Dynamics of femtosecond-laser-ablated liquid-aluminum nanoparticles probed by means of spatiotemporally resolved X-ray absorption spectroscopy

We investigated spatiotemporal evolution of expanding ablation plume of aluminum created by a 100-fs, 10¹⁴–10¹⁵-W/cm² laser pulse. For diagnosing dynamic behavior of ablation plume, we employed the spatiotemporally resolved X-ray absorption spectroscopy (XAS) system that consists of a femtosecond-laser-plasma soft X-ray source and a Kirkpatrick–Baez (K–B) microscope. We successfully assigned the ejected particles by analyzing structure of absorption spectra near the L _II,III absorption edge of Al, and we clarified the spatial distribution of Al⁺ ions, Al atoms, and liquid droplets of Al in the plume. We found that the ejected particles strongly depend the irradiated laser intensity. The spatial distribution of atomic density and the expansion velocity of each type of particle were estimated from the spatiotemporal evolution of ablation particles. We also investigated a temperature of the aluminum fine particles in liquid phase during the plume expansion by analyzing the slope of the L _II,III absorption edge in case of 10¹⁴-W/cm² laser irradiation where the nanoparticles are most efficiently produced. The result suggests that the ejected particles travel in a vacuum as a liquid phase with a temperature of about 2500 to 4200 K in the early stage of plume expansion.     

Characterization of excimer laser ablation generated pepsin particles using multi-wavelength photoacoustic instrument

Preparation of organic thin layers on various special substrates using the pulsed laser deposition (PLD) technique is an important task from the point of view of bioengineering and biosensor technologies. Earlier studies demonstrated that particle ejection starts during the ablating laser pulse resulting in significant shielding effects which can influence the real fluence on the target surface and consequently the efficiency of layer preparation. In this study, we introduce a photoacoustic absorption measurement technique for in-situ characterization of ablated particles during PLD experiments. A KrF excimer laser beam (λ=248 nm, FWHM=18 ns) was focused onto pepsin targets in a PLD chamber; the applied laser fluences were 440 and 660 mJ/cm². We determined the wavelength dependence of optical absorption and mass specific absorption coefficient of laser ablation generated pepsin aerosols in the UV–VIS–NIR range. On the basis of our measurements, we calculated the absorbance at the ablating laser wavelength, too. We demonstrated that when the laser ablation generated pepsin aerosols spread through the whole PLD chamber the effect of absorptivity is negligible for the subsequent pulses. However, the interaction of the laser pulse and the just formed particle cloud generated by the same pulse is more significant.     

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.     

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     

Model for laser-induced thermal degradation and ablation of polymers

Ablation of organic polymers is described on the basis of photothermal bond breaking within the bulk material. Here, we assume a first-order chemical reaction, which can be described by an Arrhenius law. Ablation starts when the density of broken bonds at the surface reaches a certain critical value. In order to understand the ablation behavior near the threshold fluence, φ_th, non-stationary regimes must be considered. The present treatment reveals several qualitative differences with respect to models that treat ablation as a surface process: (i) Ablation starts sharply with a front velocity that has its maximum value just after the onset. (ii) The transition to the quasi-stationary ablation regime is faster. (iii) Near threshold, the ablated depth h has a square-root dependence on laser fluence, i.e., h∝(φ-φ_th)^1/2. The ablation velocity is very high even near φ_th. (iv) With φ≈φ_th ablation starts well after the laser pulse. (v) The depletion of species is responsible for the Arrhenius tail observed with fluences φ≤φ_th. (vi) Residual modification of material has maximum near the threshold. (vii) Stationary regimes of ablation demonstrate change of effective activation energy with laser intensity. The model calculations are applied to Polyimide (Kapton^TM H). Here, differences in single-pulse ablated depth determined from mass loss and profilometry should be about 10 nm. Received: 16 February 1999 / Accepted: 18 February 1999 / Published online: 28 April 1999     

Dynamics of radiation scattering by particles of condensed phase in quasicontinuous laser irradiation of metals

Radiation scattering by particles of condensed phase in an ablation plasma plume has been experimentally studied during quasicontinuous laser irradiation (λ = 1.06 μm, q = 0.1–9 MW/cm², τ ∼ 1.5 msec) of duraluminum D16T, aluminum A99, and bismuth. The particle size distribution and the nature of their dispersal during irradiation was studied in scattered light (λ = 0.69 μm) from individual particles that could be visually observed on photographs. It was found that under the pressure developed in the plume, large particles ejected from the irradiated zone can move backward and return to the target (D16T). The plume (Bi) becomes brighter due to ablation of particles in the path of the laser beam. The directional scattering coefficients for scattering from the local zone on the axis of the plume, measured during the laser pulse, were used to study the relationship between the dynamics of entry of condensed phase into the plume, shielding of the target by the particles, and brightening of the plume under the action of the incident laser radiation. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 210–219, March–April, 2006.     

Mass and kinetic energy distribution of the species generated by laser ablation of La<Subscript>0.6</Subscript>Ca<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript>

The mass distributions of the species generated by laser ablation from a La_0.6Ca_0.4MnO₃ target using laser irradiation wavelengths of 193 nm, 266 nm and 308 nm have been investigated with and without a synchronized gas pulse of N₂O. The kinetic energies of the species are measured using an electrostatic deflection energy analyzer, while the mass distributions of the species were analyzed with a quadrupole mass filter. In vacuum (pressure 10⁻⁷ mbar), the ablation plume consists of metal atoms and ions such as La, Ca, Mn, O, LaO, as well as multiatomic species, e.g. LaMnO⁺. The LaO⁺ diatomic species are by far the most intense diatomic species in the plume, while CaO and MnO are only detected in small amounts. The interaction of a reactive N₂O gas pulse with the ablation plume leads to an increase in plume reactivity, which is desired when thin manganite films are grown, in order to incorporate the necessary amount of oxygen into the film. The N₂O gas pulse appears to have a significant influence on the oxidation of the Mn species in the plume, and on the creation of negative ions, such as LaO⁻,O⁻ and O₂⁻.     

Ablation with a single micropatterned KrF laser pulse: quantitative evidence of transient liquid microflow driven by the plume pressure gradient at the surface of polyesters

A microscopic flow of a transient liquid film produced by KrF laser ablation is evidenced on targets of PET and PEN. Experiments were done by using single pulses of the excimer laser beam micropatterned with the aid of submicron projection optics and grating masks. The samples of various crystalline states, ablated with a grating-forming beam (period Λ=3.7 μm), were precisely measured by atomic force microscopy, in order to evidence any deviation from the ablation behavior predicted by the current theory (combination of ablation curve and beam profile). This was confirmed by comparing various behaviors dependent on the polymer nature (PC, PET and PEN). PC is a normally ablating polymer in the sense that the ablated profile can be predicted with previous theory neglecting liquid-flow effects. This case is called ‘dry’ ablation and PC is used as a reference material. But, for some particular samples like crystalline PET, it is revealed that during ablation a film of transient liquid, composed of various components, which are discussed, can flow under the transient action of the gradient of the pressure of the ablation plume and resolidify at the border of the spot after the end of the pulse. This mechanism is further supported by a hydrodynamics theoretical model in which a laser-induced viscosity drop and the gradient of the plume pressure play an important role. The volume of displaced liquid increases with fluence (0.5 to 2 J/cm²) and satisfactory quantitative agreement is obtained with the present model. The same experiment done on the same PET polymer but prepared in the amorphous state does not show microflow, and such an amorphous sample behaves like the reference PC (‘dry’ ablation). The reasons for this surprising result are discussed. Received: 31 October 2002 / Accepted: 4 November 2002 / Published online: 22 January 2003 RID="*" ID="*"Present address: ST Microelectronics, Crolles, France RID="**" ID="**"Corresponding author. Fax: +33-556/84-6645, E-mail: s.lazare@lpcm.u-bordeaux1.fr     

UV laser irradiation of IR laser generated particles ablated from nitrobenzyl alcohol

Particles generated by 2.94 μm pulsed IR laser ablation of liquid 3-nitrobenzyl alcohol were irradiated with a 351 nm UV laser 3.5 mm above and parallel to the sample target. The size and concentration of the ablated particles were measured with a light scattering particle sizer. The application of the UV laser resulted in a reduction in the average particle size by one-half and an increase in the total particle concentration by a factor of nine. The optimum delay between the IR and UV lasers was between 16 and 26 μs and was dependent on the fluence of the IR laser: higher fluence led to a more rapid appearance of particulate. The ejection velocity of the particle plume, as determined by the delay time corresponding to the maximum two-laser particle concentration signal, was 130 m/s at 1600 J/m² IR laser fluence and increased to 220 m/s at 2700 J/m². The emission of particles extended for several ms. The observations are consistent with a rapid phase change and emission of particulate, followed by an extended emission of particles ablated from the target surface.     

Noble metal nanoparticles produced by nanosecond laser ablation

Silver and gold thin films were deposited by pulsed laser ablation in a controlled Ar atmosphere at pressures between 10 and 100 Pa. Different morphologies, ranging from isolated nanoparticle arrays up to nanostructured thin films were observed. Fast imaging of the plasma allowed deducing the expansion dynamics of the ablated plume. Plasma velocity and volume were used together with the measured average ablated mass per pulse as input parameters in a model to estimate the average size of nanoparticles grown in the plume. The nanoparticle size is expected to decrease from 4 nm down to 1 nm with decreasing Ar pressure between 100 and 10 Pa: this was confirmed by transmission electron micrographs which indicate a reduced dispersion of particle size over narrow size ranges. The production of substrates for surface enhanced Raman scattering whose performances critically depend on nanoparticle size, shape, and structure is discussed.     

Laser impulse coupling at 130 fs

We measured the momentum coupling coefficient C_m and laser-generated ion drift velocity and temperature in the femtosecond (fs) region, over a laser intensity range from ablation threshold to about one hundred times threshold. Targets were several pure metals and three organic compounds. The organic compounds were exothermic polymers specifically developed for the micro-laser plasma thruster, and two of these used “tuned absorbers” rather than carbon particles for laser absorption. The metals ranged from Li to W in atomic weight. We measured time of flight (TOF) profiles for ions. Specific impulse reached record values for this type of measurement and ablation efficiency was near 100%. These measurements extend the laser pulsewidth three orders of magnitude downward in pulsewidth relative to previous reports. Over this range, we found C_m to be essentially constant. Ion velocity ranged from 60 to 180 km/s.     

Spectroscopy of laser-produced cerium plasma for remote isotope analysis of nuclear fuel

A cerium oxide sample was ablated by 2nd harmonic radiation of Nd:YAG laser at a power density of 0.1 GW/cm². Time evolution of the ablation plume was investigated by laser absorption time-of-flight (TOF) measurement. It was found that the ablated ionic plume in vacuum consisted of two components having different velocities whereas the ablated neutral atoms had mainly a single component. The flow velocity perpendicular to the sample surface in vacuum was determined to be 3.5 km/s for neutral atoms, and 4.7 km/s and 9.3 km/s for singly charged ions. From the detailed plume evolution in ambient atmosphere with several pressures we obtained some experimental conditions suitable for isotope analysis of atomic cerium.     

Effect of oxygen injection on the size and compositional evolution of ZnO/Zn(OH)<Subscript>2</Subscript> nanocomposite synthesized by pulsed laser ablation in distilled water

Zinc oxide/hydroxide nanocomposite materials are synthesized by pulsed laser ablation of zinc in double distilled water. Effect of simultaneous flow of oxygen in the closed vicinity of laser ablated plasma plume on the size, morphology, crystallinity, and composition of synthesized oxide/hydroxide nanocomposite structures is investigated. As synthesized nanocomposite materials are characterized using UV–visible absorption, Scanning electron microscopy (SEM), thermo gravimetric analysis (TGA), Differential thermal analysis (DTA), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and photoluminescence spectroscopic methods. It is observed that injection of oxygen induces a new mechanism in the particle synthesis, which causes decrease in particle size, distribution as well as Zn(OH)₂/ZnO ratio and increase of order of crystallinity of product. There are some novel findings in the direction of development of pulsed laser ablation in aqueous media (PLAAM) for the synthesis of nanostructured materials.     

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.     

Laser ablation and desorption from calcite from ultraviolet to mid-infrared wavelengths

3 ) at wavelengths ranging from the ultraviolet to the mid-infrared, including a Nd:YAG laser operated at the fundamental, second and third harmonics, and a tunable infrared free-electron laser (wavelength range 2.5–8 μm). The threshold for ablation and the topography of the irradiated spot were characterized by scanning electron microscopy. A clear indication of two distinct excitation mechanisms was observed, namely, cracks and fractures followed by exfoliation at ultraviolet to near-infrared wavelengths, in contrast to evaporative holes and scattered droplets in the mid-infrared. Plume emission/absorption spectroscopy, plume transmission and photoacoustic beam deflection were used to characterize the ablation plasma. The composition of atoms, molecules, or particles in the ablation plumes also has a distinctive variation as a function of the wavelength. The excitation mechanisms leading to ablation appear to be defect activation at ultraviolet to near-infrared wavelengths, molecular impurity absorption and resonant vibrational absorption of the calcite at mid-infrared. Received: 5 December 1996/Accepted: 6 January 1997     

Phase explosion and recoil-induced ejection in resonant-infrared laser ablation of polystyrene

We investigate the phenomenon of resonant-infrared laser ablation of polymers using polystyrene as a model material. Ablation is carried out using various mid-IR laser wavelengths that are resonant with vibrational modes of a polystyrene target. Time-resolved plume imaging coupled with etch-depth measurements and thermal calculations indicate that ablation begins after a superheated surface layer reaches a temperature of ∼1000°C and undergoes spinodal decomposition. The majority of the ablated material is then expelled by way of recoil-induced ejection as the pressure of the expanding vapor plume compresses a laser-melted area.     

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.     

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.     

Modeling of vapor-droplet plumes ablated from multiple spots

The study aims at modeling of plume shielding aspects of laser ablation processes with multiple laser pulses applied to multiple targets. The main obstacle with the efficient use of multiple laser pulse technologies is an attenuation of the laser irradiation by previously ablated plumes. Dynamics of plumes is described by the axisymmetric Euler equations describing a vapor-droplet ablated mixture rolling-up in the surrounding ideal gas. For multiple laser pulses, the role of absorption of laser beam by previously ablated plumes is evaluated varying a model parameter that defines the fraction of laser energy absorbed by the ablated mixture. Absorption of laser beam by plume may cause its secondary explosion that cleans the target surface and, subsequently, increases the mass ablated by the consequent pulse. Dynamics of plumes ablated from two targets with possible time delay between two laser hits is investigated as a representative case of multiple targets. Shielding of the surface between targets appears to be significant if the second pulse occurs before the first shock wave passes the second target.