Controlling energy coupling and particle ejection from aluminum surfaces irradiated with ultrashort laser pulses

Hydrodynamic simulations are used to evaluate the potential of ultrashort laser pulses to localize energy at metallic surfaces, in our case aluminum. The emphasis is put on the dynamic sequence of laser energy deposition steps during the electron-ion nonequilibrium stage and the subsequent matter transformation phases. The simulations indicate correlated optical and thermodynamical states associated to specific electronic collisional mechanisms. The timescales of energy deposition deliver a guideline for using relevant relaxation times to improve the energy coupling into the material. We focus on a class of pump-probe experiments which investigate energy storage and particle emission from solids under ultrafast laser irradiation. Moreover, we have used our model to explain the experimentally observed optimization of energy coupling by tailoring temporal laser intensity envelopes and its subsequent influence on the ablation rate and on the composition of ablation products. Potential control for nanoparticle generation is discussed.     

Laser ablation with short and ultrashort laser pulses: Basic mechanisms from molecular-dynamics simulations

Laser ablation is a technology widely used in many applications. Understanding in detail the mechanisms that lead to ablation remains a formidable challenge because of the complexity of the processes taking place, the variety of species involved, and the range of length and time scales covered. Atomic-level experimental information is difficult to obtain and must be augmented by theory. In this article, we briefly review the progresses that we have accomplished using a simple two-dimensional molecular-dynamics model, insisting on the importance of considering the thermodynamics of the evolution of the systems in order to understand ablation. Through the identification of the thermodynamic pathways followed by the material after irradiation, our model has provided significant insights on the physical mechanisms leading to ablation. It has been demonstrated in particular that these depend strongly on the fluence, and are actually determined by the effective amount of energy received within different regions of the target. Further, internal or external factors, such as inertial confinement, play a key role in determining the route to ablation - and thus the types and sizes of particles ejected - by constraining the thermodynamical evolution of the system. We have established that, for ultrashort pulses in strongly absorbing materials, ablation proceeds by either spallation, phase explosion or fragmentation; the latter, we demonstrate, is the most important mechanism. For longer pulses, ablation may also proceed by trivial fragmentation.     

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.     

A nonlinear correlation method using multiphoton ionization for the measurement of uv ultrashort pulses

A new nonlinear correlation method which makes it possible to measure the duration of uv ultrashort pulses has been proposed. In this method the multiphoton ionization of gases is used as a nonlinear process and the ion current caused by the process is detected. We have also experimentally demonstrated its usefulness in the uv region by observing the second- and the third-order auto-correlation profiles of picosecond pulses at 2661 Å (the fourth harmonic of a mode-locked YAG laser), using NO and Xe gases, respectively.     

Morphology and composition on Al surface irradiated by femtosecond laser pulses

We study the surface chemicals and structures of aluminum plates irradiated by scanning femtosecond laser pulses in air for a wide range of laser fluence from 0.38 to 33.6 J/cm². X-ray photoelectron spectroscopy and X-ray diffraction analyses indicate clearly that crystalline anorthic Al(OH)₃ is formed under femtosecond laser pulse irradiation. Besides aluminum hydroxide, crystalline Al₂O₃ is also found in the samples irradiated at high laser fluence. Field emission scanning electron microscopy demonstrates that the surfaces of the samples irradiated with low laser fluence are colloidal-like and that nanoparticles with a few nanometers in size are embedded in glue-like substances. For high laser fluence irradiated samples, the surfaces are highly porous and covered by nanoparticles with uniform size of less than 20 nm.     

Periodic surface structures on crystalline silicon created by 532 nm picosecond Nd:YAG laser pulses

Creation of laser-induced morphology features, particularly laser-induced periodic surface structures (LIPSS), by a 532 nm picosecond Nd:YAG laser on crystalline silicon is reported. The LIPSS, often termed ripples, were produced at average laser irradiation fluences of 0.7, 1.6, and 7.9 J cm⁻². Two types of ripples were registered: micro-ripples (at micrometer scale) in the form of straight parallel lines extending over the entire irradiated spot, and nano-ripples (at nanometer scale), apparently concentric, registered only at the rim of the spot, with the periodicity dependent on laser fluence. There are indications that the parallel ripples are a consequence of the partial periodicity contained in the diffraction modulated laser beam, and the nano-ripples are very likely frozen capillary waves. The damage threshold fluence was estimated at 0.6 J cm⁻².     

Sub-wavelength surface structures on silicon irradiated by femtosecond laser pulses at 1300 and 2100 nm wavelengths

We present periodic ripples and arrays of protrusions formed on the surface of silicon after irradiation by low-fluence linearly polarized femtosecond laser pulses. Laser-induced periodic surface structures (LIPSS) are observed for irradiation at center wavelengths of 800, ∼ 1300, and ∼ 2100 nm, with the structure periods somewhat less than the incident wavelengths in air. Additionally, we observe structures with spatial periods substantially less than the incident laser wavelengths. These sub-wavelength periodic structures form only when the photon energy is less than the silicon bandgap energy. We discuss a number of factors which may contribute to the generation of this surface morphology.     

Enhanced two temperature modeling of ultrashort laser ablation for the investigation of thermionic emission characteristics

Characteristics of thermionic electron emission during femtosecond laser ablation of gold film are studied numerically. For the rigorous calculation of electron and lattice temperatures, an enhanced two-temperature model with transient thermal and optical properties is developed and it is demonstrated that the model predicts the damage threshold fluences closely matching experimental data. From the calculated electron emission characteristics, quantum efficiency and electron current density are estimated.     

Surface structures on crystalline silicon irradiated by 10 ps laser pulses at 694.3 nm

The grating-like spatially periodic structures are produced on the (100) surfaces of the single crystal silicon by the trains of 10 ps mode-locked ruby laser pulses at the wavelength of 694.3 nm. The periods and orientations of the structures are consistent with the model which involves the interference of the incident light with the surface electromagnetic wave excited through the coupling by surface roughness. Previously unappreciated elliptic ripple patterns are found and explained as the trails of the capillary wave excited on the molten Si surface due to the radially non-uniform deposition of energy.     

Direct observation of the temperature field during ablation of materials by multiple femtosecond laser pulses

We report a direct observation of the temperature field on a steel specimen during ablation by multiple femtosecond laser pulses using an infrared thermography technique. From the experimental results and simulation study of the temperature field, we quantified the deposited thermal power into the specimen during the ablation process. We found that more than two thirds of the incident laser power was deposited in the steel specimen when ablated by multiple femtosecond laser pulses. This result provides further understanding of the heating effect in materials processing by ultrashort laser pulses.     

Selective ablation of thin films with short and ultrashort laser pulses

Micromachining of CuInSe₂ (CIS)-based photovoltaic devices with short and ultrashort laser pulses has been investigated. Therefore, ablation thresholds and ablation rates of ZnO, Mo and CuInSe₂ thin films have been measured for irradiation with nanosecond laser pulses of ultraviolet and visible light and subpicosecond laser pulses of a Ti:sapphire laser. The experimental results were compared to the theoretical evaluation of the samples heat regime. In addition, the cells photo-electrical properties were measured before and after laser machining. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analyses were employed to characterise the laser-induced ablation channels. Using nanosecond laser pulses, two phenomena were found to limit the laser-machining process. Residues of Mo that were projected onto the walls of the ablation channel and the metallization of the CuInSe₂ semiconductor close to the channel lead to a shunt. The latter causes the decrease of the photovoltaic efficiency. As a consequence of these limiting effects, only subpicosecond laser pulses allowed the selective or complete ablation of the thin layers without a relevant change of the photo-electrical properties.     

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.     

Surface modification of a WTi thin film on Si substrate by nanosecond laser pulses

Interaction of a nanosecond transversely excited atmospheric (TEA) CO₂ laser, operating at 10.6 μm, with tungsten-titanium thin film (190 nm) deposited on silicon of n-type (1 0 0) orientation, was studied. Multi-pulse irradiation was performed in air atmosphere with laser energy densities in the range 24-49 J/cm². The energy absorbed from the laser beam was mainly converted to thermal energy, which generated a series of effects. The following morphological changes were observed: (i) partial ablation/exfoliation of the WTi thin film, (ii) partial modification of the silicon substrate with formation of polygonal grains, (iii) appearance of hydrodynamic features including nano-globules. Torch-like plumes started appearing in front of the target after several laser pulses.     

Nonlinear photoionization and laser-induced damage in silicate glasses by infrared ultrashort laser pulses

We show that photoionization of wide band gap silicate glasses by infrared ultrashort laser pulses can occur without laser-induced damage. Two glasses are studied, fused silica and a multi-component silicate photo-thermo-refractive (PTR) glass. Experiments are performed by low numerical aperture focusing of ultrashort laser pulses (100 fsec<τ<1.5 psec) at the wavelengths 780 nm, 1430 nm, and 1550 nm. Filaments form inside both glasses and are visibly observable due to intrinsic luminescence. Keldysh’s theory of nonlinear photoionization is used to model the formation of filaments and values of about 10¹³ W cm⁻² for the laser intensity and 10¹⁹ cm⁻³ for the free electron density are estimated for stable filaments to arise. Laser-induced damage is studied by the generation of a third harmonic from an interface created between a damage site and the surrounding glass matrix. It is found that third harmonic generation occurs only after several thousands of laser shots indicating that damage is not a single-shot phenomena. The ability to photoionize PTR glass without damage by ultrashort laser pulses offers a new approach for fabricating diffractive optical elements in photosensitive glass.     

Minimization of cavitation effects in pulsed laser ablation illustrated on laser angioplasty

Cavitation effects in pulsed laser ablation can cause severe deformation of tissue near the ablation site. In angioplasty, they result in a harmful dilatation and invagination of the vessel walls. We suggest to reduce cavitation effects by dividing the laser pulse energy into a pre-pulse with low and an ablation pulse with high energy. The pre-pulse creates a small cavitation bubble which can be filled by the ablation products of the main pulse. For suitable energy ratios between the pulses, this bubble will not be enlarged by the ablation products, and the maximal bubble size remains much smaller than after a single ablation pulse. The concept was analyzed by numerical calculations based on the Gilmore model of cavitation dynamics and by high-speed photography of the effects of single and double pulses performed with a silicone tube as vessel model. The use of double pulses prevents the deformation of the vessel walls. The concept works with an energy ratio of up to about 1:30 between the pulses. For the calculated optimal ratio of 1:14.6, the bubble volume is reduced by a factor of 17.7. The ablation pulse is best applied when the pre-pulse bubble is maximally expanded, but the timing is not very critical.     

Analyses of surface coloration on TiO2 film irradiated with excimer laser

TiO₂ film of around 850 nm in thickness was deposited on a soda-lime glass by PVD sputtering and irradiated using one pulse of krypton-fluorine (KrF) excimer laser (wavelength of 248 nm and pulse duration of 25 ns) with varying fluence. The color of the irradiated area became darker with increasing laser fluence. Irradiated surfaces were characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy and atomic force microscopy. Surface undergoes thermal annealing at low laser fluence of 400 and 590 mJ/cm². Microcracks at medium laser fluence of 1000 mJ/cm² are attributed to surface melting and solidification. Hydrodynamic ablation is proposed to explain the formation of micropores and networks at higher laser fluence of 1100 and 1200 mJ/cm². The darkening effect is explained in terms of trapping of light in the surface defects formed rather than anatase to rutile phase transformation as reported by others. Controlled darkening of TiO₂ film might be used for adjustable filters.     

Interaction of laser radiation with TNT with respect to the laser neutralisation of AP mines

According to UN estimations there are between 80 and 115 million activated landmines worldwide. These mines, or other unexploded ordnance (UXO), can be triggered accidentally and kill or injure more than 2000 civilians per month. The most common explosive in these mines is trinitrotoluene (TNT). In this paper, the potential of some of the most promising lasers for mine neutralisation is investigated, namely an ArF laser, a KrF excimer laser and a Nd:YAG solid-state laser. We have studied the interaction between laser beams emitting at λ=193 nm, 248 nm and 1060 nm and a bare solid sample of TNT of approximately 15 mg. Using pulsed excimer radiation at λ=193 nm, with an energy density up to 1 J/mm², ablation of the TNT without any deflagration has been achieved. At λ=248 nm, using the KrF excimer laser with a pulse duration of 30 ns and a repetition rate of 5 Hz, the TNT sample started melting and burning after an irradiation of 10 s. Preliminary results with the Nd:YAG solid-state laser operating in cw emission have shown that the irradiated sample exhibits the desired burning behaviour even after the exposure is stopped. Received: 14 December 2000 / Accepted: 18 December 2000 / Published online: 20 June 2001     

Optical extinction for determining the size distribution of gold nanoparticles fabricated by ultra-short pulsed laser ablation

This work presents a method, based on measurements of the optical extinction spectra, to determine the size of spherical gold nanoparticles produced using the femtosecond laser ablation process in deionized water. By using an improved theoretical model that modifies the contribution of the free electrons to the dielectric function introducing a size-dependent term, it is possible to fit the full experimental extinction spectrum considering a certain size distribution. Additionally, in order to obtain complementary measurements of the size distribution, TEM analysis was performed. The results obtained showed that the predominant nanoparticle size distribution ranges from 1 to 11 nm in terms of radii. An optical extinction measurement together with an appropriate theoretical model based on Mie’s theory represents a simple, low-cost, fast and easy method to describe a multimodal size distribution of spherical gold nanoparticles.     

Crystalline orientation effects on conical structure formation in femtosecond laser irradiation of silicon and germanium

Irradiation of Si(1 0 0), Si(1 1 1), Si(1 1 0), Ge(1 0 0), and Ge(1 1 1) is compared for 150 fs, 800 nm wavelength pulses in a rough vacuum atmosphere. The surface crystalline orientation of the material is found to affect the final morphology, with (1 1 1)- and (1 1 0)-surface orientations exhibiting a much higher tendency for conical structure formation under multiple-pulse irradiation. Using cross-sectional transmission electron microscopy, the structures on Si(1 1 1) are found to have primarily crystalline cores with the same crystalline orientation as the substrate. The results show that the crystalline orientation of the target should be considered in laser machining applications.     

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.