Silicon nanoparticles generated by femtosecond laser ablation in a liquid environment

Silicon nanoparticles were generated by femtosecond laser [387 nm, 180 fs, 1 kHz, pulse energy = 3.5 μJ (fluence = 0.8 J/cm²)] ablation of silicon in deionized water. Nanoparticles with diameters from ~5 up to ~200 nm were observed to be formed in the colloidal solution. Their size distribution follows log-normal function with statistical median diameter of ≈20 nm. Longer ablation time leads to a narrowing of the nanoparticle size distribution due to the interaction of the ablating laser beam with the produced nanoparticles. Raman spectroscopy measurements confirm that the nanoparticles exhibit phonon quantum confinement effects and indicate that under the present conditions of ablation they are partially amorphous.     

Morphology studies of the metal surfaces with enhanced absorption fabricated using interferometric femtosecond ablation

Recently, the enhancing of bulk metals optical absorption with focused femtosecond pulses was demonstrated. This absorption enhancement is caused by different nano- and micro-structures which are formed during laser ablation with ultrashort pulses. In this paper we study the evolution of the surface structures using interferometric ablation and compare it to normal fs-ablation. Previously we have shown that interferometric femtosecond ablation is an efficient method to fabricate absorbing metal surfaces. In this study we ablated large areas of hole-array structures with different pulse numbers in polished stainless steel and copper samples. The evolution of surface morphology and the depth of the holes for these structured surfaces are presented. In addition, the reflectance of laser generated surface structures are measured at the wavelength range of 200–2300 nm using a standard spectrophotometer.     

Fabrication of gold nanoparticles in water by laser ablation technique and their characterization

A colloidal solution of gold nanoparticles in deionized nanopure water was produced by laser ablation technique without the use of any chemical/surfactant. Spectral characterization and morphological studies of these nanoparticles were carried out by UV-Vis Spectroscopy and Scanning Electron Microscopy, respectively. A number of variables of the ablating laser pulse have been used to control the size of the fabricated nanoparticles. Excellent correlation between ablating laser pulse parameter and optical and morphological parameters of the gold colloids were obtained. The peak of the extinction spectra shows a monotonic blue shift for laser fluence of 410 J/cm² and above. Below this the extinction peak remains fairly constant in wavelength. Blue shifts of the extinction spectra were also observed with increasing re-ablation time of previously ablated gold colloids. Possible explanations of all these observations are discussed.     

Nonadiabatic nondegenerate excitation by optical near-field and its application to optical pulse-shape measurement

Using DCM dye grains and light of different wavelengths generated by two CW laser diodes that oscillate in the near-infrared wavelength region, visible light emission from dye grains due to near-infrared excitation based on a nonadiabatic, nondegenerate excitation process was observed for the first time. Unlike sum-frequency generation with nonlinear polarization, the difference in polarization angles of the two beams did not affect the emitted light intensity. Optical sampling based on this nonadiabatic, nondegenerate excitation principle was demonstrated for the first time. The optical pulse shape in the wavelength band of λ=1250–1350 nm, which is close to the wavelength range used for optical fiber communications, was measured with a temporal resolution of 0.8–1.1 ps.     

Time-resolved dynamics analysis of nanoparticles applying dual femtosecond laser pulses

The evolution of a fs laser generated plume on copper was studied by dual laser pulses. The plume generated by the first pulse (620 nm) was excited by the second, delayed pulse (310 nm). The actual state of the plume was monitored by detecting the intensities of the emitted light and the reflected delayed pulse from the interaction range, i.e. 0–150 μm above the surface. Four peaks were observed in the 0–1400 ps time range and assigned to appearance of electrons, ions, atomic species and nanoparticles. Accordingly, the timing of the creation and ejection of these species was determined. By integrating the intensity of the nanoparticle peak, the production yield of the nanoparticles and its dependence on the ablating laser fluence was calculated. The ablation products were deposited on a Si substrate, too, and analyzed by atomic force microscopy and scanning electron microscopy. The results of the deposition and the dual-pulse experiments are in good agreement with the theory. PACS 52.38.Mf; 79.20.Ds; 61.80.Ba     

Optical absorption in early stage low temperature laser produced plasma

We describe a new technique to measure the UV/visible absorption spectrum of the ablated material during the laser pulse. The technique utilizes the continuum emission from one laser produced plasma as a light source to measure the absorption properties of a second laser produced plasma which is formed on a semi-transparent target with an array of 40 μm holes. A 6 ns, 1064 nm laser was used to ablate a Ag target and the plasma absorption was measured in the range 450–625 nm for a laser fluence of 1 J cm⁻². The total absorption cross-section is (0.5–1.5)×10⁻¹⁷ cm² in the range 450–540 nm. By comparing the measured absorption with a calculation using the plasma spectroscopy code FLYCHK it can be concluded that, in the wavelength region examined here, the absorption is mainly due to bound-bound transitions.     

Efficient and widely step-tunable terahertz generation with a dual-wavelength CO<Subscript>2</Subscript> laser

Coherent terahertz radiation in a widely step-tunable range of 72.3–2706 μm (0.11–4.15 THz) has been generated in GaAs crystal by difference-frequency generation using one CO₂ laser with dual-wavelength output. The peak power of THz pulse reaches 35 W at the wavelength of 236.3 μm, which corresponds to a pulse energy of 2.1 μJ. An average power of 10 μW has been achieved when working repetitively. This efficient terahertz radiation source is more compact and widely tunable than other THz sources pumped by CO₂ laser.     

In-situ bioconjugation in stationary media and in liquid flow by femtosecond laser ablation

In-situ functionalization of gold nanoparticles with fluorophore-tagged oligonucleotides is studied by comparing femtosecond laser ablation in stationary liquid and in biomolecule flow. Femtosecond laser pulses induce significant degradation to sensitive biomolecules when ablating gold in a stationary solution of oligonucleotides. Contrary, in-situ conjugation of nanoparticles in biomolecule flow considerably reduces the degree of degradation studied by gel electrophoresis and UV–Vis spectrometry. Ablating gold with 100 μJ femtosecond laser pulses DNA sequence does not degrade, while the degree of fluorophore tag degradation was 84% in stationary solution compared to 5% for 1 mL/min liquid flow. It is concluded that femtosecond laser-induced degradation of biomolecules is triggered by absorption of nanoparticle conjugates suspended in the colloid and not by ablation of the target. Quenching of nanoparticle size appears from 0.5 μM biomolecule concentration for 0.3 μg/s nanoparticle productivity indicating the successful surface functionalization. Finally, increasing the liquid flow rate from stationary to 450 mL/min enhances nanoparticle productivity from 0.2 μg/s to 1.5 μg/s, as increasing liquid flow allows removal of light absorbing nanoparticles from the ablation zone, avoiding attenuation of subsequent laser photons.     

All-optical ion generation for ion trap loading

We have investigated the all-optical generation of ions by photo-ionisation of atoms generated by pulsed laser ablation. A direct comparison between a resistively heated oven source and pulsed laser ablation is reported. Pulsed laser ablation with 10 ns Nd:YAG laser pulses is shown to produce large calcium flux, corresponding to atomic beams produced with oven temperatures greater than 650 K. For an equivalent atomic flux, pulsed laser ablation is shown to produce a thermal load more than one order of magnitude smaller than the oven source. The atomic beam distributions obey Maxwell–Boltzmann statistics with most probable speeds corresponding to temperatures greater than 2200 K. Below a threshold pulse fluence between 280 mJ/cm² and 330 mJ/cm², the atomic beam is composed exclusively of ground-state atoms. For higher fluences ions and excited atoms are generated.     

Temporal pulsewidth and the wavelength dependences of the product ions obtained by laser ablation of solid C<Subscript>60</Subscript>

By ablating solid C₆₀ with a laser pulse, we observe various processes such as the prompt- and the delayed-ionization of C₆₀, the fragmentation into molecular ions and the formation of cluster ions. We found these processes show distinct dependences on the temporal pulse width, the power and the wavelength of the ablation laser. From the observations, we could confirm efficient coupling of laser energy to C₆₀ through the molecular absorption even with a laser pulse width less than the electron-phonon coupling time of the C₆₀ molecule.     

Critical role of laser wavelength on carbon films grown by PLD of graphite

The structure of thin films deposited by pulsed laser ablation (PLD) is strongly dependent on experimental conditions, like laser wavelength and fluence, substrate temperature and pressure. Depending on these parameters we obtained various kinds of carbon materials varying from dense, mainly tetrahedral amorphous carbon (ta-C), to less compact vertically oriented graphene nano-particles. Thin carbon films were grown by PLD on n-Si 〈100〉 substrates, at temperatures ranging from RT to 800°C, from a rotating graphite target operating in vacuum. The laser ablation of the graphite target was performed by a UV pulsed ArF excimer laser (λ=193 nm) and a pulsed Nd:YAG laser, operating in the near IR (λ=1064 nm). The film structure and texturing, characterised by X-ray diffraction analysis, performed at grazing incidence (GI-XRD), and the film density, evaluated by X-ray reflectivity measurements, are strongly affected both by laser wavelength and fluence and by substrate temperature. Micro-Raman and GI-XRD analysis established the progressive formation of aromatic clusters and cluster condensation into vertically oriented nano-sized graphene structures as a direct function of increasing laser wavelength and deposition temperature. The film density, negatively affected by substrate temperature and laser wavelength and fluence, in turn, results in a porous bulk configuration and a high macroscopic surface roughness as shown by SEM characterisation. These structural property modifications induce a relevant variation also on the emission properties of carbon nano-structures, as evidenced by field emission measurements. This work is dedicated to our friend Giorgio who passed away 20th August.     

Dynamics of femtosecond-laser-ablated liquid-aluminum nanoparticles probed by means of spatiotemporally resolved X-ray absorption spectroscopy

We investigated spatiotemporal evolution of expanding ablation plume of aluminum created by a 100-fs, 10¹⁴–10¹⁵-W/cm² laser pulse. For diagnosing dynamic behavior of ablation plume, we employed the spatiotemporally resolved X-ray absorption spectroscopy (XAS) system that consists of a femtosecond-laser-plasma soft X-ray source and a Kirkpatrick–Baez (K–B) microscope. We successfully assigned the ejected particles by analyzing structure of absorption spectra near the L _II,III absorption edge of Al, and we clarified the spatial distribution of Al⁺ ions, Al atoms, and liquid droplets of Al in the plume. We found that the ejected particles strongly depend the irradiated laser intensity. The spatial distribution of atomic density and the expansion velocity of each type of particle were estimated from the spatiotemporal evolution of ablation particles. We also investigated a temperature of the aluminum fine particles in liquid phase during the plume expansion by analyzing the slope of the L _II,III absorption edge in case of 10¹⁴-W/cm² laser irradiation where the nanoparticles are most efficiently produced. The result suggests that the ejected particles travel in a vacuum as a liquid phase with a temperature of about 2500 to 4200 K in the early stage of plume expansion.     

Generation of coherent tunable deep UV radiation for detection and absorption studies of explosives RDX and TNT

We report a technique for the efficient generation of tunable coherent deep UV radiation and its application in studies of RDX and TNT at the ppm level on the basis of their absorption characteristics. The obtained experimental absorption data are compared with conventional spectrophotometric data. The UV radiation in the range 200–260 nm has been generated by the type-I noncollinear third harmonic of the dye laser radiation (600–700 nm) and also by sum frequency mixing (SFM) of Nd:YAG output (1064 nm) with the second harmonic of the dye laser in β-barium borate (BBO) crystal. The maximum conversion efficiency of the generated signal is estimated to be 57.5% at λ = 218.9 nm wavelength. Apart from measurements of the absorbance of RDX and TNT at different concentrations in their respective solutions, the minimum detection concentrations have also been ascertained. The estimated minimum detectable concentration of RDX is 8.47·10⁻⁹ M, whereas that for TNT is 35.7·10⁻⁹ M. The data were obtained using only ∼100 μJ/pulse of laser energy. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 516–521, July–August, 2007.     

Nonlinear absorption in undoped and Ge doped layered GaSe semiconductor crystals

P type-GaSe and 0.01 at% Ge doped GaSe crystal were grown using the conventional Bridgman–Stochbarger method from a stoichiometric mixture of starting materials in quartz ampoules, and the nonlinear absorption properties of both crystals have been studied by using an open aperture Z-scan technique under 1064 nm wavelength with 4 ns or 65 ps pulse durations. GaSe crystal exhibits two-photon absorption (TPA) at all input irradiances. On the other hand, at low input irradiance the Ge doped GaSe crystal exhibits saturable absorption (SA). At higher input irradiances TPA becomes dominant. A monotonic increase of the nonlinear absorption coefficient with increasing laser pulse duration from 65 ps to 4 ns is observed for the GaSe and Ge doped GaSe crystals.     

Laser ablation and micropatterning of thin TiN coatings

Laser ablation of thin TiN films deposited on steel substrates has been studied under wide-range variation of irradiation conditions (pulsewidth, wavelength, energy density and spot size). It has been demonstrated that both picosecond (150–300 ps) and nanosecond (5–9 ns) laser pulses were suitable for controllable ablation and microstructuring of a 1-μm-thick TiN film unlike longer 150-ns pulses. The ablation rate was found to be practically independent of the wavelength (270–1078 nm) and pulsewidth (150 ps–9 ns), but it increased substantially when the size of a laser spot was reduced from 15–60 μm to 3 μm. The laser ablation technique was applied to produce microstructures in the thin TiN films consisting of microcraters with a typical size of 3–5 μm in diameter and depth less than 1 μm. Tests of lubricated sliding of the laser-structured TiN films against a steel ball showed that the durability of lubricated sliding increased by 25% as compared to that of the original TiN film. Received: 28 July 1999 / Accepted: 17 April 2000 / Published online: 20 September 2000     

High resolution patterning of sapphire by F<Subscript>2</Subscript>-laser ablation

The ablation behavior of single crystalline sapphire with nanosecond laser pulses at 157 nm wavelength is investigated. Ablation rates of about 10 to 100 nm/pulse are obtained at fluences ranging from 1 to 9 J/cm². At moderate fluences, incubation behavior is observed, i.e. ablation starts after material modification by a number of laser pulses. The ablation can be utilized to fabricate sapphire micro-optics. The capability of creating lenses or gratings on the tip of sapphire fibers is demonstrated. Multilevel diffractive optical elements and high resolution gratings with 1 μm period are fabricated on planar sapphire substrates.     

Laser ablation of liquid surface in air induced by laser irradiation through liquid medium

The pulse laser ablation of a liquid surface in air when induced by laser irradiation through a liquid medium has been experimentally investigated. A supersonic liquid jet is observed at the liquid–air interface. The liquid surface layer is driven by a plasma plume that is produced by laser ablation at the layer, resulting in a liquid jet. This phenomenon occurs only when an Nd:YAG laser pulse (wavelength: 1064 nm) is focused from the liquid onto air at a low fluence of 20 J/cm². In this case, as Fresnel’s law shows, the incident and reflected electric fields near the liquid surface layer are superposed constructively. In contrast, when the incident laser is focused from air onto the liquid, a liquid jet is produced only at an extremely high fluence, several times larger than that in the former case. The similarities and differences in the liquid jets and atomization processes are studied for several liquid samples, including water, ethanol, and vacuum oil. The laser ablation of the liquid surface is found to depend on the incident laser energy and laser fluence. A pulse laser light source and high-resolution film are required to observe the detailed structure of a liquid jet.     

Incubation effect and its influence on laser patterning of ITO thin film

Results are presented on the surface damage thresholds of ITO thin films induced by single- and multi-pulse laser irradiation at a pulse duration of 10 ps and a wavelength of 1064 nm. For multi-pulse ablation the incubation effect results in a reduction of the damage threshold, especially apparent at low pulse numbers and very small film thicknesses. The incubation effect attributes to the accumulation of defect sites and/or the storage of thermal stress-strain energy induced by the incident laser pulses. An incubation coefficient of S=0.82 has been obtained which is independent on the film thickness in the range of 10–100 nm. In practical applications, the incubation effect determines the laser patterning structure of ITO films while increasing the pulse overlapping rate. The width of the patterned line can be predicted by the proposed model involving the laser fluence, the overlapping rate and the incubation coefficient.     

Picosecond laser ablation of SiO2 layers on silicon substrates

In this work, we report on laser ablation of thermally grown SiO₂ layers from silicon wafer substrates, employing an 8–9 ps laser, at 1064 (IR), 532 (VIS) and 355 nm (UV) wavelengths. High-intensity short-pulse laser radiation allows direct absorption in materials with bandgaps higher than the photon energy. However, our experiments show that in the intensity range of our laser pulses (peak intensities of <2×10¹² W/cm²) the removal of the SiO₂ layer from silicon wafers does not occur by direct absorption in the SiO₂ layer. Instead, we find that the layer is removed by a “lift off” mechanism, actuated by the melting and vaporisation of the absorbing silicon substrate. Furthermore, we find that exceeding the Si melting threshold is not sufficient to remove the SiO₂ layer. A second threshold exists for breaking of the layer caused by sufficient vapour pressure. For SiO₂ layer ablation, we determine layer thickness dependent minimum fluences of 0.7–1.2 J/cm² for IR, 0.1–0.35 J/cm² for VIS and 0.2–0.4 J/cm² for UV wavelength. After correcting the fluences by the reflected laser power, we show that, in contrast to the melting threshold, the threshold for breaking the layer depends on the SiO₂ thickness.     

Picosecond laser micromachining of nitinol and platinum–iridium alloy for coronary stent applications

The demand for micromachining of coronary stents by means of industrial lasers rises quickly for treating coronary artery diseases, which cause more than one million deaths each year. The most widely used types of laser for stent manufacturing are Nd:YAG laser systems with a wavelength of 1064 nm with pulse lengths of 10⁻³–10⁻² seconds. Considerable post-processing is required to remove heat-affected zones (HAZ), and to improve surface finishes and geometry. Using a third harmonic laser radiation of picosecond laser (6×10⁻¹² s pulse duration) in UV range, the capability of the picosecond laser micromachining of nitinol and platinum–iridium alloy for coronary stent applications are presented. In this study dross-free cut of nitinol and platinum–iridium alloy tubes are demonstrated and topography analysis of the cut surface is carried out. The HAZ characteristics have been investigated by means of microscopic examinations and measurement of micro-hardness distribution near the cut zones.