deposits diagnosis

Nanostructured CdS and ZnS films on Si (100) substrates were obtained by nanosecond pulsed laser deposition at the wavelengths of 266 and 532 nm. The effect of laser irradiation wavelength on the surface structure and crystallinity of deposits was characterized, together with the composition, expansion dynamics and thermodynamic parameters of the ablation plume. Deposits were analyzed by environmental scanning electron microscopy, atomic force microscopy and X-ray diffraction, while in situ monitoring of the plume was carried out with spectral, temporal and spatial resolution by optical emission spectroscopy. The deposits consist of 25–50 nm nanoparticle assembled films but ablation in the visible results in larger aggregates (150 nm) over imposed on the film surface. The aggregate free films grown at 266 nm on heated substrates are thicker than those grown at room temperature and in the former case they reveal a crystalline structure congruent with that of the initial target material. The observed trends are discussed in reference to the light absorption step, the plasma composition and the nucleation processes occurring on the substrate.