Mechanism of ablation of CdS at laser wavelengths in the visible and in the UV

The mechanisms of laser ablation of CdS targets at different laser wavelengths have been investigated. (CdS)_n⁺ cluster formation is only observed upon 532 nm ablation. The time and energy distributions of neutral S, S₂, Cd and CdS show significant dependence on laser wavelength. Bimodal distributions are observed at 266 and 308 nm. For the former, the average kinetic energy increases significantly with mass, taking values in the range of 0.3-1.7 eV. At 308 nm the slow component of the time distribution disappears at distances above the target larger than 1 cm. At this wavelength, the observed time distribution appears to reflect mainly the dynamics of the expansion. At 532 nm the time distribution is monomodal and the average kinetic energies are below 0.2 eV. Clear indications of the participation of thermal (at 532 nm) and non-thermal mechanisms (at 266 nm) have been found. It is tentatively concluded that the cluster formation observed upon ablation at 532 nm can be related to the thermal ablation mechanisms in which the low kinetic energy of the species in the plume and their similar velocities favor the aggregation processes.     

Nanocomposite ZnO/Au formation by pulsed laser irradiation

The ZnO/Au nanocomposite formation involves synthesis of Au and ZnO colloidal solutions by 532 nm pulse laser ablation of metal targets in deionized water followed by laser irradiation of the mixed colloidal solution. The transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) images show evolution of spherical particles into ZnO/Au nanonetworks with irradiation time. The formation mechanism of the nanonetwork can be explained on the basis of near resonance absorption of 532 nm irradiation by gold nanoparticles which can cause selective melting and fusion of gold nanoparticles to form network. The ZnO/Au nanocomposites show blue shift in the ZnO exciton absorption and red shift in the Au plasmon resonance absorption due to interfacial charge transfer.     

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.     

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.     

Photodegradation of PAMAM G5-stabilized aqueous suspensions of gold nanoparticles

Gold nanoparticles are produced in the form of colloidal suspensions in water by ps laser ablation of a metallic target. The fifth generation of ethylenediamine-core poly(amidoamine) (PAMAM G5) is used as a capping agent. Thanks to the ability of PAMAM to encapsulate and stabilize gold cations within its inner cavities, it is possible to evidence, by simple UV-visible spectroscopy, a photo-fragmentation process induced by the 532 nm radiation, which is resonant with the absorption plasmon band of gold nanoparticles. This effect, that can be also exploited to control the size and shape of gold nanoparticles obtained with different procedures, arises from electron photo-ejection and subsequent charging and disintegration of existing gold nanoparticles into smaller size products.     

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.     

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).     

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.     

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.     

Rapid synthesize of gold nanoparticles by microwave irradiation method and its application as an optical limiting material

We present rapid synthesis of gold nanoparticles by microwave irradiation method. Sample with average particle size 7.7 nm is obtained from TEM. Linear and nonlinear optical studies of the prepared samples are discussed. Reverse saturable absorption (RSA) at longitudinal surface plasmon resonance (SPR) in gold nanoparticles (Au NPs) have been observed using Z-scan and transient absorption techniques with 532 nm laser pulses. Such RSA behavior makes Au NPs an ideal candidate for optical limiting applications.     

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-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.     

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.     

Analysis of surface and material modifications caused by laser drilling of AlN ceramics

For the laser drilling of aluminum nitride ceramic the processing results and the effects related to pulsed irradiation were investigated. Images of the drilled surface revealed regular, cylindrically shaped holes of about 100 μm in diameter independently of the laser wavelength (1064/532/355 or 266 nm). The holes were surrounded by circular heat-affected zones of larger diameter. A comparison of the elemental compositions of the original material and the processed one indicated a decrease of the nitrogen concentration in the affected area. The spectral analysis of the ablated material composition revealed the presence of ions and neutrals in dependence on the laser intensity applied. It was found that at intensity values close to the ablation threshold the ejected material consisted mainly of neutrals, while doubling of the intensity resulted in appearance of single-ionized Al species, which were also observed together with Al clusters in the mass spectra of the UV-excited plasma. Their prevailing content was revealed for drilling at higher intensities around 15 GW/cm² at 532 nm. Results of model calculations indicated, in agreement with the experiment, that at the threshold the ceramic decomposes into gaseous nitrogen and solid Al particulates, while at a higher fluence the material particles vaporize and influence the quality of drilling.     

Photoluminescent zinc oxide polymer nanocomposites fabricated using picosecond laser ablation in an organic solvent

Nanocomposites made of ZnO nanoparticles dispersed in thermoplastic polyurethane were synthesized using picosecond laser ablation of zinc in a polymer-doped solution of tetrahydrofuran. The pre-added polymer stabilizes the ZnO nanoparticles in situ during laser ablation by forming a polymer shell around the nanoparticles. This close-contact polymer shell has a layer thickness up to 30 nm. Analysis of ZnO polyurethane nanocomposites using optical spectroscopy, high resolution transmission electron microscopy and X-ray diffraction revealed that oxidized and crystalline ZnO nanoparticles were produced. Those nanocomposites showed a green photoluminescence emission centred at 538 nm after excitation at 350 nm, which should be attributed to oxygen defects generated during the laser formation mechanism of the monocrystalline nanoparticles. Further, the influence of pulse energy and polymer concentration on the production rate, laser fluence and energy-specific mass productivity was investigated.     

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。     

Interaction of gold nanoparticles with nanosecond laser pulses: Nanoparticle heating

Theoretical and experimental results on the heating process of gold nanoparticles irradiated by nanosecond laser pulses are presented. The efficiency of particle heating is demonstrated by in-vitro photothermal therapy of human tumor cells. Gold nanoparticles with diameters of 40 and 100 nm are added as colloid in the cell culture and the samples are irradiated by nanosecond pulses at wavelength of 532 nm delivered by Nd:YAG laser system. The results indicate clear cytotoxic effect of application of nanoparticle as more efficient is the case of using particles with diameter of 100 nm. The theoretical analysis of the heating process of nanoparticle interacting with laser radiation is based on the Mie scattering theory, which is used for calculation of the particle absorption coefficient, and two-dimensional heat diffusion model, which describes the particle and the surrounding medium temperature evolution. Using this model the dependence of the achieved maximal temperature in the particles on the applied laser fluence and time evolution of the particle temperature is obtained.     

High power single-shot laser ablation of silicon with nanosecond 355 nm

We report on high intensity single-shot laser ablation of monocrystalline silicon with a nanosecond Nd:YAG at 355 nm. It is shown that for incident laser intensities exceeding ∼11.5 GW/cm² on the silicon surface, unusually high etch depths can be achieved reaching values up to 60 μm. The results support previous observations of dramatic increase in etch rates in single-shot laser ablation at 266 nm. A laser-induced explosive boiling mechanism together with secondary plasma heating is believed to be associated with this effect.     

Femtosecond pulsed laser deposition of nanostructured TiO2 films

Nanostructured deposits of TiO₂ were grown on Si (1 0 0) substrates by laser ablating a TiO₂ sintered target in vacuum or in oxygen using a Ti:sapphire laser delivering 80 fs pulses. The effect of the laser irradiation wavelength on the obtained nanostructures, was investigated using 800, 400 and 266 nm at different substrate temperatures and pressures of oxygen. The composition of the deposits was characterized using X-ray photoelectron spectroscopy (XPS) and the surface morphology was studied by environmental scanning electron microscopy (ESEM) and atomic force microscopy (AFM). Deposits are absent of microscopic droplets in all conditions explored. The best deposits, constituted by nanoparticles of an average diameter of 30 nm with a narrow size distribution, were obtained at the shorter laser wavelength of 266 nm under vacuum at substrate room temperature.     

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.