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The present review attempts to comprehensively overview the progress in the field of nanoparticle-related analytical laser and plasma spectroscopy research, focusing on the results of the past decade. The discussion involves the brief description of the motivation and principle of operation behind all existing technologies. As a novel approach, the connection between nanoparticles and laser and plasma spectroscopy is discussed in all three major areas: monitoring of nanoparticle synthesis, nanoparticle characterization, as well as plasmonic signal enhancement achieved by using nanoparticles. In each area, a detailed description of methodological developments and modern applications is provided.

Identification and quantification of human fingernail calcium is demonstrated by laser-induced breakdown spectroscopy (LIBS) using the modified external standardization. Since cow’s horn and hoof have structures very similar to the fingernail, either of them is individually selected as the matrix of standard samples. In total, 12 standard samples for each matrix are prepared using CaCO3 as the standard substance. In order to achieve accurate calibration curves associated with the method of modified external standard, foremost, the calcium concentration of each of matrices (horn and hoof) is determined by the method of standard additions. The results indicate that there exist 4887 µg/g (ppm) and 4156 µg/g (ppm) of calcium in the pure horn and hoof matrices, respectively. Then, the external calibration curves related to the two matrices are plotted using the information of standard samples. Finally, by the use of signals obtained from LIBS experiment for three different fingernails and inserting their amounts into the calibration curves, the calcium concentration of the fingernails under test is measured to be 10,814 µg/g (ppm), 13,106 µg/g (ppm) and 14,974 µg/g (ppm). The difference of the calcium concentrations between three specimens, as will be discussed, may be due to different physical conditions of people who have donated their fingernails.

In this paper, we investigate a new method to control the plasma electron number density of copper metal using a near-infrared (NIR) picosecond Nd:YAG laser-induced plasma spectroscopy (LIPS) technique. The applied laser parameters are as follows; laser pulse energy and intensity varied from 29.2 to 59.4 mJ ± 3% and from 6.01×1010 to 12.35×1010 W/cm2 ± 5%, respectively, for a single pulse at 170 ps pulse duration, and beam diameter about 0.5 ± 0.1 mm. By considering the Stark broadening of a specific spectral line, electron density can be calculated using a neutral copper line at 521.8 nm, assuming the local thermodynamic equilibrium (LTE) condition. The observed electron density values were 1.09×1016, 2.24×1016, 3.60×1016, and 4.75×1016 cm–3 for the laser pulse energies 29.2, 41, 52.4, and 59.4 mJ, respectively. The plasma electron density values are increased with the increase in laser pulse energy. Such findings were interpreted due to an increase in the mass ablation rates with laser pulse energy. The obtained results explore the ability to control the plasma electron density by controlling the picosecond pulse energy. These results can contribute to the development of plasma technologies and their applications in many fields.

Researchers had conducted an experiment by using an Nd-YAG laser at third harmonic mode to generate plasma from the sample of meatballs containing borax as a contaminant with various concentrations. The plasma emission was investigated by using a gated Optical Multichannel Analyzer (OMA). The boron emission line (B I 249.7 nm) was used as an indicator of the existence of borax in meatballs food. The optimum conditions of plasma generation in this experiment were 21 mJ laser energy, surrounding gas pressure was air at 10Torr, and the OMA delay was set at 1 µs. In this experiment, the existence of 105 ppm (w) borax could be detected by using a boron emission line. The experimental results showed that laser-induced plasma spectroscopy was a rapid analysis method for any kind of samples.

We developed an echelle spectrometer for the simultaneous observation of the whole visible range with a high instrumental resolution, for example, 0.055 nm (full width at the half maximum) at 400 nm and 0.10 nm at 750 nm. With the spectrometer, the emission from an ablation cloud of an aluminum pellet injected into a high-temperature plasma generated in the Large Helical Device (LHD) was measured. We separated the emission lines into Al I, II, III and IV groups, and estimated the electron temperature and density of the ablation cloud from the line intensity distribution and Stark broadening respectively, of each of the Al I, II and III groups. We also determined the Stark broadening coefficients of many Al II and III lines from the respective Stark widths with the estimated electron temperature and density.

An influence of SAS (Тriton Х-100) concentration and ultrasound treatment time on the value of analytical signal at atomic absorption and atomic emission with inductive connected plasma detection of analytes in strata water was studied. Maximal analytical signal at of Lead and Iron was reached at using nonionogenic SAS which let us to decrease surface tension of the analyzed solution and to increase absorptivity at analytes detection. It was shown that using of the modern sample preparation increase sensibility of atomic absorption detection of Lead in 1,5 times and Iron in 1,8 times. By the methods of atomic absorption and atomic emission with inductive connected plasma spectroscopy and using acetylacetonates of Lead and Iron as standard composition samples, that let us to increase sensitivity of the detection of analytes, contain of Lead and Iron in strata water was determined. By variation of the sample volume and by "injected-found out" method we have proved that systematic error is not significant. The results, obtained by two independent methods were compared according to F- and t-criteria. It was proved that dispersions are homogenous and run of the means is not sufficient and proved by random scatter. By atomic absorption method we estimated the detection limit of the analytes according to the developed methodic and show that the obtained results are lower than the same data from literature. The developed methodic, according to its metrological characteristics, is competitive at international level.

This article discusses laser-induced laboratory-air plasma measurements and analysis of hydroxyl (OH) ultraviolet spectra. The computations of the OH spectra utilize line strength data that were developed previously and that are now communicated for the first time. The line strengths have been utilized extensively in interpretation of recorded molecular emission spectra and have been well-tested in laser-induced fluorescence applications for the purpose of temperature inferences from recorded data. Moreover, new experiments with Q-switched laser pulses illustrate occurrence of molecular recombination spectra for time delays of the order of several dozen of microseconds after plasma initiation. The OH signals occur due to the natural humidity in laboratory air. Centrifugal stretching of the Franck-Condon factors and r-centroids are included in the process of determining the line strengths that are communicated as a Supplementary File. Laser spectroscopy applications of detailed OH computations include laser-induced plasma and combustion analyses, to name but two applications. This work also includes literature references that address various diagnosis applications.

This article reports new measurements of laser-induced plasma hypersonic expansion measurements of diatomic molecular cyanide (CN). Focused, high-peak-power 1064 nm Q-switched radiation of the order of 1 TW/cm 2 generated optical breakdown plasma in a cell containing a 1:1 molar gas mixture of N 2 and CO 2 at a fixed pressure of 1.1 &times, 10 5 Pascal and in a 100 mL/min flow of the mixture. Line-of-sight (LOS) analysis of recorded molecular spectra indicated the outgoing shockwave at expansion speeds well in excess of Mach 5. Spectra of atomic carbon confirmed increased electron density near the shockwave, and, equally, molecular CN spectra revealed higher excitation temperature near the shockwave. Results were consistent with corresponding high-speed shadowgraphs obtained by visualization with an effective shutter speed of 5 nanoseconds. In addition, LOS analysis and the application of integral inversion techniques allow inferences about the spatiotemporal plasma distribution.

This study presents the investigation of optical emission spectroscopy of plasma using interpretable convolutional neural network (CNN) for real-time volatile organic compounds (VOCs) classification. A microplasma-generation platform was developed to efficiently collect 64 k spectra from various types of VOCs at different concentrations, as training and testing sets for machine learning. A CNN model was trained to classify VOCs with accuracy of 99.9%. To interpret the CNN model and its predictions, the spectral processing mechanism of the CNN was visualized by feature maps and the critical spectral features were identified by gradient-weighted class activation mapping. Such approaches brought insights on how CNN analyzes the spectra and enables the CNN operation to be explainable. Finally, the CNN model was incorporated with the microplasma platform to demonstrate the application of real-time VOC monitoring. The type of VOCs can be identified and reported via messages within 10 s once the microplasma is ignited. We believe that using CNN brings a novel route for plasma spectroscopy analysis for VOC classification and impacts the fields of plasma, spectroscopy, and environmental monitoring.

Chemical analysis is commonly used in the field of forensic science where the precise discrimination of primary evidence is of significant importance. Laser-Induced Breakdown Spectroscopy (LIBS) exceeds other spectroscopic methods in terms of the time required for pre- and post-sample preparation, the insensitivity to sample phase state be it solid, liquid, or gas, and the detection of two-dimensional spectral mapping from real time point measurements. In this research, fingerprint samples on various surface materials are considered in the chemical detection and reconstruction of fingerprints using the two-dimensional LIBS technique. Strong and distinct intensities of specific wavelengths represent visible ink, natural secretion of sweat, and contaminants from the environment, all of which can be present in latent fingerprints. The particular aim of the work presented here is to enhance the precision of the two-dimensional recreation of the fingerprints present on metal, plastic, and artificially prepared soil surface using LIBS with principal component analysis. By applying a distinct wavelength discrimination for two overlapping fingerprint samples, separation into two non-identical chemical fingerprints was successfully performed.

A hand-held laser-induced breakdown spectroscopy device was used to acquire spectral emission data from laser-induced plasmas created on the surface of cerium-gallium alloy samples with Ga concentrations ranging from 0&ndash, 3 weight percent. Ionic and neutral emission lines of the two constituent elements were then extracted and used to generate calibration curves relating the emission line intensity ratios to the gallium concentration of the alloy. The Ga I 287.4-nm emission line was determined to be superior for the purposes of Ga detection and concentration determination. A limit of detection below 0.25% was achieved using a multivariate regression model of the Ga I 287.4-nm line ratio versus two separate Ce II emission lines. This LOD is considered a conservative estimation of the technique&rsquo, s capability given the type of the calibration samples available and the low power (5 mJ per 1-ns pulse) and resolving power ( &lambda, / &Delta, &lambda, = 4000) of this hand-held device. Nonetheless, the utility of the technique is demonstrated via a detailed mapping analysis of the surface Ga distribution of a Ce-Ga sample, which reveals significant heterogeneity resulting from the sample production process.

Laser-induced breakdown spectroscopy (LIBS), known also as laser-induced plasma spectroscopy (LIPS), is a well-known spectrochemical elemental analysis technique. The field of LIBS has been rapidly matured as a consequence of growing interest in real-time analysis across a broad spectrum of applied sciences and recent development of commercial LIBS analytical systems. In this brief review, we introduce the contributions of the research groups in the African continent in the field of the fundamentals and applications of LIBS. As it will be shown, the fast development of LIBS in Africa during the last decade was mainly due to the broad environmental, industrial, archaeological, and biomedical applications of this technique.

On-chip microplasmas have previously been used in designing a compact and portable device for identifying pollutants in a water sample. By exciting a liquid sample with a high energy microdischarge and recording the spectral wavelengths emitted, the individual elements in the liquid are distinguishable. In particular, this study focuses on cesium, a contaminant from nuclear incidents such as the collapse of the nuclear power plant in Fukushima, Japan. This article shows that not only can the presence of cesium be clearly determined at concentrations as low as 10 ppb, but the relative concentration contained in the sample can be determined through the discharges’ relative spectral intensity.

The elemental detection of green bean of arabica and robusta coffee from Gayo Highland, Aceh-Indonesia, has been identified by using fundamental Nd-YAG Laser at 10 Torr of surrounding air gas pressure for distinguishing the characteristics of both coffees. As the preliminary study, we have detected the elements of K 766.49 nm, Na 588.9 nm, Ca 393.3 nm, CN band at 388.3 nm, N 337.13 nm and C 247.8 nm of both coffees. It is noticed that the order of elements concentration from highest to lowest are Ca>K>CN> Na>N> C for arabica and K>Ca>CN >Na>C>N for robusta. The emission intensity of K 766.49 nm is almost same for both of coffee. However, the emission intensity of Na 588.9 nm is lower in Arabica coffee. To distinguish the Arabica coffee and Robusta Coffee, we take the ratio intensity of K/C, Na/C, CN/C, and Ca/C. It is found that the ratio intensities of CN/C and Ca/C in arabica bean are significantly different with robusta bean. That ratio intensities can be used as a marker to discriminate kind of coffee...

This work presents new calibration procedures for deep elemental depth profile analysis of bronze artifacts. A simple ablation model is developed for the estimation of the ablation rate and hence for deriving the depth spatial calibration scale. Elemental quantification is obtained through the construction of calibration surfaces, using reference samples of known composition, relating laser-induced plasma spectroscopy (LIPS) intensity ratios, content of atomic species and number of laser pulses. Such a method represents a refinement of the standard LIPS quantification approach based on calibration curves, which is extended here to the generation of significantly deep craters into the material under investigation up to several hundred microns. The depth dependence of the calibration surfaces measured is discussed in the framework of a simplified model of depth-dependent plasma temperature.

Experimentally determined ion temperatures of different charge states and elements in minimum-B confined electron cyclotron resonance ion source (ECRIS) plasma are reported. It is demonstrated with optical emission spectroscopy, complemented by the energy spread measurements of the extracted ion beams, that the ion temperature in the JYFL 14 GHz ECRIS is 5–28 eV depending on the plasma species and charge state. The reported ion temperatures are an order of magnitude higher than previously deduced from indirect diagnostics and used in simulations, but agree with those reported for a quadrupole mirror fusion experiment. The diagnostics setup and data interpretation are discussed in detail to demonstrate adequate understanding of the line broadening mechanisms and instrumental effects, which justifies the use of the measured Doppler broadening of the emission lines to derive the corresponding ion temperature. The ion temperatures of the high charge state plasma of the minimum-B ECRIS are compared to those measured from low temperature singly charged microwave and arc discharge plasmas to exclude systematic errors. The ion temperatures in the minimum-B ECRIS plasmas are shown to increase with the charge state and injected microwave power whereas two-frequency heating and plasma instabilities have only a minor effect on them. Possible mechanisms causing the higher-than-expected ion temperatures are hypothesized and assessed based on the reported experimental data. Finally, the implications of the results are discussed, demonstrating the need for further experiments especially with charge breeder ECR ion sources, and experimental data on ion confinement times. peerReviewed

In this work, measurements of cyanide (CN) molecular spectra following laser-induced optical breakdown are communicated. The recorded time-resolved data are Abel inverted to determine the spatial distributions of the maximum CN signals and to evaluate molecular excitation temperatures. The experiments are conducted in a 1:1 CO2:N2 gas mixture contained in a cell kept at atmospheric pressure, and the micro-plasma is generated using 150 mJ, 6 ns Q-switched Nd:YAG laser radiation. The optical emissions from the micro-plasma are dispersed using a 0.64 m spectrometer and are recorded along the wavelength and slit dimensions using an intensified charge-coupled device.

Ablation of titanium wafers in air is accomplished with 60 µs pulsed, 2.94 µm laser radiation. Titanium monoxide spectra are measured in the wavelength range of 500 nm to 750 nm, and molecular signatures include bands of the C3 Δ → X3 Δ α, B3 Π → X3 Δ γ′, and A3 Φ → X3 Δ γ transitions. The spatially and temporally averaged spectra appear to be in qualitative agreement with previous temporally resolved studies that employed shorter wavelengths and shorter pulse durations than utilized in this work. The background signals in the current study are possibly due to particulate content in the plume. A chemical kinetic model of the plume is being developed that will be coupled to a diatomic emission model in order to extract a molecular temperature from the observed spectra.

In this paper, we investigate the basic characteristics of "magnetron sputtering plasma" using the target V2O5. The "magnetron sputtering plasma" is produced using "radio frequency (RF)" power supply and Argon gas. The intensity of the light emission from atoms and radicals in the plasma measured by using "optical emission spectrophotometer", and the appeared peaks in all patterns match the standard lines from NIST database and employed are to estimate the plasma parameters, of computes electron temperature and the electrons density. The characteristics of V2O5 sputtering plasma at multiple discharge provisos are studied at the "radio frequency" (RF) power ranging from 75 - 150 Watt and gas pressure (0.03, 0.05 and 0.007) torr. One can observe that the intensity of the emission lines increases with increasing the sputtering power. We find that the electron temperature excess drastically from 0.95 eV to 1.11eV when the emptying gas pressure excess from 0.03 to 0.05 Torr. On other hand excess electron temperature from 0.9 to 1.01 eV with increasing sputtering power from 100 to 125 Watt, while the electron density decrease from 5.9×1014 to 4.5×1014 cm-3 with increasing sputtering power. and electron density decrease with increasing of pressure from 4.25×1014 to 2.80×1014 cm-3, But the electron density maximum values 5.9×1014 at pressure 0.03 Torr.

Two-dimensional mapping of the laser-induced breakdown spectroscopy (LIBS) signal of chemical species information in liquefied petroleum gas (LPG) and electrolytic oxy-hydrogen (EOH) flames was performed with in situ flame diagnostics. Base LIBS signals averaged from measurements at wavelengths of 320 nm to 350 nm describe the density information of a flame. The CN LIBS signal provides the concentration of fuel, while the H/O signal represents the fuel/air equivalence ratio. Here, we demonstrate the meaningful use of two-dimensional LIBS mappings to provide key combustion information, such as density, fuel concentration, and fuel/air equivalence ratio.

X-ray diffraction (XRD), scanning electron microscopy (SEM), inductive-coupled plasma spectroscopy (ICP), oxygen analyzer were used to investigate the solid state reaction of Nd2Fe14B powders with carbon. The experiment results revealed that Nd-rich phase (FCC-NdO) was formed after sintering when the samples contain oxygen (1 percent). With the carbon content of Nd-rich phase increasing, the Nd-rich phase changed from FCC-NdO phase to h-Nd2O3 phase. And the phase evolution of Nd-rich phase was sensitive to the carbon concentration as well as the sintering time. When the oxygen free samples sintering over 1100 °C, the phase evolution of iron was sensitive to the sintering temperature. With the temperature increased to 1300 °C, the Nd-rich compounds (NdFeC compounds) decreased and the NdC2 increased.

In this work we have studied corroded archaeological artefacts by combining THz and laser induced plasma spectroscopy (LIPS). The main aim of the work was the assessment of the potential of the THz TDS reflectometry for achieving stratigraphic information and the presence of the metal bulk beneath encrustations and alteration layers before measuring LIPS elemental depth profiles. The behaviour of the reflected THz pulses was formerly investigated by preparing a set of suitable mock-ups, then measurements were carried out on a set of authentic archaeological samples exhibiting different stratigraphic situations, and eventually a deeply corroded Egyptian bronze figurine was characterised. The results achieved show the range of stratigraphic information, which can be provided by THz and the advantages of the present analytical combination.

Estimating the tritium amount retained in the plasma facing components and their surface layer composition is of crucial importance for ITER. Laser-induced breakdown spectroscopy (LIBS) is an analytical technique suitable for in situ measurements of both these quantities. For improving its sensitivity, the double pulse (DP) variant can be used, instead of the standard single pulse (SP). In this work Mo samples coated with 1.5-1.8 μm thick W-Al (as a proxy for Be) mixed layer, with co-deposited deuterium were analyzed under vacuum (∼5 10-5 mbar) by SP and DP LIBS, showing enhancement of the spectral intensity for the latter. Calibration free method was applied to the LIBS data for getting the elemental concentration of W and Al. Results are in satisfactory agreement with those obtained from preliminary, ion beam analysis measurements. Deuterium concentration was tentatively estimated by accounting for the intensity ratio between Dα and nearby WI lines. © 2016 EUROfusion.

In this paper we describe a novel spectroscopic closed loop control system capable of stabilizing the penetration depth during laser welding processes by controlling the laser power. Our novel approach is to analyze the optical emission from the laser generated plasma plume above the keyhole, to calculate its electron temperature as a process-monitoring signal. Laser power has been controlled by using a quantitative relationship between the penetration depth and the plasma electron temperature. The sensor is able to correlate in real time the difference between the measured electron temperature and its reference value for the requested penetration depth. Accordingly the closed loop system adjusts the power, thus maintaining the penetration depth.

The plasma optical radiation emitted during CO2 laser welding of stainless steel samples has been detected with a Si-PIN photodiode and analyzed under different process conditions. The discrete wavelet transform (DWT) has been used to decompose the optical signal into various discrete series of sequences over different frequency bands. The results show that changes of the process settings may yield different signal features in the range of frequencies between 200 Hz and 30 kHz. Potential applications of this method to monitor in real time the laser welding processes are also discussed.

Plasma optical spectroscopy is widely employed in on-line welding diagnostics. The determination of the plasma electron temperature, which is typically selected as the output monitoring parameter, implies the identification of the atomic emission lines. As a consequence, additional processing stages are required with a direct impact on the real time performance of the technique. The line-to-continuum method is a feasible alternative spectroscopic approach and it is particularly interesting in terms of its computational efficiency. However, the monitoring signal highly depends on the chosen emission line. In this paper, a feature selection methodology is proposed to solve the uncertainty regarding the selection of the optimum spectral band, which allows the employment of the line-to-continuum method for on-line welding diagnostics. Field test results have been conducted to demonstrate the feasibility of the solution.

We report the development of a novel portable and low-cost laser induced plasma spectroscopy (LIPS) system and describe the application method for quantitative characterisation of quaternary copper alloy artefacts. The device was carefully calibrated and phenomenologically characterised using a set of reference samples. The reliability of the quantitative measurement of the depth profile and bulk compositions was assessed through crossed comparisons with traditional analytical techniques. Finally, the LIPS system was applied to investigate a museum figurine of unknown origin composed of several pieces, which is representative of a typical authentication problem.

A new spectral processing technique designed for application in the on-line detection and classification of arc-welding defects is presented in this paper. A noninvasive fiber sensor embedded within a TIG torch collects the plasma radiation originated during the welding process. The spectral information is then processed in two consecutive stages. A compression algorithm is first applied to the data, allowing real-time analysis. The selected spectral bands are then used to feed a classification algorithm, which will be demonstrated to provide an efficient weld defect detection and classification. The results obtained with the proposed technique are compared to a similar processing scheme presented in previous works, giving rise to an improvement in the performance of the monitoring system.

Nanostructured thin films were deposited by excimer laser ablation of silver targets in controlled atmospheres of He and Ar. The film structural properties were investigated by means of scanning electron microscope and transmission electron microscope imaging. The film growth mechanism was identified as the result of coalescence of nanometric clusters formed during plume flight. Cluster formation involves plume confinement as a consequence of the increased collisional rate among plasma species. Fast photography imaging of the laser-generated silver plasma allowed to identify plasma confinement, shock wave formation and plasma stopping.