Xianglei Mao

Laser ablation in analytical chemistry - A review

Laser ablation is becoming a dominant technology for direct solid sampling in analytical chemistry. Laser ablation refers to the process in which an intense burst of energy delivered by a short laser pulse is used to sample (remove a portion of) a material. The advantages of laser ablation chemical analysis include direct characterization of solids, no chemical procedures for dissolution, reduced risk of contamination or sample loss, analysis of very small samples not separable for solution analysis, and determination of spatial distributions of elemental composition. This review describes recent research to understand and utilize laser ablation for direct solid sampling, with emphasis on sample introduction to an inductively coupled plasma (ICP). Current research related to contemporary experimental systems, calibration and optimization, and fractionation is discussed, with a summary of applications in several areas.

Evidence for phase-explosion and generation of large particles during high power nanosecond laser ablation of silicon

The craters resulting from high-irradiance (1×109–1×1011 W/cm2) single-pulse laser ablation of single-crystal silicon show a dramatic increase in volume at a threshold irradiance of 2.2×1010 W/CM2. Time-resolved shadowgraph images show ejection of large particulates from the sample above this threshold irradiance, with a time delay ∼300 ns. A numerical model was used to estimate the thickness of a superheated layer near the critical state. Considering the transformation of liquid metal into liquid dielectric near the critical state (i.e., induced transparency), the calculated thickness of the superheated layer at a delay time of 200–300 ns agreed with the measured crater depths. This agreement suggests that induced transparency promotes the formation of a deep superheated layer, and explosive boiling within this layer leads to particulate ejection from the sample.

Femtosecond laser ablation ICP-MS

Femtosecond laser ablation was investigated for direct solid sample chemical analysis. The phonon relaxation time in a solid is of the order of 100 fs, which is the same as the laser pulse duration. For such excitation, there should be little time for the matrix to experience a “temperature” during the laser pulse. If the surface explodes before the photon energy is dissipated as heat in the lattice, the ablation process should produce stoichiometric vapor (elemental fractionation should be negligible). Based on this hypothesis, NIST glasses were ablated using 100 fs laser pulses at 800 nm, with subsequent elemental analysis using the ICP-MS. Pb and U intensities, and Pb/U ratios in the ICP, were measured during repetitively femtosecond-pulsed ablation. These data show that fluence (laser energy/spot area) has a significant influence on the amount of mass ablated and on the degree of fractionation. An optimal fluence was found at which the fractionation index approached unity; negligible fractionation. Infrared femtosecond laser ablation produced similar characteristics to UV nanosecond laser ablation.

Early phase laser induced plasma diagnostics and mass removal during single-pulse laser ablation of silicon

The electron number density and temperature during the early phase (<300 ns) of laser-induced plasmas from silicon using a 266-nm, 3-ns Nd:YAG laser were deduced via spectroscopic methods. These parameters were measured as a function of delay time vs. irradiance in the range of 2–80 GW/cm2, and compared with crater volume measurements. A dramatic change in plasma characteristics (electron number density, temperature, and degree of ionization) as well as a sharp increase of mass removal was observed when the irradiance was increased beyond a threshold of 20 GW/cm2. Possible mechanisms such as inverse bremsstrahlung and self-regulation were used to describe these data in the low irradiance region. Laser self-focusing and critical temperature are discussed to explain the dramatic changes after the irradiance reaches the threshold.

Laser Ablation in Analytical Chemistry

In 2002, we wrote an Analytical Chemistry feature article describing the Physics of Laser Ablation in Microchemical Analysis. In line with the theme of the 2002 article, this manuscript discusses current issues in fundamental research, applications based on detecting photons at the ablation site (LIBS and LAMIS) and by collecting particles for excitation in a secondary source (ICP), and directions for the technology.

Delayed phase explosion during high-power nanosecond laser ablation of silicon

An important parameter for high-irradiance laser ablation is the ablation crater depth, resulting from the interaction of individual laser pulses on a targeted surface. The crater depth for laser ablation of single-crystal silicon shows a dramatic increase at a laser intensity threshold of approximately 2×1010 W/cm2, above which, large (micron-sized) particulates were observed to eject from the target. We present an analysis of this threshold phenomenon and demonstrate that thermal diffusion and subsequent explosive boiling after the completion of the laser pulse is a possible mechanism for the observed dramatic increase of the ablation depth. Calculations based on this delayed phase explosion model provide a satisfactory estimate of the measurements. In addition, we find that the shielding of an expanding mass plasma during laser irradiation has a profound effect on this threshold phenomenon.

Initiation of an early-stage plasma during picosecond laser ablation of solids

Picosecond time-resolved images of plasma initiation were recorded during pulsed-laser ablation of metal targets in an air atmosphere. An early-stage plasma was observed to form before the release of a material vapor plume. Close to the target surface, interferometry measurements indicate that the early-stage plasma has an electron number density on the order of 1020 cm−3. The longitudinal expansion of the ionization front for this plasma has a velocity 109 cm/s, during the laser pulse. In contrast, a material–vapor plume forms approximately 200 ps after the laser pulse, and it moves away from the target at 106 cm/s. The experimental observations of the early-stage plasma were simulated by using a theoretical model based on a two-fluids description of laser plasmas. The results indicate that the initiation of the plasma is due to air breakdown assisted by electron emission from the target.

Laser assisted plasma spectrochemistry: laser ablation

This paper presents a brief overview of the current research issues in laser ablation for chemical analysis, discusses several fundamental studies of laser ablation using time-resolved shadowgraph and spectroscopic imaging, and describes recent data using femtosecond ablation sampling for ICP-MS and LIBS. This manuscript represents a summary of the plenary lecture presented at the 2004 Winter Conference on Plasma Spectrochemistry.

Laser ablation sampling

Abstract Laser ablation sampling provides significant benefits and capabilities for chemical analysis. It represents one of the most promising technologies for direct solid sample introduction. Despite the advantages, there are a number of issues that should be addressed to better understand and utilize this technology. Laser ablation itself is a complex process and is poorly understood, fundamentally. In this paper, we describe the current achievements and limitations in order to better understand and utilize laser ablation sampling for chemical analysis. Several current issues related to laser ablation sampling are discussed, including calibration and optimization, fractionation, sensitivity enhancements, mass loading, and particle transport.

Effects of crater development on fractionation and signal intensity during laser ablation inductively coupled plasma mass spectrometry

Abstract The effects of crater development on ICP-MS signal intensities and elemental fractionation have been presented in this work. Craters formed after repetitive 266-nm Nd/YAG laser ablation with 1.0-mJ pulses had a cone-like shape. The laser ablation rate (ng/s) depended on the laser irradiance (laser pulse energy per unit time and unit area), decreasing as irradiance increased. In contrast, the particle entrainment/transport efficiency did not significantly change with irradiance. As the crater-aspect ratio (depth/diameter) increased above some threshold value of six, the Pb/U elemental ratio departed from the stoichiometric value. However, good stoichiometry of ablated mass could be achieved when experimental conditions were carefully selected. The exact mechanism of how crater development affects fractionation is not well understood. In this work, actual irradiance was introduced instead of a nominal value. Actual irradiance decreased as the crater deepened due to changes of the effective area, sampled by the laser beam.