Real-time control of ultrafast laser micromachining by laser-induced breakdown spectroscopy

Ultrafast laser micromachining provides many advantages for precision micromachining. One challenging problem, however, particularly for multilayer and heterogeneous materials, is how to prevent a given material from being ablated, as ultrafast laser micromachining is generally material insensitive. We present a real-time feedback control system for an ultrafast laser micromachining system based on laser-induced breakdown spectroscopy (LIBS). The characteristics of ultrafast LIBS are reviewed and discussed so as to demonstrate the feasibility of the technique. Comparison methods to identify the material emission patterns are developed, and several of the resulting algorithms were implemented into a real-time computer control system. LIBS-controlled micromachining is demonstrated for the fabrication of microheater structures on thermal sprayed materials. Compared with a strictly passive machining process without any such feedback control, the LIBS-based system provides several advantages including less damage to the substrate layer, reduced machining time, and more-uniform machining features.     

Glass-batch composition monitoring by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy is an almost ideal technique for the in situ monitoring of the composition of a glass batch before it enters the glass-melting furnace, saving a significant amount of energy by the optimization of the furnace parameters for a particular composition of the glass batch. We investigate this application of laser-induced breakdown spectroscopy by determining the elemental composition of the glass batch used (i) as a surrogate for radioactive glass waste and (ii) to manufacture the most common type of flat glass. The surrogate glass-batch and flat-glass calibration curves for the major constituents have been prepared using both the line intensity and the line-intensity ratio. The analytical figure of merit of the glass-batch data obtained from the two different detection systems, namely, the Czerny-Turner spectrometer with an intensified diode-array detector and the echelle spectrometer fitted with an intensified CCD camera, are compared.     

Detection of bacteria by time-resolved laser-induced breakdown spectroscopy

A laser-induced breakdown spectroscopy technique for analyzing biological matter for the detection of biological hazards is investigated. Eight species were considered in our experiment: six bacteria and two pollens in pellet form. The experimental setup is described, then a cumulative intensity ratio is proposed as a quantitative criterion because of its linearity and reproducibility. Time-resolved laser-induced breakdown spectroscopy (TRELIBS) exhibits a good ability to differentiate among all these species, whatever the culture medium, the species or the strain. Thus we expect that TRELIBS will be a good candidate for a sensor of hazards either on surfaces or in ambient air.     

Dual-pulse laser-induced breakdown spectroscopy with combinations of femtosecond and nanosecond laser pulses

Nanosecond and femtosecond laser pulses were combined in an orthogonal preablation spark dual-pulse laser-induced breakdown spectroscopy (LIBS) configuration. Even without full optimization of interpulse alignment, ablation focus, large signal, signal-to-noise ratio, and signal-to-background ratio enhancements were observed for both copper and aluminum targets. Despite the preliminary nature of this study, these results have significant implications in the attempt to explain the sources of dual-pulse LIBS enhancements.     

Determination of an iron suspension in water by laser-induced breakdown spectroscopy with two sequential laser pulses

We have applied laser-induced breakdown spectroscopy to quantitative analysis of colloidal and particulate iron in water. A coaxial sample flow apparatus developed in our previous work, which allowed us to control the atmosphere of laser-induced plasma, was used. Using sequential laser pulses from two Q-switched Nd:YAG lasers as excitation sources, the FeO(OH) concentration in the tens of ppb range was determined with an optimum interval between two laser pulses and an optimum delay time of a detector gate from the second pulse. The detection limit of Fe decreased substantially using two sequential laser pulse excitations: the 0.6 ppm limit of single pulse excitation to 16 ppb with sequential pulse excitation. The effects of the second laser pulse on the plasma emission were studied. The concentration of iron in fine particles in boiler water sampled from a commercially operated thermal power plant has been determined successfully by this method. The results show the capability of laser-induced breakdown spectroscopy in determining suspended colloidal and particulate impurities in a simple and quick way.     

Determination of carbon in steel by laser-induced breakdown spectroscopy using a microchip laser and miniature spectrometer

Laser-induced breakdown spectroscopy using a microchip laser and a miniature spectrometer has been applied to the determination of carbon in steel. The goal was to investigate the capability of an apparatus, made up of commercial components, that could form the basis of a handheld device. The typical precision obtained in the range of C/Fe weight ratios of 0.001 to 0.01 was 4.3%, and the limit of detection was a C/Fe ratio of 400 ppm. This is higher than values reported for conventional systems and is primarily determined by systematic variations in the spectra and not by signal intensity levels. These systematic variations are ascribed to two causes: the use of an ungated detector and the spatial variability of the emission plume.     

Plasma-particle interactions in a laser-induced plasma: implications for laser-induced breakdown spectroscopy

The interaction between laser-induced plasmas and individual particles controls the rate of particle dissociation and subsequent atomic diffusion and emission processes, with implications for single-particle spectroscopy, as well as materials synthesis and other plasma sources. It is demonstrated through quantitative plasma imaging studies that discrete particles dissociate on a time scale of tens of microseconds within plasmas formed by 300-mJ Nd:YAG laser pulses. Significant spatial nonhomogeneity, as measured by localized atomic emission from particle-derived calcium atoms, persists on a comparable time scale, providing a measure of their average atomic diffusion rate of 0.04 m(2)/s. In addition, the resulting calcium atomic emission is explored using image analysis as well as traditional spectroscopic analysis.     

Topographical and chemical microanalysis of surfaces with a scanning probe microscope and laser-induced breakdown spectroscopy

Spatially resolved chemical imaging is achieved by combining a fiber-optic scanning probe microscope with laser-induced breakdown spectroscopy in a single instrument, TOPOLIBS. Elemental composition of surfaces can be mapped and correlated with topographical data. The experiment is conducted in air with minimal sample preparation. In a typical experiment, surface topography is analyzed by scanning a sharp fiber-optic probe across the sample using shear force feedback. The probe is then positioned over a feature of interest and pulsed radiation is delivered to the surface using a nitrogen laser. The pulse vaporizes material from the surface and generates a localized plasma plume. Optical emission from the plume is analyzed with a compact UV/visible spectrometer. Ablation crater size is controlled by the amount of laser power coupled into the probe. Sampling areas with submicrometer dimensions are achieved by using reduced laser power.     

Practical high-resolution detection method for laser-induced breakdown spectroscopy

A Fabry-Perot etalon was coupled to a Czerny-Turner spectrometer to acquire high-resolution measurements in laser-induced breakdown spectroscopy (LIBS). The spectrometer was built using an inexpensive etalon coupled to a standard 0.5 m imaging spectrometer. The Hg emission doublet at 313.2 nm was used to evaluate instrument performance because it has a splitting of 29 pm. The 313.2 nm doublet was chosen due to the similar splitting seen in isotope splitting from uranium at 424.437 nm, which is 25 pm. The Hg doublet was easily resolved from a continuous-source Hg lamp with a 2 s acquisition. The doublet was also resolved in LIBS spectra of cinnabar (HgS) from the accumulation of 600 laser shots at rate of 10 Hz, or 1 min, under a helium atmosphere. In addition to the observed splitting of the 313.2 nm Hg doublet, the FWHM of the 313.1844 nm line from the doublet is reported at varying helium atmospheric pressures. The high performance, low cost, and compact footprint make this system highly competitive with 2 m double-pass Czerny-Turner spectrometers.     

Fiber-optic spark delivery for gas-phase laser-induced breakdown spectroscopy

This article reports what are to the authors' knowledge the first gas-phase laser-induced breakdown spectroscopy (LIBS) measurements using a fiber-optically delivered spark. A silver- and polymer-coated hollow fiber delivered high-energy nanosecond 1064 nm Nd:YAG laser pulses, which were focused to generate high-energy-density plasmas in ultra-lean methane-air mixtures. Emissions from these plasmas were collected and spectroscopically analyzed to quantify relative fuel-to-air ratio. These measurements were compared with others made using traditional LIBS techniques without the fiber-optically delivered spark. Similar results were obtained, but with larger shot-to-shot variability, for the case of the fiber-optically delivered spark.     

Absolute analysis of particulate materials by laser-induced breakdown spectroscopy

We have developed a new data acquisition approach followed by a suitable data analysis for Laser-induced breakdown spectroscopy. It provides absolute concentrations of elements in particulate materials (e.g., industrial dusts and soils). In contrast to the known calibration procedures (based on the ratio of spectral lines), which are applicable only when one component is constant, this approach requires no constant constituent and results in absolute (rather than relative) concentrations. Thus, the major drawback of this analytical method, namely, the signals' instability (especially when particulate materials are concerned) is partially solved. Unlike the commonly used integrated data acquisition, we use a sequence of signals from single breakdown events. We compensate for pulse to pulse fluctuations in an intrinsic way, and the final results do not depend on the presence of any constant component. Extended linear calibration curves are obtained, and limits of detection are improved by 1 order of magnitude relative to previous methods applied to the same samples (e.g., detection limit of 10(-12) g of Zn in aerosol samples). The proposed compensation for pulse variations is based on the assumption that they can be described as a multiplicative effect for both the spectral peaks and a component of the baseline. In other words, we assume that the same fluctuation pattern observed in the spectral peaks is present in the baseline as well. This assumption is shown to hold and is utilized in the proposed method. In addition, a proper data-filtering process, which eliminates ill-conditioned spectra, is shown to partially compensate for problems due to the nature of analysis of particulate materials.     

Helium detection in gas mixtures by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been evaluated as a tool for monitoring trace levels of helium in gas mixtures consisting mostly of hydrogen. Calibration data for helium in hydrogen was investigated at different helium concentration levels. At high concentrations of helium (>7.25%), the LIBS signal is quenched due to Penning ionization. The hydrogen alpha line (656.28 nm) was observed to broaden as the concentration of helium impurities in the hydrogen gas mixture increased. The helium line at 587.56 nm was selected as the analyte line for helium impurity detection. The effects of laser energy, the delay time between the laser pulse and data acquisition, and the gas pressure on the LIBS signal of helium were investigated to determine the optimum conditions for helium detection. The LIBS signal from the helium line at 587.56 nm shows good linear correlation with helium concentration for He concentrations below 1%. Thus, LIBS can be reliably used to detect the low levels of helium. The limit of detection for helium was found to be 78 ppm.     

Characterization of malignant tissue cells by laser-induced breakdown spectroscopy

Cancer diagnosis and classification is extremely complicated and, for the most part, relies on subjective interpretation of biopsy material. Such methods are laborious and in some cases might result in different results depending on the histopathologist doing the examination. Automated, real-time diagnostic procedures would greatly facilitate cancer diagnosis and classification. Laser-induced breakdown spectroscopy (LIBS) is used for the first time to our knowledge to distinguish normal and malignant tumor cells from histological sections. We found that the concentration of trace elements in normal and tumor cells was significantly different. For comparison, the tissue samples were also analyzed by an inductively coupled plasma emission spectroscopy (ICPES) system. The results from the LIBS measurement and ICPES analysis were in good agreement.     

Single-pollen analysis by laser-induced breakdown spectroscopy and Raman microscopy

The application of laser-induced breakdown spectroscopy to the analysis of single biological microparticles (bioaerosols) is described, exemplified here for a range of pollens. Spectra were recorded by exposure of the pollen to a single laser pulse from a Nd:YAG laser (lambda = 1064 nm, Ep approximately 30 mJ). The intensities of the single-pulse laser-induced breakdown spectra fluctuated dramatically, but an internal signal calibration procedure was applied that referenced elemental line intensities to the carbon matrix of the sample (represented by molecular bands of CN and C2). This procedure allowed us to determine relative element concentration distributions for the different types of pollen. These pollens exhibited some distinct concentration variations, for both major and minor (trace) elements in the biomatrix, through which ultimately individual pollens might be identified and classified. The same pollen samples were also analyzed by Raman microscopy, which provided molecular compositional data (even with spatial resolution). These data allowed us to distinguish between biological and nonbiological specimens and to obtain additional classification information for the various pollen families, complementing the laser-induced breakdown spectroscopy measurement data.     

Detection of uranium in solids by using laser-induced breakdown spectroscopy combined with laser-induced fluorescence

Detection of uranium in solids by using laser-induced breakdown spectroscopy has been investigated in combination with laser-induced fluorescence. An optical parametric oscillator wavelength-tunable laser was used to resonantly excite the uranium atoms and ions within the plasma plumes generated by a Q-switched Nd:YAG laser. Both atomic and ionic lines can be selected to detect their fluorescence lines. A uranium concentration of 462 ppm in a glass sample can be detected by using this technique at an excitation wavelength of 385.96 nm for resonant excitation of U II and a fluorescence line wavelength of 409.0 nm from U II.     

The detection of palladium particles in proton exchange membrane fuel-cell water by laser-induced breakdown spectroscopy (LIBS)

Laser-induced breakdown spectroscopy (LIBS) using conditional data analysis was applied to aqueous suspensions of palladium particles in the reformate water of palladium-based proton exchange membrane fuel cells. A significant amount of palladium was found in the water, indicating degradation of the fuel-cell cathode catalytic layers. The palladium particle-size detection limit was found to be about 400 nm. Calibration procedures to quantify the palladium concentration are discussed.     

H-type microchannel fiber humidity sensor by femtosecond laser-induced water breakdown

H-type microchannel in single-mode fiber was fabricated using femtosecond laser-induced water breakdown. The air can be brought into the fiber core position through H-type microchannel. As the relative humidity of the air changing from 25 to 60%, the transmission power of the fiber without coating any absorbent material on the fiber decreased more than ?23 dB. The relative humidity sensitivity gets to as high as ?1.00 dB/1%RH. The fiber with H-type microchannel structure can be used as humidity sensor as its high sensitivity, quick response, and low cost.     

Detection and mapping of latent fingerprints by laser-induced breakdown spectroscopy

Detection of latent fingerprints on a Si wafer by laser-induced breakdown spectroscopy (LIBS) is demonstrated using approximately 120 fs pulses at 400 nm with energies of 84 +/- 7 microJ. The presence of a fingerprint ridge is found by observing the Na emission lines from the transferred skin oil. The presence of the thin layer of transferred oil was also found to be sufficient to suppress the LIBS signal from the Si substrate, giving an alternative method of mapping the latent fingerprint using the Si emission. A two-dimensional image of a latent fingerprint can be successfully collected using these techniques.     

Rapid determination of zinc in soils by laser-induced breakdown spectroscopy

The possibility of quantitative detection of trace zinc levels in soils per single laser pulse using laser-induced breakdown spectroscopy is shown. The development of laser plasma and the signal-to-noise ratio are studied when evaporating soils by the second (532 nm) and the third (355 nm) harmonics of an Nd:YAG pulse laser. The use of the third harmonics permits one to reach the zinc detection limit (18 ppm) below Occupational Exposure Limits (OEL) in soil (150 ppm) and below the mean abundance in the earth’s crust of zinc (83 ppm). This allows the use of the suggested technique for the rapid determination of soil pollution with zinc and searching for geochemical anomalies.     

Multiband sensor using thick holographic gratings for sulfur detection by laser-induced breakdown spectroscopy

Detection of sulfur by optical emission spectroscopy generally presents some difficulties because the strongest lines are in the vacuum UV below 185 nm and therefore are readily absorbed by oxygen molecules in air. A novel concept for a low-cost and efficient system to detect sulfur using near-IR bands by laser-induced breakdown spectroscopy is here proposed. This concept is based on customized thick holographic gratings as spectral filtering elements. The signal integration and the temporal synchronization are performed using built-in custom electronics that amplify and integrate or trigger photodiode output signals. In this work, we use the near-IR lines at 921.287 nm and a background reference at 900 nm. Preliminary results show a limit of detection comparable to that of a conventional high-end system.