Nanosecond and femtosecond excimer-laser ablation of oxide ceramics

The uv laser-ablation behavior of various oxide ceramics (Al₂O₃, MgO, ZrO₂) has been studied using different wavelengths (248 nm, 308 nm) and pulse durations (30 ns, 500 fs). Time-resolved absorption measurements of the sample and the ablation plume during ablation were performed.Using sub-ps pulses the ablation threshold fluence is generally lower than for ns pulses; the ablation rate is higher in the whole investigated fluence range up to 20 J/cm².The study of the morphology of the ablation structures and the results of the absorption experiments lead to the conclusion that different ablation mechanisms are involved. Using ns pulses plasma mediated ablation is dominating, whereas in the fs case the process is controlled by multi-photon absorption enabling microstructuring of the material.     

Nanosecond and femtosecond excimer laser ablation of fused silica

Ablation of fused silica using standard excimer lasers (20–30 ns pulse duration at 193, 248, and 308 nm) and a short pulse laser system (500 fs at 248 nm) is reported. Ablation rates range from several hundred nm/pulse (193 nm or fs-laser) up to about 6 m/pulse (308 nm). The performance of the ablation is found to depend not only on wavelength and pulse duration but also on the existing or laser induced surface quality (e.g., roughness) of the material. Special ablation phenomena are observed. At 193 nm and moderate fluence (3 J/cm²) ablation takes place at the rear side of a plate without affecting the front side, whereas at higher fluence normal ablation at the front side occurs. At 248 nm (standard excimer) the existence of two consecutive ablation phases is observed: smooth ablation at low rate is followed by explosive ablation at high rate. Using fs-pulses smooth shaped holes are formed during the first pulses, whereas high pulse numbers cause the development of a ripple structure in the ablation craters.The results lead to the conclusion that two different ablation mechanisms are involved: the first is based on two photon bulk absorption, the second on controlled surface damage in relation with (partially laser induced) singularity conditions at the surface.Presented at LASERION '91, June 12–14, 1991, München (Germany)     

Influence of laser fluence and irradiation timing of F2 laser on ablation properties of fused silica in F2-KrF excimer laser multi-wavelength excitation process

A collinear irradiation system of F₂ and KrF excimer lasers for high-quality and high-efficiency ablation of hard materials by the F₂ and KrF excimer lasers’ multi-wavelength excitation process has been developed. This system achieves well-defined micropatterning of fused silica with little thermal influence and little debris deposition. In addition, the dependence of ablation rate on various conditions such as laser fluence, irradiation timing of each laser beam, and pulse number is examined to investigate the role of the F₂ laser in this process. The multi-wavelength excitation effect is strongly affected by the irradiation timing, and an extremely high ablation rate of over 30 nm/pulse is obtained between -10 ns and 10 ns of the delay time of F₂ laser irradiation. The KrF excimer laser ablation threshold decreases and its effective absorption coefficient increases with increasing F₂ laser fluence. Moreover, the ablation rate shows a linear increase with the logarithm of KrF excimer laser fluence when the F₂ laser is simultaneously irradiated, while single KrF excimer laser ablation shows a nonlinear increase. The ablation mechanism is discussed based on these results. Received: 16 July 2001 / Accepted: 27 July 2001 / Published online: 2 October 2001     

Removal of doped poly(methylmetacrylate) from tungsten and titanium substrates by femto- and nanosecond laser cleaning

The influence of different laser pulse lengths on the removal of a polymer layer from metal substrates was investigated. As model systems, doped poly(methylmetacrylate) (PMMA) on titanium and tungsten substrates were selected.The ablation threshold and irradiation spot morphology of titanium and tungsten were compared for femtosecond (fs) and nanosecond (ns) laser irradiation and different pulse numbers. Nanosecond laser treatment resulted in a non-homogeneous surface morphology for both titanium and tungsten substrates. Femtosecond irradiation of tungsten revealed a homogeneous ablation spot with little changes in the surface morphology. For titanium, the formation of columnar structures within the irradiation spot was observed.Two different dopant concentrations were used for PMMA to achieve an equal linear absorption coefficient for the femto- and nanosecond laser wavelengths of 790 and 1064 nm. The best results were achieved for the removal of doped PMMA by femtosecond laser irradiation, where only a minimal modification of the metal surface was detected. In the case of nanosecond laser exposure, a pronounced change of the structure was observed, suggesting that damage-free cleaning of the selected metal may only be possible using femtosecond laser pulses. Different experimental parameters, such as laser fluence, pulse repetition rate and sample speed were also investigated to optimize the cleaning quality of doped PMMA from tungsten substrates with femtosecond laser pulses.     

Plasma effects in picosecond-femtosecond UV laser ablation of polymers

Laser ablation of polyimide (PI) and polymethyl-methacrylate (PMMA) at 248 nm with pulse lengths ranging from 200 fs to 200 ps was investigated. The measured ablation rates show minima for pulse lengths of about 5 ps (PMMA) or 50 ps (PI).The reflected fraction of the ablating laser pulse was measured as a function of the pulse length. In the case of PMMA maximum reflectance corresponds to a minimum ablation rate.This behavior can be explained by a dynamic plasma reflection model: A fast build up of a dense plasma is followed by high obscuration for a brief transition time and a self-regulating opacity for the rest of the pulse. This model of plasma mediated ablation leads to a ^1/4-dependence of the ablation rate at fixed fluence, which fits very well to the measured data, in particular if an extension to nanosecond ablation data of PI and PMMA is considered. PACS 52.50.Jm; 61.80.Ba; 42.65.Re     

Excimer-laser-induced permanent electrical conductivity in solid C60 films

After being irradiated in air by a XeCI (308 nm) excimer laser, the electrical conductivity of solid thin-film C₆₀ has been improved by more than six orders of magnitudes. The products resulting from laser irradiation of C₆₀ films have been investigated by Raman scattering and the onset of conductivity can be attributed to laser-induced oxygenation and disintegration of the fullerene. Irradiated by 40 ns laser pulses with different fluence, products with different microstructure were observed. At lower fluence, the Raman features of microcrystalline graphite and fullerene polymer were observed. At a fluence just below the ablation threshold (36 mJ/cm²), the fullerene molecules in the film were disintegrated completely and transformed to amorphous graphite.     

Non-Thermal Laser Ablation Model for Micro-Surgical Applications

We have developed a non-thermal laser ablation model which may reduce thermal damage to neighboring structures. Based on this model, the three critical parameters for a well controlled non-thermal microsurgery are (1) the laser wavelength with its photon energy matching closely the bond dissociation energy, (2) the energy fluence must be above threshold to avoid thermal process due to non-radiative relaxation from the excited electronic states to vibrational, (3) ultra short laser pulses (few fs) to completely eliminate thermal and direct biomolecular reactions. In this model the UV laser photon dissociates the molecular bonds which leads to the splitting of longer polymer chains into small fragments. The excess energy if any may appear as kinetic energy in the polymer-fragments. The extreme rapidity of the bond breaking process reduces heat conduction. The model establishes a relationship between ablation depth per pulse, the absorption coefficient, the incident laser energy fluence, and the threshold energy fluence. The ablation depths per pulse were calculated for the polymers Polymethyl methacrylate (PMMA) and polyimide for various commercially available UV lasers. It has been found that the minimum ablations depth occurs at 193 nm for both PMMA and polyimide. This assures a well defined incision with minimal thermal damage to the surrounding structures at this wavelength. There exists a definite threshold energy fluence for non-thermal ablation for any given biomolecule and below the threshold the non-radiative relaxation process may cause thermal ablation. New ultra fast lasers (few femtoseconds) (fs) will completely eliminate thermal diffusion as well as direct biomolecular reactions.     

Enhanced ablation of silica by the superposition of femtosecond and nanosecond laser pulses

We investigate the ablation process in SiO₂ by the superposition of 180 fs laser pulse (_center=800 nm) with a 15 ns laser pulse (_center=532 nm). Compared to femtosecond laser pulses alone, we measured an increase of 270±30% in volume of the ejected material with only a total increase of 40% of lasers fluences. This increase of ablation is the result of thermal and incubation effects generated by the femtosecond laser pulse. PACS 78.20.Nv; 61.80.Ba     

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.     

Incubation/ablation patterning of polymer surfaces with sub-μm edge definition for optical storage devices

By exposure to low fluence UV laser radiation, the optical absorption coefficient of subsurface polymer material can be increased (incubation) with spatial control, using a suitable contact mask, proper imaging of the mask, or laser direct writing. Spatially selective ablation of polymethylmethacrylate (PMMA) is then achieved with large area XeCl excimer laser pulses at 308 nm. In this way, the transfer of spatial information to the material can be decoupled from the high laser fluence removal (ablation) step. The advantages are: The mask is exposed to only low fluence laser radiation — damage is avoided. Since the mask can be removed before the ablation step, mask contamination by the ablated plume cannot occur. Using this incubation/ablation method, PMMA surfaces can be patterned (248 nm/308 nm) with submicrometer spatial control and edge contrasts better than 0.2 m. This has impact on optical storage technology and laser surface processing techniques in general. The smallest single structure obtained was somewhat smaller than 0.5 m in diameter up to now, given by the mask.Presented at Laserion '91, June 12–14, 1991     

Dopant-induced excimer laser ablation of poly(tetrafluoroethylene)

Clean ablation of poly(tetrafluoroethylene) (PTFE) at etch rates in excess of 7µm/pulse has been achieved with an excimer laser using 308nm radiation and a 25 ns pulse width. This was accomplished by doping the ultraviolet-transparent PTFE polymer with polyimide. Ablation rates were investigated as a function of fluence in the range from 1 to 12J/cm² and dopant levels up to 15% (wt/wt). Results show that at a given fluence there exists an optimum absorption coefficient _max, for which maximum ablation rates are achieved. The value of _max was found to decrease with increasing fluence. The relationship between _max and fluence was determined from existing ablation rate models and found to compare favorably with empirical results.     

Photoablation of polyurethane films using UV laser pulses

Pulsed ultraviolet laser ablation of two polyurethane films has been studied in terms of ablation rate behaviour and time-of-flight mass spectroscopy of the positively charged photofragments. Three excimer laser wavelengths (193, 248 and 308 nm; 17–30 ns pulse duration) and short-pulse laser system (pulse duration 500 fs or 5 ps, at 248 nm) were employed. The results of the influence of energy fluence on the ablation rate are tested against other photoablation models and a table of fitted physical constants is presented. The upper limit of the mean activation energy for desorption is found to be considerably lower than the energy required to break single covalent bonds. The mass analysis of the positively charged species produced during the photoablation process provides valuable insight into the photofragmentation mechanism.     

超短脉冲激光烧蚀石墨产生的喷射物的时间分辨发射光谱研究

本文使用不同激光能流(18 J/cm²–115 J/cm²)和脉冲宽度(50 fs–4 ps)的超短脉冲激光在真空中(4×10^-4 Pa)烧蚀高定向热解石墨. 通过测量烧蚀喷射物的时间分辨发射光谱研究喷射物的超快时间演化. 在喷射物发射光谱中, 观察到了C₂基团的天鹅带光谱系统, 416 nm附近C₁₅基团的由电子能级¹Σ_u⁺ 和¹Σ_g⁺之间的振动跃迁产生的光谱峰以及连续谱. 50 fs, 115 J/cm²的脉冲激光烧蚀产生的喷射物的连续谱的强度衰减分为快速下降和慢速下降两个阶段(以20 ns时间延迟为分界). 这表明连续谱是由两种不同的组分贡献的. 快速下降阶段, 连续谱主要由碳等离子体通过韧致辐射产生; 慢速下降阶段, 连续谱主要由烧蚀后期产生的大颗粒碳簇的热辐射贡献. 实验结果还揭示了激光能流的提高, 会明显增加喷射物中碳等离子体和激发态C₂的含量, 但对质量稍大的C₁₅的影响较小; 此外, 50 fs脉冲激光烧蚀产生的连续谱的存在时间会随着激光能流的减小而增大, 这说明低能流更有利于在烧蚀后期产生碳簇. 脉宽主要影响喷射物连续谱的时间演化. 4 ps脉冲激光烧蚀产生的连续谱的整个时间演化过程明显慢于50 fs脉冲产生的连续谱.     

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     

Influence of thermal diffusion on the laser ablation of thin polymer films

The laser ablation of a photosensitive triazene polymer was investigated with a ns XeCl excimer laser over a broad range of thicknesses (10–400 nm). We found that the ablation threshold fluence increased dramatically with decreasing film thickness for films thinner than 50 nm. Ablation on substrates with different thermal properties (sapphire, fused silica, PMMA) was investigated as well, and a clear influence of the substrate material was obtained. A mathematical model combining thermal diffusion and absorption effects was used to explain the experimental data. The model is in good agreement with the experimental data and shows that heat diffusion into the substrate plays a crucial role for the ablation process of very thin films. PACS 52.38.Mf; 44.05.+e; 81.05.Lg     

Femtosecond-pulse laser ablation of human corneas

A femtosecond pulse laser in the visible spectral region shows promise as a potentially new powerful corneal sculpting tool. It combines the clinical and technical advantages of visible wavelengths with the high ablation quality observed with nanosecond-pulse excimer lasers at 193 nm. A femtosecond and a nanosecond dye laser with pulse durations of 300 fs and 7 ns, and centre wavelengths at 615 nm and 600 nm, respectively, both focused to an area of the order of 10^–5 cm², have been applied to human corneal ablation. Nanosecond laser pulses caused substantial tissue disruption within a 30–100 m range from the excision edge at all fluences above the ablation threshold of F _th60 J cm^–2 (I _th9 GW cm^–2). Completely different excisions are produced by the femtosecond-pulse laser: high quality ablations of the Bowman membrane and the stroma tissue characterised by damage zones of less than 0.5 m were observed at all fluences above ablation threshold of F _th1 J cm^–2 or I _th3 TW cm^–2 (3×10¹² W cm^–2). The transparent cornea material can be forced to absorb ultrashort pulses of extremely high intensity. The fs laser generates its own absorption by a multiphoton absorption process.     

Single-shot ablation threshold of chromium using UV femtosecond laser pulses

Single-shot ablation threshold for thin chromium film was studied using 266 nm, femtosecond laser pulses. Chromium is a useful material in the nanotechnology industry and information on ablation threshold using UV femtosecond pulses would help in precise micromachining of the material. The ablation threshold was determined by measuring the ablation crater diameters as a function of incident laser pulse energy. Absorption of 266 nm light on the chromium film was also measured under our experimental conditions, and the absorbed energy single-shot ablation threshold fluence was \(46 \pm 5\)  mJ/cm². The experimental ablation threshold fluence value was compared to time-dependent heat flow calculations based on the two temperature model for ultrafast laser pulses. The model predicts a value of 31.6 mJ/cm² which is qualitatively consistent with the experimentally obtained value, given the simplicity of the model.     

Ad-hoc design of temporally shaped fs laser pulses based on plasma dynamics for deep ablation in fused silica

We have analyzed the ablation depth yield of fused silica irradiated with shaped pulse trains with a separation of 500 fs and increasing or decreasing intensity envelopes. This temporal separation value is extracted from previous studies on ablation dynamics upon irradiation with transform-limited 100 fs laser pulses. The use of decreasing intensity pulse trains leads to a strong increase of the induced ablation depth when compared to the behavior, at the same pulse fluence, of intensity increasing pulse trains. In addition, we have studied the material response under stretched (500 fs, FWHM) and transform-limited (100 fs, FWHM) pulses, for which avalanche or multiphoton ionization respectively dominates the carrier generation process. The comparison of the corresponding evolution of the ablated depth vs. fluence suggests that the use of pulse trains with decreasing intensity at high fluences should lead to enhanced single exposure ablation depths, beyond the limits corresponding to MPI- or AI-alone dominated processes.     

Effect of laser radiation parameters on the conductivity of structures produced on the polycrystalline diamond surface

Graphitized structures are fabricated on the polycrystalline diamond surface using an excimer KrF (λ = 248 nm, τ = 20 ns) and a Ti:Al₂O₃ (λ = 400 nm, τ = 120 fs) lasers. It is shown that the conductivity of formed structures is independent of the energy density and the number of pulses per surface point in the case of the excimer laser, whereas such a dependence was observed for femtosecond pulses. The causes of the dependence of the conductivity of surface structures on laser irradiation parameters are discussed.     

Selective ablation of thin SiO<Subscript>2</Subscript> layers on silicon substrates by femto- and picosecond laser pulses

The selective ablation of thin (∼100 nm) SiO₂ layers from silicon wafers has been investigated by applying ultra-short laser pulses at a wavelength of 800 nm with pulse durations in the range from 50 to 2000 fs. We found a strong, monotonic decrease of the laser fluence needed for complete ablation of the dielectric layer with decreasing pulse duration. The threshold fluence for 100% ablation probability decreased from 750 mJ/cm² at 2 ps to 480 mJ/cm² at 50 fs. Significant corruption of the opened Si surface has been observed above ∼1200 mJ/cm², independent of pulse duration. By a detailed analysis of the experimental series the values for melting and breaking thresholds are obtained; the physical mechanisms responsible for the significant dependence on the laser pulse duration are discussed.