Nanosecond and femtosecond UV laser ablation of polymers: Influence of molecular weight

We examine the nanosecond and femtosecond UV laser ablation of poly(methyl methacrylate) (PMMA) as a function of molecular weight (M_w). For laser ablation with nanosecond laser pulses, at the excimer wavelengths 248 nm and 193 nm, we show that high temperatures develop; yet the dynamics of material ejection differs depending on polymer M_w. The results on the nanosecond ablation of polymers are accounted within the framework of bulk photothermal model and the results of molecular dynamics simulations. Turning next to the 248 nm ablation with 500 fs laser pulses, the ablation threshold and etching rates are also found to be dependent on polymer M_w. In addition, ablation results in morphological changes of the remaining substrate. Plausible mechanisms are advanced.     

Parametric study on femtosecond laser pulse ablation of Au films

Ablation process of 1 kHz rate femtosecond lasers (pulse duration 148 fs, wavelength 775 nm) with Au films on silica substrates has been systemically studied. The single-pulse threshold can be obtained directly. For the multiple pulses the ablation threshold varies with the number of pulses applied to the surface due to the incubation effect. From the plot of accumulated laser fluence N × ?_th(N) and the number of laser pulses N, incubation coefficient of Au film can be obtained (s = 0.765). As the pulse energy is increased, the single pulse ablation rate is increasing following two ablation logarithmic regimes, which can be explained by previous research.     

SOA-based actively mode-locked fiber ring laser by forward injecting an external pulse train

An actively mode-locked fiber ring laser based on cross-gain modulation (XGM) in a semiconductor optical amplifier (SOA) is demonstrated to operate stably with a simple configuration. By forward injecting an easily-generated external pulse train, the mode-locked fiber laser can generate an optical-pulse sequence with pulsewidth about 6 ps and average output power about 7.9 mW. The output pulses show an ultra-low RMS jitter about 70.7 fs measured by a RF spectrum analyzer. The use of the proposed forward-injection configuration can realize the repetition-rate tunability from 1 to 15 GHz for the generated optical-pulse sequences. By employing a wavelength-tunable optical band-pass filter in the laser cavity, the operation wavelength of the designed SOA-based actively mode-locked fiber laser can be tuned continuously in a wide span between 1528 and 1565 nm. The parameters of external-injection optical pulses are studied experimentally to optimize the mode-locked fiber laser.     

Measurements of nanoparticle size distribution produced by laser ablation of tungsten and boron-carbide in N2 ambient

Nanoparticles (NPs) were produced by ablating tungsten and boron-carbide (B₄C) target materials in atmospheric pressure nitrogen ambient using ArF excimer laser pulses. The size distributions of the NPs formed during the ablation were monitored—within a 7-133 nm size window—by a condensation particle counter connected to a differential mobility analyzer. The laser repetition rate was varied between 1-50 Hz, and the fluence was systematically changed in the range of 0.5-15 J/cm², for both materials, allowing a comparative study in an extended laser parameter regime. The multishot ablation threshold (Φ_th) of B₄C was determined to be ∼1.9 J/cm² for the laser used (ArF excimer, λ = 193 nm). Similarly to earlier studies, it was shown that the size distributions consist of mainly small nanoparticles (<∼20 nm) attributed to a non-thermal ablation mechanism below Φ_th. An additional broad peak appears (between 20 and 40 nm) above Φ_th as a consequence of the thermally induced macroscopic ablation. Chemical composition of deposited polydisperse nanoparticles was studied by X-ray photoelectron spectroscopy showing nitrogen incorporation into the boron-carbide.     

Laser ablation of metals by femtosecond pulses: Theoretical and experimental study

We have investigated ultrashort laser micromachining of metals, both from the point of view of the basic physical processes, and the technological implications. The process of hole drilling of Ni with ≈300 fs SHG (λ = 527 nm) Nd-glass and Al samples with 100 fs Ti:sapphire (λ = 800 nm) laser pulses, respectively, has been experimentally addressed by using time-gated optical emission spectroscopy of the ablated material and SEM analysis of the targets. The ablation process has also been analyzed by classical, molecular dynamics (MD) simulations, by using a Morse potential to describe the interaction between the atoms, and taking into account the electron heat diffusion contribution. The dependence of the ablation depth on laser fluence, as measured by SEM analysis, is in good agreement with the numerical simulations and is also well correlated with the optical emission yield of the expanding plume.     

Laser fluence, repetition rate and pulse duration effects on paint ablation

The efficiency (mm³/(J pulse)) of laser ablation of paint was investigated with nanosecond pulsed Nd:YAG lasers (λ = 532 nm) as a function of the following laser beam parameters: pulse repetition rate (1-10,000 Hz), laser fluence (0.1-5 J/cm²) and pulse duration (5 ns and 100 ns). In our study, the best ablation efficiency (η ≅ 0.3 mm³/J) was obtained with the highest repetition rate (10 kHz) at the fluence F = 1.5 J/cm². This ablation efficiency can be associated with heat accumulation at high repetition rate, which leads to the ablation threshold decrease. Despite the low thermal diffusivity and the low optical absorption of the paint (thermal confinement regime), the ablation threshold fluence was found to depend on the pulse duration. At high laser fluence, the ablation efficiency was lower for 5 ns pulse duration than for the one of 100 ns. This difference in efficiency is probably due to a high absorption of the laser beam by the ejected matter or the plasma at high laser intensity. Accumulation of particles at high repetition rate laser ablation and surface shielding was studied by high speed imaging.     

Early stage expansion and time-resolved spectral emission of laser-induced plasma from polymer

In the nanosecond laser ablation regime, absorption of laser energy by the plasma during its early stage expansion critically influences the properties of the plasma and thus its interaction with ambient air. These influences can significantly alter spectral emission of the plasma. For organic samples especially, recombination of the plasma with the ambient air leads to interfering emissions with respect to emissions due to native species evaporated from the sample. Distinguishing interfering emissions due to ambient air represents a critical issue for the application of laser-induced breakdown spectroscopy (LIBS) to the analysis of organic materials. In this paper, we report observations of early stage expansion and interaction with ambient air of the plasma induced on a typical organic sample (nylon) using time-resolved shadowgraph. We compare, in the nanosecond ablation regime, plasmas induced by infrared (IR) laser pulses (1064 nm) and ultraviolet (UV) laser pulses (266 nm). Nanosecond ablation is compared with femtosecond ablation where the post-ablation interaction is absent. Subsequent to the early stage expansion, we observe for each studied ablation regime, spectral emission from CN, a typical radical for organic and biological samples. Time-resolved LIBS allows identifying emissions from native molecular species and those due to recombination with ambient air through their different time evolution behaviors.     

Femtosecond pulsed laser ablation of diamond-like carbon films on silicon

Femtosecond pulsed laser ablation (τ = 120 fs, λ = 800 nm, repetition rate = 1 kHz) of thin diamond-like carbon (DLC) films on silicon was conducted in air using a direct focusing technique for estimating ablation threshold and investigating the influence of ablation parameter on the morphological features of ablated regions. The single-pulse ablation threshold estimated by two different methods were ?_th(1) = 2.43 and 2.51 J/cm². The morphological changes were evaluated by means of scanning electron microscopy. A comparison with picosecond pulsed laser ablation shows lower threshold and reduced collateral thermal damage.     

Ablation characteristics of aluminum oxide and nitride ceramics during femtosecond laser micromachining

Femtosecond laser ablation of aluminum oxide (Al₂O₃) and aluminum nitride (AlN) ceramics was performed under normal atmospheric conditions (λ = 785 nm, τ_p = 185 fs, repetition rate = 1 kHz), and threshold laser fluencies for single- and multi-pulse ablation were determined. The ablation characteristics of the two ceramics showed similar trends except for surface morphologies, which revealed virtually no melting in Al₂O₃ but clear evidence of melting for AlN. Based on subsequent X-ray photoelectron spectroscopy (XPS) analyses, the chemistry of these ceramics appeared to remain the same before and after femtosecond laser ablation.     

Emission spectra investigation of fs induced NPs probed by the ns laser pulse of a fs/ns DP-LIBS orthogonal configuration

A dual-pulse fs/ns laser induced breakdown spectroscopy configuration, where an initial 250 fs ablating pulsed laser followed by a delayed ns laser beam placed at a fixed distance, orthogonally with the expanding plasma plume, has been used in air on a Al₆₅Cu₂₃Fe₁₂ quasicrystal. The obtained emission data were acquired with a set-up arrangement providing space detections, with a resolution up to 15 μm, of the ns laser pulse generated signals. Assuming the fulfillment of local thermodynamic equilibrium conditions, the role played by the time lag between the two laser beams on the induced plasma excitation temperatures and electronic densities, as well as a space resolved process survey, has been followed. The spatial and time resolved spectra show, almost, steady values of the determined elementary plasma features with the development of nanoparticles occurring during the fs laser pulsed ablation process. The ns laser probe of the dual-pulse LIBS configuration here presented confirms that the nanoparticles induced can be largely widespread in both space and time whose compositions, overall, could retain the starting target stoichiometry. It is shown that these nanoparticles formation can actually take place at different times following the initial ultra-short laser beam incidence and that, especially at long inter-pulse delays (>100 μs), modest compositional changes can be observed.     

Elimination of cracking during UV laser ablation of SrTiO3 single crystals by employing a femtosecond laser

We have performed a comparative study of UV laser ablation of SrTiO₃ with nanosecond- and sub-picosecond sources, respectively. The experiments were performed with lasers at a wavelength of 248 nm and pulse durations of 34 ns and 500 fs. Femtosecond ablation turns out to be more efficient by one order of magnitude and eliminated the known problem of cracking of SrTiO₃ during laser machining with longer pulses. In addition, the cavities ablated with femtosecond pulses display a smoother surface with no indication of melting and well-defined, sharp edges. These effects can be explained by the reduced thermal shock effect on the material by using ultrashort pulses.     

Laser heating and ablation at high repetition rate in thermal confinement regime

Laser heating and ablation of materials with low absorption and thermal conductivity (paint and cement) were under experimental and theoretical investigations. The experiments were made with a high repetition rate Q-switched Nd:YAG laser (10 kHz, 90 ns pulse duration and λ = 532 nm). High repetition rate laser heating resulted in pulse per pulse heat accumulation. A theoretical model of laser heating was developed and demonstrated a good agreement between the experimental temperatures measured with the infrared pyrometer and the calculated ones. With the fixed wavelength and laser pulse duration, the ablation threshold fluence of paint was found to depend on the repetition rate and the number of applied pulses. With a high repetition rate, the threshold fluence decreased significantly when the number of applied pulses was increasing. The experimentally obtained thresholds were well described by the developed theoretical model. Some specific features of paint heating and ablation with high repetition rate lasers are discussed.     

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.     

Effects of laser operating parameters on metals micromachining with ultrafast lasers

180 femtoseconds (1 kHz) and 10 picoseconds (1-50 kHz) ultrafast laser micro-structuring of the metals Ti alloy, Al and Cu have been studied for the purpose of industrial application. The effects of some key laser operating parameters were investigated. The evolution of surface morphology revealed that laser pulses overlap in a range around the spatial FWHM can help to achieve optimal residual surface roughness. While observed ablation rate (unit: μm³ per pulse) changed dramatically with repetition rate due to the combined effects of plasma absorption, residual thermal energy and phase transition, higher throughput can be achieved with higher repetition rate. This study also indicated that residual surface roughness is almost independent of repetition rate at 10 ps temporal pulse length. The ablation depth is approximately proportional to the number of overscan; however, machining accuracy deteriorates, especially for femtosecond laser processing and metals with low thermal conductivity and short electron-phonon coupling time.     

Ablation mechanism study on metallic materials with a 10 ps laser under high fluence

Single shot ablation of metallic materials of aluminium, titanium alloy (Ti6Al4V) and gold has been studied with 10 picoseconds (ps) laser pulses experimentally and theoretically. The ablation rate variation at high fluence was explained by a simplified predictive model based on critical-point phase separation (CPPS) theory. A comparison between experimental and numerical results inferred that CPPS may well be the dominant ablation mechanism for high fluence laser ablation at 10 ps laser duration.     

Femtosecond laser-induced damage of gold films

Single- and multi-shot ablation thresholds of gold films in the thickness range of 31-1400 nm were determined employing a Ti:sapphire laser delivering pulses of 28 fs duration, 793 nm center wavelength at 1 kHz repetition rate. The gold layers were deposited on BK7 glass by an electron beam evaporation process and characterized by atomic force microscopy and ellipsometry. A linear dependence of the ablation threshold fluence F_th on the layer thickness d was found for d ≤ 180 nm. If a film thickness of about 180 nm was reached, the damage threshold remained constant at its bulk value. For different numbers of pulses per spot (N-on-1), bulk damage thresholds of ∼0.7 J cm⁻² (1-on-1), 0.5 J cm⁻² (10-on-1), 0.4 J cm⁻² (100-on-1), 0.25 J cm⁻² (1000-on-1), and 0.2 J cm⁻² (10000-on-1) were obtained experimentally indicating an incubation behavior. A characteristic layer thickness of L_c ≈ 180 nm can be defined which is a measure for the heat penetration depth within the electron gas before electron-phonon relaxation occurs. L_c is by more than an order of magnitude larger than the optical absorption length of α⁻¹ ≈ 12 nm at 793 nm wavelength.     

Three-level operation of a diode-bar-pumped Yb:S-FAP laser

We present an all solid-state Yb:S-FAP laser system running on the three-level laser transition at 985 nm. The pump source was a high fill-factor laser diode bar, with the output reformatted using a two-mirror beamshaping system to produce a rectangular pump beam that focused to a square spot. A nearly on-axis multipassing system was used to obtain four pump passes through a 1.6 mm Yb:S-FAP laser crystal. Gain-switched three-level laser output was achieved with an efficiency of 4.3% with respect to incident pump power. Electro-optic Q-switching produced 0.12 mJ pulses for a pump pulse energy of 11 mJ. Intra-cavity second-harmonic generation yielded a maximum pulse energy at 492.5 nm of 12 μJ.     

Subwavelength ripple formation induced by tightly focused femtosecond laser radiation

Subwavelength ripples (<λ/4) are obtained by scanning a tightly focused beam (∼1 μm) of femtosecond laser radiation (λ = 800 nm, t_p = 100 fs) over the surface of either bulk fused silica and silicon and Er:BaTiO₃. The ripple pattern extends coherently over many overlapping laser pulses parallel and perpendicular to the polarisation. Investigated are the dependence of the ripple spacing on the spacing of successive pulses, the direction of polarisation and the material. The evolution of the ripples is investigated by applying pulse bursts with N = 1 to 20 pulses. The conditions under which these phenomena occur are specified, and some possible mechanisms of ripple growth are discussed. Potential applications are presented.     

Femtosecond pulsed laser deposition of diamond-like carbon films: The effect of double laser pulses

The bonding structure of carbon films prepared by pulsed laser deposition is determined by the plasma properties especially the change of the kinetic energy. Using double laser pulses the ablation process and the characteristics of the generated plasma can be controlled by the setting of the delay between the pulses. In our experiments, amorphous carbon films have been deposited in vacuum onto Si substrates by double pulses from a Ti:sapphire laser (180 fs, λ = 800 nm, at 1 kHz) and a KrF laser system (500 fs, λ = 248 nm, at 5 Hz). The intensities have been varied in the range of 3.4 × 10¹² to 2 × 10¹³ W/cm². The morphology and the main properties of the thin layers were investigated as a function of the time delay between the two ablating pulses (0-116.8 ps) and as a function of the irradiated area on the target surface. Atomic force microscopy, spectroscopic ellipsometry and Raman-spectroscopy were used to characterize the films. It was demonstrated that the change of the delay and the spot size results in the modification of the thickness distribution of the layers, and the carbon sp²/sp³ bonding ratio.     

The potential of UV femtosecond laser ablation for varnish removal in the restoration of painted works of art

Despite significant advances, laser ablation with nanosecond pulses presents limitations in dealing with the restoration of classes of painted works of art, such as paintings with a very thin layer of varnish. Femtosecond laser processing promises the means for overcoming such limitations. To this end, femtosecond ablation of two typical varnishes, dammar and mastic, is examined. For these varnishes, processing by Ti:Sapphire irradiation (800 nm) turns out to be ineffective. In contrast, irradiation with 248 nm ∼500 fs laser pulses results in a higher etching resolution (etching rates of ∼1 μm/pulse or less). For irradiation with few laser pulses at moderate laser fluences, etched morphology is far smoother than in the processing with nanosecond laser pulses. Furthermore, chemical modifications are considerably reduced (by nearly an order of magnitude), and exhibit a number of additional novel differences. Both etching rates and extent of chemical modifications are largely independent of varnish absorptivity. In all, femtosecond UV laser irradiation is indicated to hold a high potential, offering new perspectives for the restoration of painted works of art. Finally, a tentative model is advanced accounting in a consistent way for the observations.