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.     

Picosecond laser ablation of thin copper films

The ablation process of thin copper films on fused silica by picosecond laser pulses is investigated. The ablation area is characterized using optical and scanning electron microscopy. The single-shot ablation threshold fluence for 40 ps laser pulses at 1053 nm has been determinated toF _thres = 172 mJ/cm². The ablation rate per pulse is measured as a function of intensity in the range of 5 × 10⁹ to 2 × 10¹¹ W/cm² and changes from 80 to 250 nm with increasing intensity. The experimental ablation rate per pulse is compared to heat-flow calculations based on the two-temperature model for ultrafast laser heating. Possible applications of picosecond laser radiation for microstructuring of different materials are discussed.     

Concentrations and velocity distributions of positive ions in laser ablation of copper

It is shown that the generation of secondary electrons by excited neutrals hitting a surface makes the so-called probe method unsuited for measuring the positive ion fraction in laser ablation plumes. Experiments have been performed in a modified set-up, in which the disturbance by secondary electrons is avoided. For a typical case of Cu irradiated in ultra-high vacuum by nanosecond excimer laser pulses of 3 J cm^–2 the ionized fraction is about 10^–8 at a distance of 60 cm. This number is in fair agreement with Saha-Langmuir predictions based on the assumption of local thermal equilibrium at an estimated temperature of about 3000K. Angular-resolved time-of-flight measurements show that there are three different ion velocity distributions. A slow contribution (kinetic energy 2eV) with an angular distribution peaked along the normal, and two fast, isotropic contributions (kinetic energy 20–50 eV). The fast contributions are attributed to ions involved in a Coulomb explosion.     

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.     

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.     

Fabrication of Mg-doped ZnO thin films by laser ablation of Zn:Mg target

Mg-doped ZnO thin films were fabricated by laser ablation of Zn:Mg targets consisting of Mg metallic strips and Zn disk in oxygen atmosphere with a goal to facilitate convenient control of Mg contents in the films. The characteristics of the deposited films were examined by analyzing their photoluminescence (PL), X-ray diffraction and X-ray photoelectron spectroscopy (XPS) spectra. Mg contents as analyzed by XPS indicate that the target composition is fairly transferred to the deposited films. The wurtzite structure of ZnO was conserved even for the highly doped ZnO films and there was no Mg- or MgO-related XRD peaks. With increase in the Mg content, the bandgap and PL peak energy shifted to blue and the Stokes shift became larger.     

Measurements of multiphoton ionization coefficients with ultrashort ultraviolet laser pulses

Multiphoton ionization coefficients of atmospheric gases were measured with ultrashort ultraviolet laser pulses. The values were obtained using two different experimental setups and the pressure range covered four orders of magnitude. The coefficients were pressure-independent and consistent with numbers predicted by the nonresonant Keldysh theory. Received: 13 June 2000 / Revised version: 5 October 2000 / Published online: 7 February 2001     

Nonlinear absorption of ultrashort laser pulses in thin metal films

Self-consistent simulations of the ultrafast electron dynamics in thin metal films were performed. A regime of nonlinear oscillations was observed that corresponds to ballistic electrons bouncing back and forth against the films' surfaces. When an oscillatory laser field is applied to the film, the field energy is partially absorbed by the electron gas. Maximum absorption occurs when the period of the external field matches the period of the nonlinear oscillations, which, for sodium films, lies in the infrared range. Possible experimental implementations are discussed.     

Selective ablation of thin Mo and TCO films with femtosecond laser pulses for structuring thin film solar cells

We report on recent results on selective ablation of TCO (SnO₂, ZnO) and metallic layers as a possible process for structuring thin film solar cells. The multipulse ablation thresholds determined for substrate and various thin films show a parameter window where the films can be completely removed by a single scan without at the same time damaging the underlying material. By employing ultrashort pulsed lasers, nonthermal ablation at repetition rates up to the megahertz regime enables high quality structuring combined with process speeds meeting industrial demands. PACS 42.65.Re; 42.55.Xi; 42.62.-b; 84.60.Jt     

XPS studies of short pulse laser interaction with copper

The effect of laser ablation on copper foil irradiated by a short 30 ns laser pulse was investigated by X-ray photoelectron spectroscopy. The laser fluence was varied from 8 to 16.5 J/cm² and the velocity of the laser beam from 10 to 100 mm/s. This range of laser fluence is characterized by a different intensity of laser ablation. The experiments were done in two kinds of ambient atmosphere: air and argon jet gas.The chemical state and composition of the irradiated copper surface were determined using the modified Auger parameter (α′) and O/Cu intensity ratio. The ablation atmosphere was found to influence the size and chemical state of the copper particles deposited from the vapor plume. During irradiation in air atmosphere the copper nanoparticles react with oxygen and water vapor from the air and are deposited in the form of a CuO and Cu(OH)₂ thin film. In argon atmosphere the processed copper surface is oxidized after exposure to air.     

Synthesis of chromium silicide with laser pulses

Thin chromium films, 60 nm thick, were deposited onto single-crystal silicon wafers. The samples were irradiated with 30 ns single pulses from a Nd: glass laser at fluences ranging from 0.4 to 2.25 J/cm². Rutherford backscattering spectrometry, transmission electron microscopy and electron diffraction measurements evidence the formation of CrSi₂ layers at the Cr/Si interface. The silicide thickness depends on the laser fluence.     

Microdeposition of metal and oxide structures using ultrashort laser pulses

2 O₃ on glass and silicon substrates is performed. The superior quality of the results allows the direct, one-step fabrication of binary-amplitude and multilevel optical diffractive structures. Received: 4 February 1998/Accepted: 9 February 1998     

Modeling of UV pulsed-laser ablation of metallic targets

A model to describe the laser ablation of metallic targets is presented. It accounts for the main physical processes involved in the laser–solid–plasma interaction by considering the photon absorption and the ionization mechanisms that are active in the plasma, as well as the laser-produced plasma kinetics. The model is used to simulate the laser ablation of aluminum targets irradiated with a 6-ns UV laser pulse at 0.35 μm, and the results are compared with experimental findings. Calculations show that all the investigated plasma parameters strongly depend on the laser intensity until a roll-off is reached at irradiance ≥1.5 GW cm^-2. The satisfactorily good agreement between model predictions and experimental findings confirms that laser–plasma interaction processes and plasma kinetics play a relevant role during nanosecond laser ablation of metals in the laser intensity range of concern in this study. Received: 12 February 1999 / Accepted: 12 April 1999 / Published online: 7 July 1999     

The influence of thermal diffusion on laser ablation of metal films

Single-shot ablation thresholds of nickel and gold films in the thickness range from 50 nm to 7 m have been measured for 14 ns laser pulses at 248 nm, using photoacoustic shock wave detection in air. The metal films were deposited on fused silica substrates. The ablation threshold was found to increase linearly with film thickness up to the thermal diffusion length of the film. Beyond this point it remains independent of film thickness. The proportionality between threshold fluence and thickness allows the prediction of ablation thresholds of metal films from the knowledge of their optical properties, evaporation enthalpies and thermal diffusivities. Physically it proves that ablation is driven by the energy density determined by the thermal diffusion length. A simple thermodynamic model describes the data well. Thermal diffusivities, an essential input for this model, were measured using the technique of transient thermal gratings. In addition, the substrate dependence of the ablation threshold was investigated for 150 nm Ni films.     

Optimisation of direct laser structuring of printed circuit boards

A model-based optimisation of the process of printed circuit board laser structuring is presented. For this purpose, a comprehensive theoretical model of the interaction between the travelling pulsed laser beam and conductive layer, as well as between the laser beam and the induced plasma plume is employed. The model is used to calculate process speed. Based on the process speed determined, the influence of pulse power, duration, and frequency on process speed is analysed. In addition, an optimal range of process parameters with respect to process speed and quality is defined.     

Ultrafast dynamic ellipsometry measurements of early time laser ablation of titanium thin films

The dynamics of laser ablated titanium thin films are investigated using a recently developed technique that measures time-resolved and one-dimensional spatially-resolved ablation dynamics in a single shot. Ultrafast dynamic ellipsometry, a technique based on space-shifted spectral interferometry, uses the time-dependent frequency of a chirped laser pulse to provide time encoding, allowing the picosecond probing of material dynamics in a single shot. With this technique, the sample is probed at two different incident angles with both s- and p-polarized light, which measures the motion of the material and any change in its complex refractive index. Ultrafast dynamic ellipsometry is applied to study the mechanism of initiation by laser-based optical detonators that employ the ablation of titanium thin films. The resulting data indicate that the titanium is ablated as a fragmented flyer and not as an expanding plasma.     

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.     

Femtosecond laser patterning of Ta0.1W0.9Ox/ITO thin film stack

Selective laser patterning of thin films in a multilayered structure is an emerging technology for process development and fabrication of optoelectronics and microelectronics devices. In this work, femtosecond laser patterning of electrochromic Ta_0.1W_0.9O_x film coated on ITO glass has been studied to understand the selective removal mechanism and to determine the optimal parameters for patterning process. A 775 nm Ti:sapphire laser with a pulse duration of 150 fs operating at 1 kHz was used to irradiate the thin film stacks with variations in process parameters such as laser fluence, feedrate and numerical aperture of objective lens. The surface morphologies of the laser irradiated regions have been examined using a scanning electron microscopy and an optical surface profiler. Morphological analysis indicates that the mechanism responsible for the removal of Ta_0.1W_0.9O_x thin films from the ITO glass is a combination of blistering and explosive fracture induced by abrupt thermal expansion. Although the pattern quality is divided into partial removal, complete removal, and ITO film damage, the ITO film surface is slightly melted even at the complete removal condition. Optimal process window, which results in complete removal of Ta_0.1W_0.9O_x thin film without ablation damage in the ITO layer, have been established. From this study, it is found that focusing lens with longer focal length is preferable for damage-free pattern generation and shorter machining time.