Modeling of plume dynamics with shielding in laser ablation of carbon

The process of laser ablation of carbon in presence of background gas is simulated numerically. The plume dynamics in laser ablation is important to study for many reasons including temperature of plume particles and shielding of target by previously ablated plumes. Shielding leads directly to the change in energy deposition of incident laser pulse at the target surface and in turn influences the ablation dynamics and amount of material removed. Carbon ablation is studied for single and multiple laser hits typical for synthesis of nanotubes. Two models of correction of ablated velocity and pressure resulting from shielding effect are proposed and investigated. Numerical modeling of this plume dynamics and its integral effect of shielding is challenging due to inherent high nonlinearity of the problem. Some of available numerical techniques handles nonlinearity but are dissipative, e.g. Godunov type schemes. Other techniques are less dissipative but fail to account for strong nonlinearity typical for initial stages of ablation, e.g. the ENO-Roe. To effectively model this highly nonlinear plume dynamics a combination of two of above mentioned schemes is developed so as the numerical evaluation of fluxes is close to their physical values and the scheme has minimum dissipation. The non-monotonic behavior of ablated mass as a function of time duration between two laser pulses is studied.     

Probe studies of laser erosion plume arising at silicon ablation in vacuum

An erosion plume arising at the ablation of silicon by a solid-state laser (λ = 1.06 μm) is studied with a Langmuir probe. The time-of-flight curves of the probe ion current are obtained for a plasma beam formed by intersecting plumes from two targets and for an erosion plume from one silicon target. The probe-target distance is varied in the range 40–157 mm. The time-of-flight curves for the ions of the erosion plume are sums of the velocity one-dimensional Maxwell distributions for four groups of ions. It is found that a plasma beam formed by intersecting plumes from two targets does not contain all groups of ions present in initial plumes.     

Optical transmission and reflection of aluminum film irradiated by nanosecond laser beam and experimental studying of phase-explosion

In this paper we present evidence for a phase explosion during the laser-induced ablation process by studying the optical reflectivity of the ablated plume. The ablation was produced by irradiating thin film aluminum coated on a quartz substrate with a single pulse laser beam in ambient air. The laser pulse was provided by the second harmonic of a Q-switched Nd:YAG laser with ∼10 ns pulse duration. The transmission of a low power He–Ne laser beam through the hot ablated material plume and its reflection (from the front surface, and rear surface of aluminum film) were also monitored during the duration of the ablation event. The results show that the front surface reflectivity is enhanced at an early time of ablation which is described as strong evidence for the creation of a phase explosion in this process.     

Double-pulse laser ablation applied to reactive PLD method for synthesis of carbon nitride film: A second laser shot delay

Carbon nitride films were deposited using ablation of graphite target by second harmonic radiation of Nd:YAG laser in nitrogen atmosphere. To produce high hardness films, the deposited particles should have sufficient kinetic energy to provide their efficient diffusion on a substrate surface for formation of crystal structure. However, a shock wave is arisen in ambient gas as a consequence of laser plasma explosive formation. This shock wave reflected from the substrate interacts with plume particles produced by the first laser pulse and decreases their kinetic energy. This results in decrease of film crystallinity. To improve film quality, two successive laser pulses was proposed to be used. At adjusting time delay, the particles induced by the second pulse wilt serve as a piston, which will push forward both stopped particles ablated by the first pulse and arisen from chemical reactions in ambient gas. An X-ray photoelectron spectroscopy (XPS) analysis of deposited films has shown an increase of content of sp ³ carbon atoms corresponding to crystalline phase, if double-pulse configuration is employed. The luminescence of excited C₂ and CN molecules in laser plume at different distances from the target was studied to optimize the delay between laser pulses.     

Analysis of plume deflection in the silicon laser ablation process

Changes in target surface morphology and ablation plume direction have been experimentally observed during the initial stages of the silicon laser ablation process. A relationship between both phenomena can be observed upon analysing the temperature field induced by the laser beam in a rough surface material. Theoretical studies on the deflection of the ablation plume are presented. These analyses are based on the hypothesis that particles that reach evaporation temperature will exit normally to the target surface with a velocity that is proportional to the surface temperature and the amount of the ablated material. Numerical solutions and experimental results of laser ablation process of silicon targets are found to agree with theoretical studies. PACS 42.25.Lc; 79.20.Dc; 02.70.Dc     

Modified crossed-beam PLD method for the control of ion energy spectrum

The modified crossed-beam pulsed laser deposition method, which allows wide-range variations in the energy of deposited particles, is presented for the first time. Time-of-flight curves (TFCs) of silicon ions that are formed by the crossed plumes from two silicon targets and the erosion plume from one silicon target are measured using the Langmuir probe technique. It is demonstrated that the TFCs of ions from the erosion plume are approximated by sums of the one-dimensional Maxwell velocity distributions. Variations in the ion concentrations that result from the interaction are measured. Transformations of the energy spectrum of the plasma beam formed by crossed plumes are determined using variations in the angle between the plumes.     

fs Laser surface nano-structuring of high refractory ceramics to enhance solar radiation absorbance

The surface and structural modification of titanium (Ti) has been explored after the interaction of ultrashort laser pulses with the surface target. The targets were exposed by femtosecond Ti: Sapphire laser pulses in liquid (ethanol) and dry (air) environment. In order to explore the effect of pulse energy, the targets were exposed to 1,000 succeeding pulses for various pulse energies ranging from 200 to 500 μJ for pulse duration of 25 fs. SEM analyses were performed for central as well as the peripheral ablated areas of the target. It was found that in the case of ethanol (both for central and peripheral ablated areas) there is a grain growth along with nanoscale pores and dots when the target was irradiated for 200 μJ. For intermediate energies (300–400 μJ), grains of 1–2 μm with distinct boundaries are formed in the central ablated area. Whereas in the peripheral ablated area, laser-induced periodic surface structures (LIPSS) and globules are grown. For the highest pulse energy (500 μJ), distinct grains are observed for both regions. However, in the peripheral area the grains are of bigger size with cracks along the boundaries. In case of ablation in air, in the center of ablated areas, island-like structures with multiple ablative layer or LIPSS and nanoscale spheres are observed both for lower and intermediate pulse energies. For the highest pulse energy only nanoscale LIPSS could be observed. For ablation in air at the peripheral areas, well-defined, laser-induced periodic surface structures are observed for all pulse energies. Raman spectroscopy reveals that the liquid (ethanol) environment forms the carbonyl compounds with the metal and induces C–C stretching vibration, whereas in case of air, hydroxo complexes are formed. It has been found that surface treatment of Ti with ultrashort (25 fs) laser radiation in ethanol environment allows the growth of particular surface structures in the form of grains and simultaneously induces changes in its chemical composition.     

Theoretical determination of the ablation rate of metals in multiple-nanosecond laser pulses irradiation regime

A detailed understanding of the physical determinants of the ablation rate in multiple nanosecond laser pulses regime is of key importance for technological applications such as patterning and pulsed-laser deposition. Here, theoretical modeling is employed to investigate the ablation of thick metallic plates by intense, multiple nanosecond laser pulses. A new photo-thermal model is proposed, in which the complex phenomena associated to the ablation process are accounted for as supplementary terms of the classical heat equation. The pulsed laser ablation in the nanosecond regime is considered as a competition between thermal vapourization and melt ejection under the action of the plasma recoil pressure. Computer simulations using the photo-thermal model presented here and the comparison of the theoretical results with experiment indicate two different mechanisms that contribute to the decrease of the ablation efficiency. First, during the ablation process the vapour/plasma plume expanding above the irradiated target attenuates the laser beam that reaches the sample, leading to a marked decrease of the ablation efficiency. Additional attenuation of the laser beam incident on the sample is produced due to the heating of the plasma by the absorption of the laser beam into the plasma plume. The second mechanism by which the ablation efficiency decreases consists of the reduction of the incident laser intensity with the lateral area, and of the melt ejection velocity with the depth of the hole.     

Dynamics and spectroscopy of the laser plume from solid targets

The dynamics and the spectral kinetic characteristics of the plume emerging in the vicinity of graphite targets, pressed pellets consisting of zirconium oxide powder stabilized with yttrium (YSZ) and yttrium-aluminum oxides with neodymium (YAO:Nd), and single-crystal YAG:Cr are studied. The targets are irradiated in air at room temperature using a repetitively pulsed CO₂ laser with a wavelength of 10.6 μm, a peak power of up to 9 kW, a pulse energy of 1.69 J, and a pulse duration of 330 μs at a level of 0.1. The plume propagates normally to the target surface at an angle of 45° relative to the laser radiation. The spectral kinetic characteristics of the plume luminescence are discretely measured along the entire length. It is demonstrated that the plumes of all targets (except for the single-crystal YAG:Cr) represent the flows of a weakly nonequilibrium gas plasma with a temperature of 10 kK (graphite) and 3.1–4.7 kK (YSZ and YAO:Nd pressed pellets). The plume size is determined by the peak power of the laser pulse. The luminescence of the two-atom radicals (C₂ in graphite; ZrO and YO in YSZ; and YO, AlO, and NdO in YAO:Nd) dominates in all of the plumes. A single radical (YO) and the spectral lines of atoms and atomic ions are observed in the YAG:Cr plume. A relatively high temperature of the graphite plume is maintained owing to the energy of the exothermic reaction involving the association of carbon atoms and the energy of the vibrationally excited molecules resulting from this reaction. Original Text ? Astro, Ltd., 2006.     

Background gas collisional effects on expanding fs and ns laser ablation plumes

The collisional effects of a background gas on expanding ultrafast and short pulse laser ablation plumes were investigated by varying background pressure from vacuum to atmospheric pressure levels. For producing Cu ablation plumes, either 40 fs, 800 nm pulses from a Ti: Sapphire laser or 6 ns, 1,064 nm pulses from a Nd:YAG laser were used. The role of background pressure on plume hydrodynamics, spectral emission features, absolute line intensities, signal to background ratios and ablation craters was studied. Though the signal intensities were found to be maximum near to atmospheric pressure levels, the optimum signal to background ratios are observed ~20–50 Torr for both ns and fs laser ablation plumes. The differences in laser–target and laser–plasma couplings between ns and fs lasers were found to be more engraved in the crater morphologies and plasma hydrodynamic expansion features.     

Material ablation and plasma plume expansion study from Fe and graphite targets in Ar gas atmosphere

Study of expansion dynamics of pulsed-laser ablation plasmas from Fe and graphite targets is presented. A 532 nm Q-switched Nd:YAG laser with fluence of 30 J cm⁻² is used to ablate the Fe and graphite targets in various Ar ambient gas pressures. Plasma ablation parameters for the two target materials are estimated using snow-plow and shock-wave models, which show that the laser beam energy deposited to ablated species remains at 70% for both targets at all ambient pressures. The plume splitting was observed, more prominently, for Fe plasma as it moves faster compared to graphite plasma. The difference in plasma plume fronts’ speeds for different targets was attributed to the significant difference in mass of the ablated plasma for two targets, as estimated from simulation results.     

Ultrafast two-color ablation of fused silica

Two ultrafast laser pulses at the fundamental Ti:sapphire laser wavelength of 800 nm and the second harmonic at 400 nm were used to study the temporal evolution of the transmissivity in fused silica and resulting material ablation. It was observed that there was a sharp drop in the transmissivity of the probe pulse at zero delay between the two pulses, indicating that there was enhanced absorption/reflection due to the creation of defect states or free electron plasma by the pump pulse. Subsequent atomic force microscopy measurements of the ablated holes revealed that the ablated volume increased by about 50% when the separations of the two pulses are within 300 fs. Two-color machining of channels at the surface also showed a similar increase in the machined depth and width when the pulses are overlapped in time. PACS 52.38.Mf; 78.47.+p; 79.20.Ds     

The influence of wavelength,temporal sequencing,and pulse duration on resonant infrared matrix-assisted laser processing of polymer films

We have carried out a systematic investigation of laser ablation plume interactions in resonant infrared matrix-assisted pulsed laser evaporation. The laser source utilized in this study was a mid-infrared OPO capable of dual sequential ns pulses with adjustable delay ranging from 1 to 100 μs. This unique capability enabled us both to probe the ablation plume with a second laser pulse, and to effectively double the laser fluence. The primary ablation target used for this study consisted of poly(methyl methacrylate) dissolved in a binary mixture of methanol and toluene. Both the critical thermodynamic and optical properties of the binary mixture were determined and used to interpret our results. We found that deposition rates associated with single pulse irradiation tracks with the optical absorption coefficient in the spectral range from 2,700 to 3,800 nm. In the case of dual sequential pulses, discrepancies in this trend have been linked to the rate of change in the optical absorption coefficient with temperature. The influence of fluence on deposition rate was found to follow a sigmoidal dependence. Surface roughness was observed to have a diametrically opposed trend with pulse delay depending on whether the OH or CH vibrational mode was excited. In the case of CH excitation, we suggest that the rougher films are due to the absorbance of the second pulse by droplets within the plume containing residual solvent which leads to the formation of molecular balloons and hence irregularly shaped features on the substrate.     

SIMS study of plumes generated from laser ablation of polymers

Plumes generated by ablation of polymer targets using a third-harmonic Nd:YAG laser under different atmospheres (air, N₂ and He) were deposited on a H-terminated silicon substrate. The chemical composition and distribution of deposited ablation debris were measured using time-of-flight secondary-ion mass spectrometry. Mass-resolved images show that the size and shape of the plume is dependent on the laser pulse energy and atmosphere in which the plume expanded. In air and nitrogen, plumes are hemispherical with distinct borders. In He they are mushroom-shaped without sharp borders. Since all experiments were carried out at atmospheric pressure, these differences can be related to the reactivity and molecular weight of the gas. Nitrogen-containing compounds (NCCs) and oxygen-containing compounds (OCCs) were found in plumes ablated in air but not in N₂ and He environments. We suggest that the formation of NCCs and OCCs is due to the interaction of the hot plume with air, initiating thermal dissociation of O₂ and oxygen-assisted dissociation of N₂. PACS 52.25.Kn     

Molecular imaging by Mid-IR laser ablation mass spectrometry

Mid-IR laser ablation at atmospheric pressure (AP) produces a mixture of ions, neutrals, clusters, and particles with a size distribution extending into the nanoparticle range. Using external electric fields the ions can be extracted and sampled by a mass spectrometer. In AP infrared (IR) matrix-assisted laser desorption ionization (MALDI) experiments, the plume was shown to contain an appreciable proportion of ionic components that reflected the composition of the ablated target and enabled mass spectrometric analysis. The detected ion intensities rapidly declined with increasing distance of sampling from the ablated surface to ∼4 mm. This was rationalized in terms of ion recombination and the stopping of the plume expansion by the background gas. In laser ablation electrospray ionization (LAESI) experiments, the ablation plume was intercepted by an electrospray. The neutral particles in the plume were ionized by the charged droplets in the spray and enabled the detection of large molecules (up to 66 kDa). Maximum ion production in LAESI was observed at large (∼15 mm) spray axis to ablated surface distance indicating a radically different ion formation mechanism compared to AP IR-MALDI. The feasibility of molecular imaging by both AP IR-MALDI and LAESI was demonstrated on targets with mock patterns. Presented at the 9-th International Conference on Laser Ablation, 2007 Tenerife, Canary Islands, Spain     

Generation and detection of superstrong shock waves during ablation of an aluminum surface by intense femtosecond laser pulses

Superstrong shock waves of multimegabar level generated during ablation of an aluminum surface by intense (<1 PW/cm²) femtosecond laser pulses have been detected by observing the propagation of a shock wave in air from the ablated surface to a broadband piezoelectric receiver. The estimated initial pressure and velocity of the shock wave (ablation plume) agree well with data obtained earlier by various methods for shock waves propagating inside ablated targets.     

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.     

Emission induced by collision of two plumes during pulsed laser ablation

We observed plume expansion dynamics during pulsed laser ablation when two plumes collided head-on. Si and Ge targets were placed parallel each other, and they were irradiated simultaneously by two pulsed lasers. A new emission appeared near the center of the targets from 250 ns after the irradiation. However, the predominant ejected species is neutral SiI or GeI at this time region when an individual single target is irradiated, and the new emission emerged by collision is a mixture of ionized SiII and GeII. This indicates that the kinetic energy of the collision excites the species to an ionized state. The intensity of this new emission decreased by increasing the background gas pressure. This suggests that collision between two plumes induces a higher-temperature plasma. Since the new emission is composed of ionized Si and Ge species and remains a relatively long period after the collision, this technique will provide a new reactive field to prepare a new kind of alloy nanomaterials.     

Nanoparticles size modifications during femtosecond laser ablation of nickel in vacuum

Nanoparticles were synthesized by irradiating a nickel target with femtosecond laser pulses in high vacuum, and subsequently analyzed. The proof-of-principle experiments aim to modify the size characteristics of the produced nanoparticles. For nickel it is found that: (i) ultraviolet laser pulses lead to a remarkable change in the nanoparticles size distribution with respect to visible laser pulses; (ii) irradiation of the femtosecond pulses induced ablation plume with a second, delayed ultraviolet laser pulse can change the size characteristics of the produced nanoparticles.     

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.