Langmuir probe investigation of surface contamination effects on metals during femtosecond laser ablation

Characterisation of the plasma plume induced by femtosecond laser-metal interactions has been carried out using a Langmuir probe. A double peak distribution of ablated ions and electrons has been recorded during time of flight (TOF) experiments for three metals studied (Ag, Cu and Ni). The first peak which occurs earliest in time is attributed to a surface layer of contaminants on the metal surface as it is shown to disappear after several laser shots. The re-growth of this peak, thought to be due to a recontamination process on the surface of the metal, is the subject of this paper. Two re-contamination mechanisms were considered; adsorption of contaminants from the ambient gas, and surface diffusion effects from the surrounding contaminants. Re-contamination rates for Ag, Cu and Ni were studied under two distinct gas pressures to investigate the contamination effects from the ambient. Effects arising from surface diffusion were investigated by raising the temperature of the metal sample to increase the surface mobility of the contaminants. The total contribution of contamination species present in the ablation plume was estimated by conducting angular distribution measurements of the plume. Surface diffusion of the surrounding contaminants was found to be the dominant recontamination process.     

Two-temperature relaxation and melting after absorption of femtosecond laser pulse

The theory and experiments concerned with the electron-ion thermal relaxation and melting of overheated crystal lattice constitute the subject of this paper. The physical model includes two-temperature (2T) equation of state, many-body interatomic potential, the electron-ion energy exchange, electron thermal conductivity, and optical properties of solid, liquid, and two phase solid-liquid mixture. Two-temperature hydrodynamics and molecular dynamics codes are used. An experimental setup with pump-probe technique is used to follow evolution of an irradiated target with a short time step 100 fs between the probe femtosecond laser pulses. Accuracy of measurements of reflection coefficient and phase of reflected probe light are 1% and ∼1 nm, respectively. It is found that, firstly, the electron-electron collisions make a minor contribution to a light absorption in solid Al at moderate intensities; secondly, the phase shift of a reflected probe results from heating of ion subsystem and kinetics of melting of Al crystal during  ps, where t is time delay between the pump and probe pulses measured from the maximum of the pump; thirdly, the optical response of Au to a pump shows a marked contrast to that of Al on account of excitation of d-electrons.     

Dynamics of ablation plasma induced by a femtosecond laser pulse in electric fields

Direct observations of ablation plasma dynamics in electric field is presented. A time-resolved spatial profile of the ablation plasma induced by femtosecond laser ablation (fsLA) with high fluence is visualized using a planar-laser-induced fluorescence (P-LIF) method. The external electric field is produced by installing a mesh electrode at 6 mm from a Samarium solid target. The Sm ion plasma created by the fsLA showed collective motion regardless of the external electric field, until they reached close to the electrode. When the accelerating and decelerating field was applied, the ions almost disappeared behind the electrode from the field of view. The observations are understood utilizing a SIMION simulation with a conceivable potential gradient caused by Debye shield effect, which is that the ablation plasma keeps the same potential as the target voltage and follows electric potential gradient near the mesh electrode. It is also revealed that this effect degrades time-of-flight resolution at high fluence irradiation. This work gives a new direction for further developments of a fsLA time-of-flight spectrometer.     

Study of UV laser interaction with gold nanoparticles embedded in silica

In order to resolve problems concerning the understanding and the control of laser-induced damage of silica optical elements, a collaboration between the CEA and different university laboratories has been undertaken. Ultra-pure silica model samples, seeded with gold nanoparticles whose diameter did not exceed 5 nm, were prepared. The aim in using these samples was to observe the mechanism of damage initiation that could be attributed to inclusions of nanometric size. This paper presents the different steps encountered during this study: preparation of the samples, the laser-induced damage tests, the Nomarski and atomic-force microscope observations of this damage and a series of experiments using a time-of-flight mass spectrometer at Argonne National Laboratory. The experimental data are then interpreted, and, in particular, compared to numerical simulations. A very encouraging result is the existence of a pre-damage phase at very low fluences that is not detectable by classical optical devices. The experimental means developed for such model samples should be transposable to the analysis of industrial glasses. Received: 19 July 2002 / Revised version: 23 September 2002 / Published online: 11 December 2002 RID="*" ID="*"Corresponding author. Fax: +33-1/6926-7106, E-mail: florian.bonneau@cea.fr     

Ablation and cutting of planar silicon devices using femtosecond laser pulses

Although lasers are generally able to machine silicon, the major material in many microsystems applications, doing so without influencing the physical properties of the bulk material remains an important challenge. Ultrafast lasers, in particular, with their potential to precisely ablate all kinds of solid materials, are able to perform such processes with high efficiency and accuracy. This article starts with an overview of the general interaction of ultrafast laser radiation with semiconductors, explaining the absorption processes and different fluence regimes for the ablation of silicon. Major parameter influences, especially for cutting processes in thin silicon, are described. By varying pulse energies, beam shaping methods, the beam polarization, and temperatures, the cutting quality and speed can be significantly influenced. One important quality aspect, besides kerf widths and surface roughness, is the amount of back-side chipping when cutting brittle materials. Achievements in speed enhancement using linear focus shapes are presented, with cutting speeds up to five times higher than by conventional spot-focusing. On the other hand, laser processes that cut with a spot focus offer the possibility of free-shape cutting, which is explained using the example of wafers carrying silicon chips with highly increased package densities. Received: 10 December 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +49-511/2788-100, E-mail: nb@lzh.de     

Silicon surface morphology study after exposure to tailored femtosecond pulses

Temporal pulse shaping of ultrashort laser pulses has been used for laser ablation of semiconductors. Even the simplest double pulse sequence with a delay of several picoseconds shows remarkable differences in the interaction process, compared to a single pulse of the same total energy. We discuss the interaction of double pulses with single crystal silicon sample in the context of crater morphology for multiple pulses on the same spot. The growth of the typical columnar structures in helium at atmospheric pressure is suppressed and the crater bottom is flat despite the Gaussian beam profile. The influence of the temporal pulse shape has to be treated in conjunction with the influence of the other ablation parameters.     

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.     

Effect of polarization on femtosecond laser pulses structuring silicon surface

Arrays of conical-like spikes can be formed on silicon surface after irradiated with femtosecond laser pulses in ambient of SF₆ or N₂. In this article, we report our observations on how the shape of the spikes formed on silicon surface varies with the polarization of laser beam. The experimental results show that, with circular polarized laser irradiation, the shape of the spikes is conical; however, with linearly polarized laser irradiation, the spikes show elliptic conical shape, and the long-axes are perpendicular to the direction of the polarization of laser beam. The asymmetric shape of spikes produced by linearly polarized laser beam can be explained by considering the polarization dependence of Fresnel-refraction.     

Chromium carbide thin films deposited by ultra-short pulse laser deposition

Pulsed laser deposition performed by a laser with a pulse duration of 250 fs has been used to deposit films from a Cr₃C₂ target. Due to the different processes involved in the laser ablation when it is performed by an ultra-short pulse source instead of a conventional short pulse one, it has been possible to obtain in vacuum films containing only one type of carbide, Cr₃C₂, as shown by X-ray photoelectron spectroscopy. On the other hand, Cr₃C₂ is not the only component of the films, since a large amount of amorphous carbon is also present. The films, deposited at room temperature, are amorphous and seem to be formed by the coalescence of a large number of particles with nanometric size. The film composition can be explained in terms of thermal evaporation from particles ejected from the target.     

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)].     

Mechanisms of ablation-rate decrease in multiple-pulse laser ablation

We present two sets of experimental results on the ablation-rate decrease with increase of the number of consecutive laser pulses hitting the same spot on the target surface. We have studied laser ablation of a carbon target with nanosecond pulses in two different interaction regimes: one with a XeCl laser (λ=308 nm) and the other with a Nd:YAG laser (λ=1064 nm), in both cases at the intensity ∼5×10⁸ W/cm² Two different mechanisms were found to be responsible for the ablation-rate decrease; they are directly related to the two different laser–matter interaction regimes. The UV-laser interaction is in the regime of transparent vapour (surface absorption). The increase of the neutral vapour density in the crater produced by the preceding laser pulses is the main reason for the decrease of ablation rate. With the IR laser each single laser pulse interacts with a partially ionised plume. With increase of the number of pulses hitting the same spot on the target surface, the laser–matter interaction regime gradually changes from the near-surface absorption to the volume absorption, resulting in the decrease in absorption in the target and thus in the decrease in the ablation rate. The change in the evaporation rate was considered for both vacuum and reactive-gas environments. Received: 21 February 2001 / Accepted: 26 February 2001 / Published online: 23 May 2001     

Emission spectroscopy of laser ablation plume: Composition analysis of a target in water

Emission spectra of the laser ablation plume formed by the irradiation of Cu65/Zn35 binary alloy in water at the room temperature with 150-ns pulsed laser were measured. The spectra were analyzed by comparing with the theoretical calculation based on the assumption that self-absorption effect is negligible and that the same temperature can be applied to Cu atoms and Zn atoms in the plume. The calculation reproduced the spectra very well and gave reasonable temperature as a best-fit parameter. However, the best-fit value of the Cu atomic density relative to Zn is significantly low compared with the target composition. Care should be taken to perform in situ LIBS in liquid due to the complicated plume formation mechanism and dynamics of material intake into the plume.     

Studies of craters’ dimension for long-pulse laser ablation of metal targets at various experimental conditions

Long pulse laser shots of the PALS iodine laser in Prague have been used to obtain metal target ablation at various experimental conditions. Attention is paid mainly to the dependencies of the crater diameter on the position of minimum laser-focus spot with regard to the target surface, by using different laser wavelengths and laser energies. Not only a single one, but two minima, independently of the wavelength, of the target irradiation angle and of the target material, were recorded. Significant asymmetries, ascribed to the non-linear effects of intense laser beam with pre-formed plasma, were found, too. Estimations of ejected mass per laser pulse are reported and used to calculate the efficiency of laser-driven loading. Results on metal target ablation and crater formation at high intensities (from 2 × 10¹³ to 3 × 10¹⁶ W/cm²) are presented and compared. Crater depth, crater diameter and etching yield are reported versus the laser energy, in order to evaluate the ablation threshold fluence.     

Nanofoaming in the surface of biopolymers by femtosecond pulsed laser irradiation

In this work, the nanostructuring induced in femtosecond (fs) laser irradiation of biopolymers is examined in self-standing films of collagen and gelatine. Irradiation by single 90 fs pulses at 800, 400 and 266 nm is shown to result in the formation of a modified layer with submicrometric size structures. The size and uniformity of the observed features are strongly dependent on irradiation wavelength and on the characteristics of the biopolymer (water content and mechanical strength). Examination of the films by laser induced fluorescence serves to assess the chemical modifications induced by laser irradiation, revealing changes in the emission bands assigned to the aromatic amino acid tyrosine and its degradation products. The results are discussed in the framework of a mechanism involving the generation of large free-electron densities, through multiphoton and avalanche ionization, which determine the temperature and stress distribution in the irradiated volume.     

Optical and waveguiding properties of Nd:KGW films grown by pulsed laser deposition

 Nd: KGd(WO₄)₂ thin films were deposited by KrF laser ablation on MgO, YAP, YAG and Si substrates at temperatures up to 800 °C. Film crystallinity, morphology, stoichiometry (WDX, RBS and PIXE), excitation spectra, fluorescence, refractive index and waveguiding properties were studied in connection with deposition conditions. The best films were crystalline and exhibited losses of approximately 5 dB cm^-1 at a wavelength of 633 nm. Received: 8 January 2001 / Accepted: 7 November 2001 / Published online: 11 February 2002     

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.     

Pulsed laser ablation of borax target in vacuum and hydrogen DC glow discharges

The aim of our experiment was to produce a material with BH bonds for applications in hydrogen storage and generation. By using KrF excimer laser (λ = 248 nm) ablation of borax (Na₂B₄O₇) target, thin films were deposited on KBr and silicon substrates. Ablation was performed both in vacuum and in hydrogen atmosphere. DC glow discharge technique was utilized to enhance hydrogen gas ionization. Experiments were performed using laser fluence from 5 to 20 J/cm². Films were deposited under gas pressure of 1 × 10⁻⁵ to 5 × 10⁻² mbar and substrate temperatures of 130-450 °C. Scanning electron microscopy analysis of films showed presence of circular particulates. Film thickness, roughness and particulates number increased with increase in laser fluence. Energy dispersive X-ray spectroscopy analysis shows that sodium content in the particulates is higher than in the target. This effect is discussed in terms of atomic arrangements (both at surface and bulk) in systems where ionic and covalent bonds are present and by looking at the increased surface/bulk ratio of the particulates with respect to the deposited films. The Fourier transform infrared spectroscopy measurements showed presence of BO stretching and BOB bending bonds. Possible reasons for absence of BH bonds are attributed to binding enthalpy of the competing molecules.     

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.     

Two-dimensional ‘hat-scratch’ periodic structures induced by a single femtosecond laser pulse on silica glass

Two-dimensional ‘hat-scratch’ structures are fabricated on silica glass by the interference of three non-coplanar beams originating from a single femtosecond laser pulse. The scanning electron microscope (SEM) characterizations show that the as-formed structures are composed of hat holes and scratch marks. The experimental results indicate that the structures are dependent on the intensity of laser beam. The formation of the two-dimensional ‘hat-scratch’ structures is mainly due to the combined laser ablation effects including ionization, shock wave, plasma expansion, and phase explosion.     

The effect of femtosecond laser micromachining on the surface characteristics and subsurface microstructure of amorphous FeCuNbSiB alloy

Detailed studies on the effects of femtosecond laser ablation on surface characteristics and subsurface microstructure of amorphous FeCuNbSiB alloy are reported. Three types of ripple structures were observed on the material surface in the gentle ablated (damaged) zone. As observed with X-ray diffraction (XRD), amorphous form is kept in the damaged zone, and there is few crystallization form in ablation zone.