Ablation Plume Research Articles

Pulsed IR laser ablation of organic polymers in air: shielding effects and plasma pipe formation

We report the effect of ‘plasma pipe’ formation on pulsed laser ablation of organic polymers in air under normal conditions. Ablation of polymers (PMMA, polyimide) is carried out in a wide range of CO2 laser fluences with special attention to plasma formation in the ablation products. Evolution of laser ablation plumes in air under different pressures is investigated with simultaneous registration of radiation spectra of the ablation products. An analysis based on thermo-chemical modelling is performed to elucidate the effects of laser light attenuation upon ablation, including plasma and chemical processes in a near-target space. The analysis has shown that the experimental observations of plume development in air can be explained by a combination of processes including formation of a pre-ionized channel along the laser beam propagation, laser-supported detonation wave and effective combustion of the polymer ablation products. A scenario of a streamer-like polymer plasma flow within an air plasma pipe created via laser-induced breakdown is proposed.

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.

Probing electron-phonon coupling in metals via observations of ablation plumes produced by two delayed short laser pulses

We investigate electron-phonon coupling in metals by analyzing the composition of plumes produced by laser ablation with two delayed short laser pulses. Samples of Ti, Zr, and Hf are chosen since they have similar thermo-physical properties but significant different atomic masses. It is shown that the atomic emission intensity increases with the interpulse delay, whereas the nanoparticle emission intensity decreases. The characteristic time of plume changes is found to depend linearly on the metals’ atomic mass. Theoretical considerations suggest that the measured times equal to the characteristic times of electron-lattice relaxation.

Ag and Au nanoparticles for SERS substrates produced by pulsed laser ablation

AbstractA method for the growth of films consisting of Nanoparticles (NP) of Ag and Au is presented. Nanostructured films were obtained by means of nanosecond pulsed laser ablation of a metallic target in presence of a controlled Ar atmosphere. The morphology of these films from island structures to isolated nanoparticles, measured by SEM, depends on the varying gas pressure (10‐100 Pa) and on the number of laser pulses (500‐30000), keeping other deposition parameters such as the target to substrate distance, incidence angle, laser wavelength, laser fluence constant. Fast imaging of the plasma, performed using a intensified and gateable CCD camera at different time delays with respect to the arrival of the laser pulse, allows revelation of the propagation regime of the ablation plume and inference of plasma initial velocity. This data along with the measured average ablated mass per pulse were taken as inputs to a model to estimate the average size of NPs grown in the expanding plume. The theoretical NP sizes were compared with sizes measured from TEM images. These images indicate narrow gradients of NP sizes. Hence strict control of growth parameters aids fine tuning of NP size that is essential for many applications, including Surface Enhanced Raman Spectroscopy (SERS) active substrates. UV‐Visible Spectroscopy helped in determination of appropriate laser wavelength for resonant excitation of the localized surface plasmon. SERS Spectra obtained with increasingly lower concentrations of reference dye Rhodamin 6G (Rh6G) and medical drug Apomorphine, are discussed as a perspective of application to biomedical sensors. (© 2011 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

Investigation of plasmas produced by laser ablation using single and double pulses for food analysis demonstrated by probing potato skins

We report on investigations of plasmas produced by laser ablation of fresh potatoes using infrared nanosecond laser radiation. A twin laser system consisting of two Nd:YAG oscillators was used to generate single or double pulses of adjustable interpulse delay. The potatoes were irradiated under ambient air with moderate pulse energies of about 10 mJ. The expansion dynamics of the ablation plume was characterized using fast imaging with a gated camera. In addition, time-resolved optical emission spectroscopy was applied to study the spectral line emission of the various plasma species. The electron density was deduced from Stark broadening, and the plasma temperature was inferred from the relative emission intensities of spectral lines. The relative concentrations of metals were estimated from the comparison of the measured emission spectra to the spectral radiance computed for a plasma in local thermal equilibrium. It is shown that the plasma produced by double pulses has a larger volume and a lower density. These properties lead to an increase of the signal-to-noise ratio by a factor of 2 and thus to an improved measurement sensitivity.

Laser Ablation Molecular Isotopic Spectrometry

A new method of performing optical isotopic analysis of condensed samples in ambient air and at ambient pressure has been developed: Laser Ablation Molecular Isotopic Spectrometry (LAMIS). The technique uses radiative transitions from molecular species either directly vaporized from a sample or formed by associative mechanisms of atoms or ions in a laser ablation plume. This method is an advanced modification of a known atomic emission technique called laser-induced breakdown spectroscopy (LIBS). The new method — LAMIS — can determine not only chemical composition but also isotopic ratios of elements in the sample. Isotopic measurements are enabled by significantly larger isotopic shifts found in molecular spectra relative to atomic spectra. Analysis can be performed from a distance and in real time. No sample preparation or pre-treatment is required. Detection of the isotopes of hydrogen, boron, carbon, and oxygen are discussed to illustrate the technique.

ChemInform Abstract: Laser Ablation and Thin Film Deposition

AbstractReview: 99 refs.

飞秒激光在大气及真空中烧蚀硅靶的实验研究

Femtosecond (fs) pulse laser ablation of silicon targets in air and in vacuum is investigated using a time-resolved shadowgraphic method. The observed dynamic process of the fs laser ablation of silicon in air is significantly different from that in vacuum. Similar to the ablation of metallic targets, while the shock wave front and a series of nearly concentric and semicircular stripes, as well as the contact front, are clearly identifiable in the process of ablation under 1?105 Pa, these phenomena are no longer observed when the ablation takes place in vacuum. Although the ambient air around the target strongly affects the evolution of the ablation plume, the three rounds of material ejection clearly observed in the shadowgraphs of fs laser ablation in standard air can also be distinguished in the process of ablation in vacuum. It is proven that the three rounds of material ejection are caused by different ablation mechanisms.

Dynamics of ZnO laser produced plasma in high pressure argon

Pulsed laser deposition of ZnO in high pressure gas offers a route for the catalyst-free preparation of ZnO nanorods less than 10 nm in diameter. This paper describes the results of some experiments to investigate the laser plume dynamics in the high gas pressure (5 × 10 3–10 4 Pa) regime used for PLD of ZnO nanorods. In this regime the ablation plume is strongly coupled to the gas and the plume expansion is brought to a halt within about 1 cm from the target. A 248 nm excimer laser was used to ablate a ceramic ZnO target in various pressures of argon. Time- and space-resolved UV/vis emission spectroscopy and Langmuir probe measurements were used to diagnose the plasma and follow the plume dynamics. By measuring the spatial profiles of Zn I and Zn II spectral lines it was possible to follow the propagation of the external and internal shock waves associated with the interaction of the ablation plume with the gas. The Langmuir probe measurements showed that the electron density was 10 9–10 10 cm −3 and the electron temperature was several eV. At these conditions the ionization equilibrium is described by the collisional-radiative model. The plume dynamics was also studied for ZnO targets doped with elements which are lighter (Mg), comparable to (Ga), and heavier (Er) than Zn, to see if there is any elemental segregation in the plume.

Multidiagnostic analysis of ultrafast laser ablation of metals with pulse pair irradiation

Copper targets are irradiated in the ablation regime by pairs of equal, time-delayed collinear laser pulses separated on a timescale going from ≈2 ps to ≈2 ns. The ablation plume is characterized by ion probe diagnostic, fast imaging, and temporally and spatially resolved optical emission spectroscopy. The variation in the ablation efficiency with the delay between the pulses is analyzed by measuring the ablation crater profile with a contact profilometer. The second laser pulse modifies the characteristics of the plasma plume produced by the first pulse and the ablation efficiency. The different mechanisms involved in double pulse ultrafast laser ablation are identified and discussed. The experimental findings are interpreted in the frame of a simple model of the interaction of the second pulse with the nascent ablation plume produced by the first pulse. This model yields consistent and quantitative agreement with the experimental findings predicting the observed experimental trends of the ablation depth reduction and ion yield increase with the delay between the pulses, as well as the characteristic timescale of the observed changes. The possibility of controlling the characteristics of the plumes produced during ultrafast laser ablation via an efficient coupling of the energy of the second pulse to the various ablation components produced by the first pulse is of particular interest in ultrafast pulsed laser deposition and microprobe analyses of materials.

Analysis of deposited layers on plasma facing components by laser-induced breakdown spectroscopy: Towards ITER tritium inventory diagnostics

Because of the necessity of tritium inventory diagnostics in the framework of ITER, laser-induced breakdown spectroscopy (LIBS) is under development to analyse the deposited layers on plasma facing components. By means of a fast imaging technique, the time evolutions of the plume intensity and size are investigated. Time- and space-resolved optical emission spectroscopy is applied to characterize the expansion dynamics of ionized and neutral species within the ablation plume. A parametric study (laser fluence and pulse duration, gas pressure) is performed to determine the optimized operational conditions for LIBS analyses with samples from the Tore Supra reactor. To overcome the difficulties of quantitative LIBS measurements, an analysis procedure based on the calculation of the spectral radiance of the plasma in local thermodynamic equilibrium is applied.

Ablation particles parameters influences on VLS oxide nanowire growing

MgO nanowires were grown using vapor–liquid–solid technique by using the Pulsed Laser Ablation method in special shadow-mask system geometry. We compared the MgO nanowires morphology below and outside the shadow-mask areas obtained by using two different laser beams (193nm—ArF excimer, and 266 Nd:YAG fourth harmonic) for target ablation. If for the first laser beam, an MgO nanowire grows outside the mask's shadow area and the growing morphology below the mask tends to change to island growing, in the second case, the nanowire tends rather to form below the shadow-mask. Our results interpretation is based on the ablation plume particles' flux and size. In the first case, results are interpreted based on the ablated particle flux variation in the ablation plume interaction with a plane mask. In the second case, we base our interpretation on 'big' particles filtering by the ablation plume interaction with a plane mask.

Nonstoichiometric material transfer in the pulsed laser deposition of LaAlO3

Inequivalent angular distributions have been found for La and Al in the ablation plume from LaAlO3 single crystal targets using a KrF laser during pulsed laser deposition. Angular distributions and stoichiometries in the condensate were measured and reveal decidedly nonstoichiometric transfer from target to substrate over most of the angular range. Composition varied dramatically for plume angles parallel to the long axis of the laser spot with the on-axis position exhibiting a peak in the La/Al atom ratio at ∼1.5. The distributions were more diffuse in the perpendicular direction. Stoichiometric LaAlO3 was found in the condensate only at an extreme off-axis position.

Direct Analysis of Single Cells by Mass Spectrometry at Atmospheric Pressure

Analysis of biochemicals in single cells is important for understanding cell metabolism, cell cycle, adaptation, disease states, etc. Even the same cell types exhibit heterogeneous biochemical makeup depending on their physiological conditions and interactions with the environment. Conventional methods of mass spectrometry (MS) used for the analysis of biomolecules in single cells rely on extensive sample preparation. Removing the cells from their natural environment and extensive sample processing could lead to changes in the cellular composition. Ambient ionization methods enable the analysis of samples in their native environment and without extensive sample preparation.1 The techniques based on the mid infrared (mid-IR) laser ablation of biological materials at 2.94 μm wavelength utilize the sudden excitation of water that results in phase explosion.2 Ambient ionization techniques based on mid-IR laser radiation, such as laser ablation electrospray ionization (LAESI) and atmospheric pressure infrared matrix-assisted laser desorption ionization (AP IR-MALDI), have successfully demonstrated the ability to directly analyze water-rich tissues and biofluids at atmospheric pressure.3-11 In LAESI the mid-IR laser ablation plume that mostly consists of neutral particulate matter from the sample coalesces with highly charged electrospray droplets to produce ions. Recently, mid-IR ablation of single cells was performed by delivering the mid-IR radiation through an etched fiber. The plume generated from this ablation was postionized by an electrospray enabling the analysis of diverse metabolites in single cells by LAESI-MS.12 This article describes the detailed protocol for single cell analysis using LAESI-MS. The presented video demonstrates the analysis of a single epidermal cell from the skin of an Allium cepa bulb. The schematic of the system is shown in Figure 1. A representative example of single cell ablation and a LAESI mass spectrum from the cell are provided in Figure 2.

Direct Analysis of Single Cells by Mass Spectrometry at Atmospheric Pressure

Analysis of biochemicals in single cells is important for understanding cell metabolism, cell cycle, adaptation, disease states, etc. Even the same cell types exhibit heterogeneous biochemical makeup depending on their physiological conditions and interactions with the environment. Conventional methods of mass spectrometry (MS) used for the analysis of biomolecules in single cells rely on extensive sample preparation. Removing the cells from their natural environment and extensive sample processing could lead to changes in the cellular composition. Ambient ionization methods enable the analysis of samples in their native environment and without extensive sample preparation.1 The techniques based on the mid infrared (mid-IR) laser ablation of biological materials at 2.94 μm wavelength utilize the sudden excitation of water that results in phase explosion.2 Ambient ionization techniques based on mid-IR laser radiation, such as laser ablation electrospray ionization (LAESI) and atmospheric pressure infrared matrix-assisted laser desorption ionization (AP IR-MALDI), have successfully demonstrated the ability to directly analyze water-rich tissues and biofluids at atmospheric pressure.3-11 In LAESI the mid-IR laser ablation plume that mostly consists of neutral particulate matter from the sample coalesces with highly charged electrospray droplets to produce ions. Recently, mid-IR ablation of single cells was performed by delivering the mid-IR radiation through an etched fiber. The plume generated from this ablation was postionized by an electrospray enabling the analysis of diverse metabolites in single cells by LAESI-MS.12 This article describes the detailed protocol for single cell analysis using LAESI-MS. The presented video demonstrates the analysis of a single epidermal cell from the skin of an Allium cepa bulb. The schematic of the system is shown in Figure 1. A representative example of single cell ablation and a LAESI mass spectrum from the cell are provided in Figure 2.

Atmospheric-pressure Molecular Imaging of Biological Tissues and Biofilms by LAESI Mass Spectrometry

Ambient ionization methods in mass spectrometry allow analytical investigations to be performed directly on a tissue or biofilm under native-like experimental conditions. Laser ablation electrospray ionization (LAESI) is one such development and is particularly well-suited for the investigation of water-containing specimens. LAESI utilizes a mid-infrared laser beam (2.94 μm wavelength) to excite the water molecules of the sample. When the ablation fluence threshold is exceeded, the sample material is expelled in the form of particulate matter and these projectiles travel to tens of millimeters above the sample surface. In LAESI, this ablation plume is intercepted by highly charged droplets to capture a fraction of the ejected sample material and convert its chemical constituents into gas-phase ions. A mass spectrometer equipped with an atmospheric-pressure ion source interface is employed to analyze and record the composition of the released ions originating from the probed area (pixel) of the sample. A systematic interrogation over an array of pixels opens a way for molecular imaging in the microprobe analysis mode. A unique aspect of LAESI mass spectrometric imaging is depth profiling that, in combination with lateral imaging, enables three-dimensional (3D) molecular imaging. With current lateral and depth resolutions of ~100 μm and ~40 μm, respectively, LAESI mass spectrometric imaging helps to explore the molecular structure of biological tissues. Herein, we review the major elements of a LAESI system and provide guidelines for a successful imaging experiment.

Atmospheric-pressure Molecular Imaging of Biological Tissues and Biofilms by LAESI Mass Spectrometry

Ambient ionization methods in mass spectrometry allow analytical investigations to be performed directly on a tissue or biofilm under native-like experimental conditions. Laser ablation electrospray ionization (LAESI) is one such development and is particularly well-suited for the investigation of water-containing specimens. LAESI utilizes a mid-infrared laser beam (2.94 μm wavelength) to excite the water molecules of the sample. When the ablation fluence threshold is exceeded, the sample material is expelled in the form of particulate matter and these projectiles travel to tens of millimeters above the sample surface. In LAESI, this ablation plume is intercepted by highly charged droplets to capture a fraction of the ejected sample material and convert its chemical constituents into gas-phase ions. A mass spectrometer equipped with an atmospheric-pressure ion source interface is employed to analyze and record the composition of the released ions originating from the probed area (pixel) of the sample. A systematic interrogation over an array of pixels opens a way for molecular imaging in the microprobe analysis mode. A unique aspect of LAESI mass spectrometric imaging is depth profiling that, in combination with lateral imaging, enables three-dimensional (3D) molecular imaging. With current lateral and depth resolutions of ~100 μm and ~40 μm, respectively, LAESI mass spectrometric imaging helps to explore the molecular structure of biological tissues. Herein, we review the major elements of a LAESI system and provide guidelines for a successful imaging experiment.

Optimization of La0.7Ba0.3MnO3−δ complex oxide laser ablation conditions by plume imaging and optical emission spectroscopy

The properties of thin films of complex oxides, such as La1−xDxMnO3−δ (D=Ba, Ca, Sr, etc.), produced by pulsed laser deposition depend critically on the experimental parameters in which laser ablation is carried out. Here, we report a comparative analysis of the pulsed laser ablation process of La0.7Ba0.3MnO3−δ, in oxygen background, in the ambient pressure range from 10−2 to 1 mbar, typically employed in pulsed laser deposition of manganites. The laser ablation plume was studied by using time-gated imaging and optical emission spectroscopy techniques. It was found that at a pressure of ≈10−2 mbar, the plume species arriving at the substrate are characterized by hyperthermal kinetic energy (≈10 eV), and high degree of excitation. On the contrary, at larger oxygen pressure (0.1–1 mbar), the velocity of plume species reaching the substrate, and their degree of excitation are much reduced by the confining effects of the background gas. These features explain why an appropriate choice of the experimental conditions in which the deposition process is carried out leads to better quality films, providing helpful indications to improve control over the growth process of both La1−xDxMnO3−δ and other perovskitic oxides.

Laboratory experiments on cluster/aerosol formation by colliding ablation plumes

First-of-a-kind experiments on cluster/aerosol formation by colliding ablation plumes have been conducted, radiating Al, Cu and C with 3ω-YAG laser at power densities between 2∼30 J/cm2/pulse. Visible spectroscopy indicates that the excitation light intensities of Cu and Al plumes are not necessarily be doubled in collision, but can rather be weakened due to atomic and molecular reactions. For colliding C plumes, Swan band radiation has been observed, indicative of C2 and/or C2+ formation, and ion mass spectrometry has identified Cn+-clusters, including C+, C2+, C3+, C4+ and C5+. From ICCD camera observations, C plumes generated at power densities above ∼15 J/cm2/pulse tend to split into two components with respective velocities, only the slow component of which appears to be interactive to form clusters. Nano structures like CNT have been identified in deposits from colliding C plumes.

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.