Femtosecond laser ablation of carbon reinforced polymers

Interaction of intense ultrashort laser pulses (120 fs at 795 nm) with polymer based composites has been investigated. We have found that carbon filled polymers exhibit different ultrafast ablation behaviour depending on whether the filling material is carbon black or carbon fiber and on the polymer matrix itself. The shape and dimensions of the filling material are responsible for some geometrical bad quality effects in the entrance and inner surfaces of drilled microholes. We give an explanation for these non-quality effects in terms of fundamentals of ultrafast ablation process, specifically threshold laser fluences and material removal paths. Since carbon fiber reinforced polymers seemed particularly concerned, this could prevent the use of ultrafast ablation for microprocessing purposes of some of these materials.     

Femtosecond laser ablation of silicon–modification thresholds and morphology

We investigated the initial modification and ablation of crystalline silicon with single and multiple Ti:sapphire laser pulses of 5 to 400 fs duration. In accordance with earlier established models, we found the phenomena amorphization, melting, re-crystallization, nucleated vaporization, and ablation to occur with increasing laser fluence down to the shortest pulse durations. We noticed new morphological features (bubbles) as well as familiar ones (ripples, columns). A nearly constant ablation threshold fluence on the order of 0.2 J/cm² for all pulse durations and multiple-pulse irradiation was observed. For a duration of ≈100 fs, significant incubation can be observed, whereas for 5 fs pulses, the ablation threshold does not depend on the pulse number within the experimental error. For micromachining of silicon, a pulse duration of less than 500 fs is not advantageous. Received: 4 December 2000 / Revised version: 29 March 2001 / Published online: 20 June 2001     

Electrical properties of boron-doped diamond-like carbon thin films deposited by femtosecond pulsed laser ablation

We report on electrical measurements and structural characterization performed on boron-doped diamond-like carbon thin films deposited by femtosecond pulsed laser deposition. The resistance has been measured between 77 and 300 K using four probe technique on platinum contacts for different boron doping. Different behaviours of the resistance versus temperature have been evidenced between pure DLC and boron-doped DLC. The a-C:B thin film resistances exhibit Mott variable range hopping signature with temperature. Potential applications of DLC thin films to highly sensitive resistive thermometry is going to be discussed.     

Femtosecond pulsed laser ablation deposition of tantalum carbide

In this work a frequency-doubled Nd:glass laser with a pulse duration of 250 fs has been used to ablate a TaC target and to deposit thin films on silicon. The results have been compared with those previously obtained by nanosecond pulsed laser deposition and evidence of large differences in the plasma characteristics has been revealed. In particular, in the femtosecond and nanosecond plumes the energy and the velocity of neutral and ionized particles are very different. The features of femtosecond ablation include the delayed emission from the target of large and slow particles. The characteristics of the femtosecond plasma are clearly related to the morphology and composition of the deposited films and the results show a nanostructure consisting of a large number of spherical particles, with a mean diameter of about 50 nm, with a stoichiometry corresponding to Ta₂C. To explain these features, an ablation-deposition mechanism, related to the ejection of hot particles from the target, is proposed.     

Femtosecond laser ablation of aluminium

We investigate femtosecond laser ablation of aluminium using a hybrid simulation scheme. Two equations are solved simultaneously: one for the electronic system, which accounts for laser energy absorption and heat conduction, the other for the dynamics of the lattice where the ablation process takes place. For the electron-temperature a generalized heat-conduction equation is solved by applying a finite difference scheme. For the lattice properties, e.g. pressure, density or temperature, we use common molecular dynamics. Energy transfer between the subsystems is allowed by introducing an electron-phonon coupling term. This combined treatment of the electronic and atomic systems is an extension of the well known two-temperature model [Anisimov, Kapeliovich, Perel’man, Electron emission from metal surfaces exposed to ultra short laser pulses, JETP Lett. 39 (2)].     

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.     

Characterization of gaseous phase and nanoparticles produced in ultra-short pulsed laser ablation of transition metal borides

The plasma produced by ultra-short laser ablation of ZrB₂ and ReB₂ has been studied by ICCD imaging and time and space resolved optical emission spectroscopy. The aim was to clarify the mechanism of deposition leading to the morphology and composition found in the deposited films. The results indicate that for all systems the film characteristics are compatible with a deposition mechanism involving a growth from nanoparticles, ejected directly from the target, whose composition can be interpreted in terms of equilibrium vaporization during the flight from the target to the substrate.     

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.     

Machining of transparent materials using an IR and UV nanosecond pulsed laser

Channels are traditionally machined in materials by drilling from the front side into the bulk. The processing rate can be increased by two orders of magnitude for transparent materials by growing the channel from the rear side. The process is demonstrated using nanosecond laser pulses to drill millimeter-sized channels through thick silica windows. Absorbing defects are introduced onto the rear surface to initiate the coupling of energy into the material. Laser drilling then takes place when the fluence exceeds a threshold. The drilling rate increases linearly with fluence above this threshold. While UV light drills about four times faster than IR light, the pulse length (in the nanosecond regime) and the pulse repetition rate (in the 0.1–10 Hz range) do not greatly influence the drilling rate per pulse. Drilling rates in excess of 100 μm per pulse are achieved by taking advantage of the propagation characteristics of the plasma created at the drilling front. The plasma during rear-side drilling generates a laser-supported detonation wave into the bulk material. The geometry also seems to increase the efficiency of the laser-induced plasma combustion and shock wave during the pulse by confining it in front of the channel tip. Received: 1 July 1999 / Accepted: 17 April 2000 / Published online: 20 September 2000     

Electrodeposition of diamond-like carbon (DLC) films on Ti

Diamond-like carbon films (DLC) were deposited on titanium substrates in acetonitrile and N,N-dimethyl formamide (DMF) liquids by the liquid-phase electrodeposition technique at ambient pressure and temperature. The applied voltage between the electrodes was high (1200 V) due to the use of resistive organic liquids. The surface morphology was examined by Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Corrosion performance of the coatings was investigated by potentiodynamic polararization tests in phosphate buffer saline solution. Raman spectroscopy analysis of the films revealed two broad bands at approximately 1360 cm⁻¹ and 1580 cm⁻¹, related to D and G-band of DLC, respectively. The coated Ti was tested in a ball-on-plate type wear test machine with Al₂O₃ balls. The films presented a low friction coefficient (about 0.1), and the films deposited from DMF presented the best wear resistance.     

Femtosecond laser-induced formation of spikes on silicon

We find that silicon surfaces develop arrays of sharp conical spikes when irradiated with 500-fs laser pulses in SF₆. The height of the spikes decreases with increasing pulse duration or decreasing laser fluence, and scales nonlinearly with the average separation between spikes. The spikes have the same crystallographic orientation as bulk silicon and always point along the incident direction of laser pulses. The base of the spikes has an asymmetric shape and its orientation is determined by the laser polarization. Our data suggest that both laser ablation and laser-induced chemical etching of silicon are involved in the formation of the spikes. Received: 10 September 1999 / Accepted: 7 January 2000 / Published online: 8 March 2000     

Early stages of laser graphitization of diamond

A mechanism for photographitization of a free diamond surface is proposed. The quantum-kinetic rate of this process is determined. The graphitization rate is close to zero if the activation energy of the graphitization process is taken as being equal to the binding energy of a carbon atom with the surface (i.e. equal to the sublimation energy of a carbon atom). On the contrary, if the activation energy is close to the energy of C–C bonds, the graphitization process may occur at a noticeable rate and be observed under ‘relatively smooth’ experimental conditions. The temperature rise leads to a considerable increase in the graphitization rates. Preliminary experimental data on the low-rate laser ablation of diamond are presented to support the proposed model of photographitization. An early stage of laser-induced graphitization in the bulk of diamond is also considered. It is found that the nucleation of a ‘tiny graphite drop’ is possible in the bulk of the diamond inside the focal area of a laser beam; the ‘graphite drop’ growth causing the appearance of mechanical stresses in the surrounding regions. The maximum size of the graphite drop is determined, which, when exceeded, leads to mechanical damage of the sample and to a change in the mechanism of laser graphitization. An evident mechanical criterion for laser-induced damage of diamond is proposed. Received: 2 October 2002 / Accepted: 5 October 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. E-mail: stvn@stankin.ru     

Femtosecond laser ablation characteristics of nickel-based superalloy C263

Femtosecond laser (180 fs, 775 nm, 1 kHz) ablation characteristics of the nickel-based superalloy C263 are investigated. The single pulse ablation threshold is measured to be 0.26±0.03 J/cm² and the incubation parameter ξ=0.72±0.03 by also measuring the dependence of ablation threshold on the number of laser pulses. The ablation rate exhibits two logarithmic dependencies on fluence corresponding to ablation determined by the optical penetration depth at fluences below ∼5 J/cm² (for single pulse) and by the electron thermal diffusion length above that fluence. The central surface morphology of ablated craters (dimples) with laser fluence and number of laser pulses shows the development of several kinds of periodic structures (ripples) with different periodicities as well as the formation of resolidified material and holes at the centre of the ablated crater at high fluences. The debris produced during ablation consists of crystalline C263 oxidized nanoparticles with diameters of ∼2–20 nm (for F=9.6 J/cm²). The mechanisms involved in femtosecond laser microprocessing of the superalloy C263 as well as in the synthesis of C263 nanoparticles are elucidated and discussed in terms of the properties of the material.     

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.     

Femtosecond laser induced submicrometer structures on the ablation crater walls of II-VI semiconductors in water

Femtosecond laser ablations (100 fs, 800 nm, 0.2 mJ/pulse) were performed to produce craters on CdS, ZnS:Cu and ZnSe wafers in water. On the surface of the crater walls, a variety of submicrostructural formations were presented, such as the ripples and network structures for CdS, the subwavelength ripples and columnar structures for ZnS:Cu, even the regular cubic-shaped submicron rods for ZnSe. Based on the field-emission scanning electron microscope (FE-SEM) study of the different characteristic surface morphologies, the possible formation mechanisms were discussed correspondingly. For example, two distinct mechanisms are contributing to the different styles of ripples formed on CdS and ZnS:Cu. The former is the interference effects between the incoming laser beam and scattered surface wave, while the latter is the self-organization structure formation. In addition, the re-crystallization of the water-confined hot plasma would play an important role in the formation of ZnS:Cu column structures and ZnSe rods.     

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.     

Femtosecond pulsed laser ablation of 3CSiC thin film on silicon

A femtosecond pulsed Ti:sapphire laser (pulse width=120 fs, wavelength=800 nm, repetition rate=1 kHz) was employed to perform laser ablation of 1-m-thick silicon carbide (3CSiC) films grown on silicon substrates. The threshold fluence and ablation rate, useful for the micromachining of the 3CSiC films, were experimentally determined. The material removal mechanisms vary depending on the applied energy fluence. At high laser fluence, a thermally dominated process such as melting, boiling and vaporizing of single-crystal SiC occurs. At low laser fluence, the ablation is a defect-activation process via incubation, defect accumulation, formation of nanoparticles and final vaporization of boundaries. The defect-activation process reduces the ablation threshold fluence and enhances lateral and vertical precision as compared to the thermally dominated mechanism. Helium, as an assistant gas, plays a major role in improving the processing quality and ablation rate of SiC thin films due to its inertness and high first ionization energy. PACS 79.20.Ds; 42.62.Cf; 42.70.Qs; 61.72; 61.46     

Characterization of ablation plumes and carbon nitride films produced by reactive pulsed laser deposition in the presence of a magnetic field

x ) films in a nitrogen atmosphere within the range 5×10^-4–4×10^-1 Torr. In the presence of a magnetic field, the emission intensities of N₂ (second positive system) and CN species in the graphite ablation plumes were altered significantly, depending on the pressure of the N₂ environment. Corresponding to an intense CN emission, a magnetic field-induced enhancement of N incorporation – for example, up to 37% at an N₂ pressure of 300 mTorr – and the formation of sp³ tetrahedral CN bonding were both observed in the films. This suggests that the arrival of CN species at the substrate surface with kinetic energies is important for film deposition. Received: 27 August 1997/Accepted: 8 September 1997     

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.