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.     

Identification of non-thermal and thermal processes in femtosecond laser-ablated aluminum

Non-thermal and thermal processes due to femtosecond laser ablation of aluminum (Al) at low, moderate, and high-fluence regimes are identified by Atomic Force Microscope (AFM) surface topography investigations. For this purpose, surface modifications of Al by employing 25 fs Ti: sapphire laser pulses at the central wavelength of 800 nm have been performed to explore different nano- and microscale features such as hillocks, bumps, pores, and craters. The mechanism for the formation of these diverse kinds of structures is discussed in the scenario of three ablation regimes. Ultrafast electronic and non-thermal processes are dominant in the lower fluence regime, whereas slow thermal processes are dominant at the higher fluence regime. Therefore, by starting from the ablation threshold three different fluence regimes have been chosen: a lower fluence regime (0.06–0.5 J cm^?2 single-shot irradiation under ultrahigh vacuum condition and 0.25–2.5 J cm^?2 single-shot irradiation in ambient condition), a moderate-fluence regime (0.25–1.5 J cm^?2 multiple-shot irradiation), and a high-fluence regime 2.5–3.5 J cm^?2 multiple-shot irradiation. For the lower fluence (gentle ablation) regime, around the ablation threshold, the unique appearance of individual, localized Nano hillocks typically a few nanometers in height and less than 100 nm in diameter are identified. These Nano hillock-like features can be regarded as a nonthermal, electronically induced phase transition process due to localized energy deposition as a result of Coulomb explosion or field ion emission by surface optical rectification. At a moderate-fluence regime, slightly higher than ablation threshold multiple-pulse irradiation produces bump-formation and is attributed to ultrafast melting (plasma formation). The high-fluence regime results in greater rates of material removal with highly disturbed and chaotic surface of Al with an appearance of larger protrusions at laser fluence well above the ablation threshold. These nonsymmetrical shapes due to inhomogeneous nucleation, cluster formation, and resolidification of a metallic surface after melting are attributable to slow thermal processes (ps time scale).     

Subpicosecond laser ablation of copper and fused silica: Initiation threshold and plasma expansion

We investigated the subpicosecond laser ablation of copper and fused silica under 100 fs laser irradiation at 800 nm in vacuum by means of fast plume imaging and time- and space-resolved optical emission spectroscopy. We found that, to the difference of copper ablation, the laser-generated plasma from a fused silica target exhibited one “main” component only. The “slow” plasma component, observed during copper ablation and usually assigned to optical emission from nanoparticles was not detected by either plasma fast imaging or optical emission spectroscopy even when fused silica targets were submitted to the highest incident fluences used in our experiments. The characteristic expansion velocity of this unique component was about three times larger than the velocity of the fast plume component observed during copper ablation. The dependence of laser fluence on both plasma expansion and ablation rate was investigated and discussed in terms of ablation efficiency and initiation mechanisms.     

Highly efficient THz emission from differently grown InN at 800 nm and 1060 nm excitation

A detailed study on differently molecular-beam epitaxy (MBE) grown InN wavers as THz surface emitters is reported. The samples were excited using 120 fs and 100 fs short laser pulses delivered by a Ti:Sapphire oscillator at 800 nm and a fiber laser amplifier at 1060 nm, respectively. The InN emission properties are compared to a p-type InAs reference sample. At 800 nm, atomically smooth InN with low background electron concentration exhibits slightly stronger THz emission than the well-established p-InAs emitter. This high THz efficiency of InN is reported for the first time. The strong emission of InN is caused by the absence of any intervalley scattering, which in the case of InAs, increases the effective mass of the photogenerated electrons and, thus, reduces the photo-Dember effect, which is most responsible for THz emission. Consequently, InN is a reliable material for strong THz emission.     

Femtosecond and nanosecond laser damage thresholds of doped and undoped triazenepolymer thin films

The influence of pulse duration on the laser-induced damage in undoped or infrared-absorbing-dye doped thin triazenepolymer films on glass substrates has been investigated for single, near-infrared (800 nm) Ti:sapphire laser pulses with durations ranging from 130 fs up to 540 fs and complementarily for infrared (1064 nm) Nd:YAG ns-laser single-pulse irradiation. The triazenepolymer material has been developed for high resolution ablation with irradiation at 308 nm. Post-irradiation optical microscopy observations have been used to determine quantitatively the threshold fluence for permanent laser damage. In contrast to our previous studies on a triazenepolymer with different composition [J. Bonse, S.M. Wiggins, J. Solis, T. Lippert, Appl. Surf. Sci. 247 (2005) 440], a significant dependence of the damage threshold on the pulse duration is found in the sub-picosecond regime with values ranging from ∼500 mJ/cm² (130 fs) up to ∼1500 mJ/cm² (540 fs). Other parameters such as the film thickness (50 nm and 1.1 μm samples) or the doping level show no significant influence on the material behavior upon irradiation. The results for fs- and ns-laser pulse irradiation are compared and analyzed in terms of existent ablation models.     

Morphology of ablation craters generated by fs laser pulses in LiNbO3

The surface morphology of the ablation craters generated in LiNbO₃ by 130 fs laser pulses at 800 nm has been investigated by AFM/SNOM microscopy. The single pulse fluence corresponding to the ablation threshold has been estimated to be ≈1.8 J/cm².A complex structure including random cone-shaped protrusions is observed inside the ablated crater. The scale of the protrusion spacing is in the submicron range and the heights are typically of a few tens of nanometers. At and outside the crater rim a novel quasi-periodic wave-like topography pattern is observed in both types of microscopy techniques. The average wavelength, that is slightly dependent on pulse fluence, is (500-800 nm) comparable to the light wavelength. This novel topography feature keeps a close similarity with a Fresnel diffraction pattern by an absorbing circular obstacle or impact wave pattern produced by a combination of heat and shock wave (resemble that of impact crater). It is proposed that the obstacle is associated to the strongly nonlinear multiphoton absorption at the peak of the pulse profile. The energy deposited by nonlinear absorption of such profile causes ablation of both the crater and the rippled structure.     

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.     

Laser surface treatment of screen-printed carbon nanotube emitters for enhanced field emission

This paper investigates the surface treatment of screen-printed carbon nanotube (CNT) emitters using a 248 nm (KrF) excimer laser. The field emission characteristics of the CNT emitters are measured following irradiation using laser fluences ranging from 80 to 400 mJ/cm². The results show that the turn-on electric field, the current density, and the distribution of the emission sites are highly dependent on the value of the laser fluence and are optimized at a fluence of 150 mJ/cm². Two distinct laser fluence regimes are identified. In the low fluence regime, i.e. 80-150 mJ/cm², the surface treatment process is dominated by a photo ablation mechanism, which results in the gradual removal of the binding material from the cathode surface and leads to an improvement in the emission characteristics of the CNT cathodes with an increasing fluence. However, in the high fluence regime, i.e. 150-400 mJ/cm², the thermal ablation mechanism dominates; resulting in a removal of the CNTs from the cathode surface and a subsequent degradation in the emission characteristics.     

Two-color two-photon excitation of indole using a femtosecond laser regenerative amplifier

The fluorescence emission from indole resulting from two-color two-photon (2C2P) excitation with 400 and 800 nm wavelengths is observed, using the second harmonic and fundamental wavelength of a 800 nm 40 fs pulsed Ti:Sapphire femtosecond (fs) regenerative amplifier operating at a repetition rate of 1 kHz. By delaying one fs laser pulse relative to the other, the cross correlation of fluorescence is observed, which indicates the generation of 2C2P fluorescence signal in the experiment. The strongest 2C2P fluorescence emission characterized by the peak of cross correlation curve suggests optimal temporal overlap of the two fs laser pulses. The 2C2P fluorescence signal is linearly dependent on the total excitation intensity. The fluorescence signals with 400 nm and 800 nm irradiation alone are also demonstrated and discussed in this paper.     

Enhanced near field mediated nanohole fabrication on silicon substrate by femtosecond laser pulse

Investigation of the process of nanohole formation on silicon surface mediated with near electromagnetic field enhancement in vicinity of gold particles is described. Gold nanospheres with diameters of 40, 80 and 200 nm are used. Irradiation of the samples with laser pulse at fluences below the ablation threshold for native Si surface, results in a nanosized surface modification. The nanostructure formation is investigated for the fundamental (λ = 800 nm, 100 fs) and the second harmonic (λ = 400 nm, 250 fs) of the laser radiation generated by ultrashort Ti:sapphire laser system. The near electric field distribution is analyzed by an Finite Difference Time Domain (FDTD) simulation code. The properties of the produced morphological changes on the Si surface are found to depend strongly on the polarization and the wavelength of the laser irradiation. When the laser pulse is linearly polarized the produced nanohole shape is elongated in the E-direction of the polarization. The shape of the hole becomes symmetrical when the laser radiation is circularly polarized. The size of the ablated holes depends on the size of the gold particles, as the smallest holes are produced with the smallest particles. The variation of the laser fluence and the particle size gives possibility of fabricating structures with lateral dimensions ranging from 200 nm to below 40 nm. Explanation of the obtained results is given on the basis simulations of the near field properties using FDTD model and Mie's theory.     

Optical emission spectroscopy investigation of an ultra-short laser induced titanium plasma reheated by a ns laser pulse

The dynamics of a titanium plasma species, induced in air by coupling a fs-ablating laser pulse with an orthogonal ns-reheating laser source placed at the fixed distance of 1.0 mm from the target surface, has been followed by temporally resolved emission spectroscopy. The temporal evolutions of plasma features such as excitation temperatures and electron densities have been evaluated by using two different laser energies of the first fs-ablating laser pulse (0.8 mJ and 3.0 mJ). Optimum inter-pulse delay times, experimentally determined, of 250 μs and 500 μs were used for the fs laser energy of 3.0 mJ and 0.8 mJ, respectively. By experimental inspections of the main plasma species electronic transitions so obtained, a strong enhancement was evaluated up to one and two orders of magnitude for Ti(I) and Ti(II), respectively. Independently from the fs laser energy employed, the plasma features showed the same temporal behaviour implying that the ns-reheating characteristics of this process belong to the reheating mechanism itself. The experimental results have been discussed and the excited species evolutions and elementary processes involved, as well as, the local thermodynamic equilibrium departures, have been outlined.     

Nanostructures on SiC surface created by laser microablation

Silicon carbide (SiC), as it is well-known, is inaccessible to usual methods of technological processing. Consequently, it is important to search for alternative technologies of processing SiC, including laser processing, and to study the accompanying physical processes. The work deals with the investigation of pulsed laser radiation influence on the surface of 6H-SiC crystal. The calculated temperature profile of SiC under laser irradiation is shown. Structural changes in surface and near-surface layers of SiC were studied by atomic force microscopy images, photoluminescence, Raman spectra and field emission current-voltage characteristics of initial and irradiated surfaces. It is shown that the cone-shaped nanostructures with typical dimension of 100-200 nm height and 5-10 nm width at the edge are formed on SiC surface under nitrogen laser exposure (λ = 0.337 μm, t_p = 7 ns, E_p = 1.5 mJ). The average values of threshold energy density 〈W_thn〉 at which formation of nanostructures starts on the 0 0 0 1 and surfaces of n-type 6H-SiC(N), nitrogen concentration n_N ≅ 2 × 10¹⁸ cm⁻³, are determined to be 3.5 J/cm² and 3.0 J/cm², respectively. The field emission appeared only after laser irradiation of the surface at threshold voltage of 1000 V at currents from 0.7 μA to 0.7 mA. The main role of the thermogradient effect in the processes of mass transfer in prior to ablation stages of nanostructure formation under UV laser irradiation (LI) was determined. We ascertained that the residual tensile stresses appear on SiC surface as a result of laser microablation. The nanostructures obtained could be applied in the field of sensor and emitting extreme electronic devices.     

Nanosecond and femtosecond laser spectroscopy of molecules of biological interest

This paper mainly concerns on nanosecond and femtosecond laser spectroscopy of aromatic organic compounds as neurotransmitters, and plume diagnostics of the ablated species, in order to characterize the plasma dynamics, i.e. the temporal and spatial evolution of the plume. Optical emission spectroscopy has been applied to characterize the transient species produced in the femtosecond (fs) and nanosecond (ns) regimes. The laser sources employed for optical emission spectroscopy are a frequency-doubled Nd:YAG Handy (λ = 532 nm, τ = 5 ns) and a frequency-doubled Nd:glass (λ = 527 nm, τ = 250 fs). These studies aim to detect and give information on the photoexcitation and photodissociation of these biological molecules and to compare the plasma characteristics in the two ablation regimes.     

Effects of electron relaxation on multiple harmonic generation from metal surfaces with femtosecond laser pulses

Calculations are presented for the first four (odd and even) harmonics of an 800 nm laser from a gold surface, with pulse widths ranging from 100 down to 14 fs. For peak laser intensities above 1 GW/cm² the harmonics are enhanced because of a partial depletion of the initial electron states. At 10¹¹ W/cm² of peak laser intensity the calculated conversion efficiency for 2nd-harmonic generation is 3 × 10⁻⁹, while for the 5th-harmonic it is 10⁻¹⁰. The generated harmonic pulses are broadened and delayed relative to the laser pulse because of the finite relaxation times of the excited electronic states. The finite electron relaxation times cause also the broadening of the autocorrelations of the laser pulses obtained from surface harmonic generation by two time-delayed identical pulses. Comparison with recent experimental results shows that the response time of an autocorrelator using nonlinear optical processes in a gold surface is shorter than the electron relaxation times. This seems to indicate that for laser pulses shorter than ∼30 fs, the fast nonresonant channel for multiphoton excitation via continuum-continuum transitions in metals becomes important as the resonant channel becomes slow (relative to the laser pulse) and less efficient.     

Depth-profile investigations of triterpenoid varnishes by KrF excimer laser ablation and laser-induced breakdown spectroscopy

The ablation properties of aged triterpenoid dammar and mastic films were investigated using a Krypton Fluoride excimer laser (248 nm, 25 ns). Ablation rate variations between surface and bulk layers indicated changes of the ablation mechanisms across the depth profiles of the films. In particular, after removal of the uppermost surface varnish layers there was a reduction of the ablation step in the bulk that was in line with a significant reduction of carbon dimer emission beneath the surface layers as detected by laser-induced breakdown spectroscopy. The results are explicable by the generation of condensation, cross-linking and oxidative gradients across the depth profile of triterpenoid varnish films during the aging degradation process, which were recently quantified and established on the molecular level.     

Mechanisms of femtosecond laser-induced breakdown and damage in MgO

Single-shot laser damage threshold of MgO for 40-986 fs, 800 nm laser pulses is reported. The pump-probe measurements with femtosecond pulses were carried out to investigate the time-resolved electronic excitation processes. A theoretical model including conduction band electrons (CBE) production and laser energy deposition was applied to discuss the roles of multiphoton ionization (MPI) and avalanche ionization in femtosecond laser-induced dielectric breakdown. The results indicate that avalanche ionization plays the dominant role in the femtosecond laser-induced breakdown in MgO near the damage threshold.     

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.     

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-induced vibrational excitation and desorption in the Cs/Cu(1 1 1) and Na/Cu(1 1 1) systems

The Cs/Cu(1 1 1) and Na/Cu(1 1 1) systems exhibit a transient excited electronic state localized on the adsorbate. Photo-excitation of this state triggers a motion of the alkali adsorbate away from the surface, leading to vibrational excitation of the adsorbate and possibly to desorption. A theoretical study of these photo-induced processes in the case of an exciting fs laser pulse is reported, based on a time-dependent approach of the adsorbate motion. The mean energy transfer from the laser photon energy to the adsorbate motion is shown to be weak, about 1% of the photon energy. Correspondingly, the vibrational excitation to high lying levels is very weak as well as the desorption process. The initial electronic state of the photo-induced process belongs to a continuum and vibrational excitation and desorption are found to vary rapidly with the energy of the initial electronic state. Initial vibrational excitation of the alkali adsorbate is also found to efficiently favour the desorption process, leading to a drastic variation of the desorption probability with the vibrational temperature of the adsorbate. The present results for the two systems are discussed and compared, in connection with available experimental data on these systems and on similar ones.     

Nanosecond and femtosecond ablation of La0.6Ca0.4CoO3: a comparison between plume dynamics and composition of the films

Thin films of La_0.6Ca_0.4CoO₃ were grown by pulsed laser ablation with nanosecond and femtosecond pulses. The films deposited with femtosecond pulses (248 nm, 500 fs pulse duration) exhibit a higher surface roughness and deficiency in the cobalt content compared to the films deposited with nanosecond pulses (248 nm, 20 ns pulse duration). The origin of these pronounced differences between the films grown by ns and fs ablation has been studied in detail by time-resolved optical emission spectroscopy and imaging. The plumes generated by nanosecond and femtosecond ablation were analyzed in vacuum and in a background pressure of 60 Pa of oxygen. The ns-induced plume in vacuum exhibits a spherical shape, while for femtosecond ablation the plume is more elongated along the expansion direction, but with similar velocities for ns and fs laser ablation. In the case of ablation in the background gas similar velocities of the plume species are observed for fs and ns laser ablation. The different film compositions are therefore not related to different kinetic energies and different distributions of various species in the plasma plume which has been identified as the origin of the deficiency of species for other materials.