Analysis of Enhanced Laser-Induced Breakdown Spectroscopy with Double Femtosecond Laser Pulses

In this paper,an experimental study of collinear geometry double-pulse femtosecond LIBS was performed on a Ni sample in ambient air in an effort to clarify the contributing processes responsible for the signal enhancement observed in comparison with the single-pulse case.Doublepulse LIBS spectra show a very clear enhancement when an optimum inter-pulse delay was used.The influences of the inter-pulse delay between two pulses on the LIBS signal intensity,electron temperature and density were investigated.It is most remarkable that the evolutions of signal enhancement and electron temperature versus the inter-pulse delay showed the same behavior and revealed two main regimes of interaction.These results provide additional insight into the possible emission enhancement mechanisms in the double pulse configuration.     

Re-Heating Effect on the Enhancement of Plasma Emission Generated from Fe Under Femtosecond Double-Pulse Laser Irradiation

In this paper, we present a study on the effect of inter-pulse delay using femtosecond double-pulse laser-induced breakdown spectroscopy in a collinear geometry. The temporal evolution of spectral intensity is performed for the lines of Fe I 423.60 nm, Fe I 425.08 nm and Fe I 427.18 nm. It is found that, by selecting appropriate inter-pulse delay, the signal enhancement can be significantly increased compared with the single-pulse case. A three-fold enhancement in the current experiment is obtained. The plasma temperature and electron density are also investigated based on the theory of Boltzmann plot and Stark broadening. We attribute the main mechanism for emission enhancement to the plasma re-heating effect.     

Influence of target temperature on AlO emission of femtosecond laser-induced Al plasmas

The influence of the target temperature on the molecular emission of femtosecond laser-induced breakdown spectroscopy(LIBS) was investigated experimentally. An Al target was ablated to produce laser-induced plasma. The Al target was uniformly heated to a maximum of 250℃. The measured molecular emission was AlO(△ν=0) from the femtosecond LIBS of the Al target.The measurements indicated that the molecular emission of AlO increased as the temperature of the Al target increased. In addition, a two-temperature model was used to simulate the evolution of the electron and lattice temperature of the Al target with different initial temperatures. The simulated results showed that the electron and lattice temperatures of Al irradiated by the femtosecond laser increased as the initial temperature of the Al target increased; also, the simulated ablated depth increased. Therefore, an increase in the initial Al target temperature resulted in an enhancement in the spectral signal of AlO from the femtosecond LIBS of Al,which was directly related to the increase in the size of the ablated crater. The study suggested that increasing the temperature of the target improves the intensity of molecular emission in femtosecond LIBS.     

Influence of target temperature on AIO emission of femtosecond laser-induced AI plasmas

The influence of the target temperature on the molecular emission of femtosecond laser-induced breakdown spectroscopy (LIBS) was investigated experimentally.An Al target was ablated to produce laser-induced plasma.The Al target was uniformly heated to a maximum of 250 ℃.The measured molecular emission was AlO (△υ =0) from the femtosecond LIBS of the Al target.The measurements indicated that the molecular emission of AIO increased as the temperature of the A1 target increased.In addition,a two-temperature model was used to simulate the evolution of the electron and lattice temperature of the Al target with different initial temperatures.The simulated results showed that the electron and lattice temperatures of Al irradiated by the femtosecond laser increased as the initial temperature of the A1 target increased;also,the simulated ablated depth increased.Therefore,an increase in the initial A1 target temperature resulted in an enhancement in the spectral signal of AlO from the femtosecond LIBS of Al,which was directly related to the increase in the size of the ablated crater.The study suggested that increasing the temperature of the target improves the intensity of molecular emission in femtosecond LIBS.     

Signal Detection of Carbon in Iron-Based Alloy by Double-Pulse Laser-Induced Breakdown Spectroscopy

Although single-pulse lasers are often used in traditional laser-induced breakdown spectroscopy (LIBS) measurements, their measurement outcomes are generally undesirable be?cause of the low sensitivity of carbon in iron-based alloys. In this article, a double-pulse laser was applied to improve the signal intensity of carbon. Both the inter-pulse delay and the combina?tion of laser wavelengths in double-pulse laser-induced breakdown spectroscopy (DP-LIBS) were optimized in our experiment. At the optimized inter-pulse delay, the combination of a first laser of 532 nm and a second laser of 1,064 nm achieved the highest signal enhancement. The proper?ties of the target also played a role in determining the mass ablation enhancement in DP-LIBS con?guration.     

Remote open-path laser-induced breakdown spectroscopy for the analysis of manganese in steel samples at high temperature

A remote open-path laser-induced breakdown spectroscopy(LIBS) system was designed and studied in the present work for the purpose of combining the LIBS technique with the steel production line. In this system, the relatively simple configuration and optics were employed to measure the steel samples at a remote distance and a hot sample temperature. The system has obtained a robustness for the deviation of the sample position because of the open-path and alloptical structure. The measurement was carried out at different sample temperatures by placing the samples in a muffle furnace with a window in the front door. The results show that the intensity of the spectral lines increased as the sample temperature increased. The influence of the sample temperature on the quantitative analysis of manganese in the steel samples was investigated by measuring ten standard steel samples at different temperatures. Three samples were selected as the test sample for the simulation measurement. The results show that, at the sample temperature of 500 ℃, the average relative error of prediction is 3.1% and the average relative standard deviation is 7.7%, respectively.     

Time-resolved spectroscopy of collinear femtosecond and nanosecond dual-pulse laser-induced Cu plasmas

In this paper,we investigate the time-resolved spectroscopy of collinear femtosecond(fs)and nanosecond(ns)dual-pulse(DP)laser-induced plasmas.A copper target was used as an experimental sample,and the fs laser was considered as the time zero reference point.The inter-pulse delay between fs and ns laser beams was 3 μs.First,we compared the time-resolved peak intensities of Cu(Ⅰ)lines from Cu plasmas induced by fs+ns and ns+fs DP lasers with collinear configuration.The results showed that compared with the ns+fs DP,the fs+ns DP laser-induced Cu plasmas had stronger peak intensities and longer lifetimes.Second,we calculated time-resolved plasma temperatures using the Boltzmann plot with three spectral lines at Cu(Ⅰ)510.55,515.32 and 521.82 nm.In addition,time-resolved electron densities were calculated based on Stark broadening with Cu(Ⅰ)line at 521.82 nm.It was found that compared with ns+fs DP,the plasma temperatures and electron densities of the Cu plasmas induced by fs+ns DP laser were higher.Finally,we observed images of ablation craters under the two experimental conditions and found that the fs+ns DP laser-produced stronger ablation,which corresponded to stronger plasma emission.     

Influence of target temperature on femtosecond laser-ablated brass plasma spectroscopy

Spectral intensity,electron temperature and density of laser-induced plasma(LIP) are important parameters for affecting sensitivity of laser-induced breakdown spectroscopy(LIBS).Increasing target temperature is an easy and feasible method to improve the sensitivity.In this paper,a brass target in a temperature range from 25℃ to 200℃ was ablated to generate the LIP using femtosecond pulse.Time-resolved spectral emission of the femtosecond LIBS was measured under different target temperatures.The results showed that,compared with the experimental condition of 25℃,the spectral intensity of the femtosecond LIP was enhanced with more temperature target.In addition,the electron temperature and density were calculated by Boltzmann equation and Stark broadening,indicating that the changes in the electron temperature and density of femtosecond LIP with the increase of the target temperature were different from each other.By increasing the target temperature,the electron temperature increased while the electron density decreased.Therefore,in femtosecond LIBS,a hightemperature and low-density plasma with high emission can be generated by increasing the target temperature.The increase in the target temperature can improve the resolution and sensitivity of femtosecond LIBS.     

Detection of K in soil using time-resolved laser-induced breakdown spectroscopy based on convolutional neural networks

One of the technical bottlenecks of traditional laser-induced breakdown spectroscopy (LIBS) is the difficulty in quantitative detection caused by the matrix effect. To troubleshoot this problem, this paper investigated a combination of time-resolved LIBS and convolutional neural networks (CNNs) to improve K determination in soil. The time-resolved LIBS contained the information of both wavelength and time dimension. The spectra of wavelength dimension showed the characteristic emission lines of elements, and those of time dimension presented the plasma decay trend. The one-dimensional data of LIBS intensity from the emission line at 766.49 nm were extracted and correlated with the K concentration, showing a poor correlation of R²_c=0.0967, which is caused by the matrix effect of heterogeneous soil. For the wavelength dimension, the two-dimensional data of traditional integrated LIBS were extracted and analyzed by an artificial neural network (ANN), showing R²_v=0.6318 and the root mean square error of validation (RMSEV)=0.6234. For the time dimension, the two-dimensional data of time-decay LIBS were extracted and analyzed by ANN, showing R²_v=0.7366 and RMSEV=0.7855. These higher determination coefficients reveal that both the non-K emission lines of wavelength dimension and the spectral decay of time dimension could assist in quantitative detection of K. However, due to limited calibration samples, the two-dimensional models presented over-fitting. The three-dimensional data of time-resolved LIBS were analyzed by CNNs, which extracted and integrated the information of both the wavelength and time dimension, showing the R²_v=0.9968 and RMSEV=0.0785. CNN analysis of time-resolved LIBS is capable of improving the determination of K in soil.     

Effect of lens focusing distance on laser-induced silicon plasmas at different sample temperatures

We investigated the dependence of laser-induced breakdown spectral intensity on the focusing position of a lens at different sample temperatures(room temperature to 300 ℃) in atmosphere.A Q-switched Nd:YAG nanosecond pulsed laser with 1064 nm wavelength and 10 ns pulse width was used to ablate silicon to produce plasma. It was confirmed that the increase in the sample's initial temperature could improve spectral line intensity. In addition, when the distance from the target surface to the focal point increased, the intensity firstly rose, and then dropped.The trend of change with distance was more obvious at higher sample temperatures. By observing the distribution of the normalized ratio of Si atomic spectral line intensity and Si ionic spectral line intensity as functions of distance and temperature, the maximum value of normalized ratio appeared at the longer distance as the initial temperature was higher, while the maximum ratio appeared at the shorter distance as the sample temperature was lower.     

Time-resolved spectroscopy of femtosecond laser-induced Cu plasma with spark discharge

The combination of spark discharge and laser-induced breakdown spectroscopy (LIBS) is called spark discharge assisted LIBS. It works under laser-plasma triggered spark discharge mode, and shows its ability to enhance spectral emission intensity. This work uses a femtosecond laser as the light source, since femtosecond laser has many advantages in laser-induced plasma compared with nanosecond laser, meanwhile, the study on femtosecond LIBS with spark discharge is rare. Time-resolved spectroscopy of spark discharge assisted femtosecond LIBS was investigated under different discharge voltages and laser energies. The results showed that the spectral intensity was significantly enhanced by using spark discharge compared with LIBS alone. And, the spectral emission intensity using spark discharge assisted LIBS increased with the increase in the laser energy. In addition, at low laser energy, there was an obvious delay on the discharge time compared with high laser energy, and the discharge time with positive voltage was different from that with negative voltage.     

Relative spectral response calibration using Ti plasma lines

This work introduces the branching ratio(BR) method for determining relative spectral responses,which are needed routinely in laser induced breakdown spectroscopy(LIBS). Neutral and singly ionized Ti lines in the 250–498 nm spectral range are investigated by measuring laser-induced micro plasma near a Ti plate and used to calculate the relative spectral response of an entire LIBS detection system. The results are compared with those of the conventional relative spectral response calibration method using a tungsten halogen lamp, and certain lines available for the BR method are selected. The study supports the common manner of using BRs to calibrate the detection system in LIBS setups.     

Application of Stand-off Double-Pulse Laser-Induced Breakdown Spectroscopy in Elemental Analysis of Magnesium Alloy

In this study,a stand-off and collinear double pulse laser-induced breakdown spectroscopy(DP LIBS) system was designed,and the magnesium alloy samples at a distance of 2.5 m away from the LIBS system were measured.The effect of inter-pulse delay on spectra was studied,and the signal enhancement was observed compared to the single pulse LIBS(SP LIBS).The morphology of the ablated crater on the sample indicated a higher efficiency of surface pretreatment in DP LIBS.The calibration curves of Ytterbium(Y) and Zirconium(Zr) were investigated.The square of the correlation coefficient of the calibration curve of element Y reached up to 0.9998.     

Cluster analysis of polymers using laser-induced breakdown spectroscopy with K-means

Laser-induced breakdown spectroscopy(LIBS) combined with K-means algorithm was employed to automatically differentiate industrial polymers under atmospheric conditions.The unsupervised learning algorithm K-means were utilized for the clustering of LIBS dataset measured from twenty kinds of industrial polymers.To prevent the interference from metallic elements,three atomic emission lines(C I 247.86 nm,H I 656.3 nm,and O I 777.3 nm) and one molecular line C–N(0,0) 388.3 nm were used.The cluster analysis results were obtained through an iterative process.The Davies–Bouldin index was employed to determine the initial number of clusters.The average relative standard deviation values of characteristic spectral lines were used as the iterative criterion.With the proposed approach,the classification accuracy for twenty kinds of industrial polymers achieved 99.6%.The results demonstrated that this approach has great potential for industrial polymers recycling by LIBS.     

Nanosecond laser preheating effect on ablation morphology and plasma emission in collinear dual-pulse laser-induced breakdown spectroscopy

Focus-offset collinear dual-pulse laser-induced breakdown spectroscopy is designed and used to investigate the laser ablation and spectral intensity with an aluminum alloy sample. The laser crater morphologies and ablation volumes were measured. An inter-pulse time delay dependent ablation efficiency on a nanosecond laser-heated sample was observed, which was similar to the trend of spectral intensity versus inter-pulse time delay in the delay time less than 3 μs. Based on the observation, the nanosecond pulse laser preheating effect on subsequent second laser ablation and signal enhancement is discussed, which will be helpful for understanding the ablation and signal enhancement mechanism in the standard collinear DP-LIBS technique.     

Development of a fiber-coupled laser-induced breakdown spectroscopy instrument for analysis of underwater debris in a nuclear reactor core

To inspect the post-accident nuclear core reactor of the TEPCO Fukushima Daiichi nuclear power plant (F1-NPP), a transportable fiber-coupled laser-induced breakdown spectroscopy (LIBS) instrument has been developed. The developed LIBS instrument was designed to analyze underwater samples in a high-radiation field by single-pulse breakdown with gas flow or double-pulse breakdown. To check the feasibility of the assembled fiber-coupled LIBS instrument for the analysis of debris material (mixture of the fuel core, fuel cladding, construction material and so on) in the F1-NPP, we investigated the influence of the radiation dose on the optical transmittance of the laser delivery fiber, compared data quality among various LIBS techniques for an underwater sample and studied the feasibility of the fiber-coupled LIBS system in an analysis of the underwater sample of the simulated debris in F1-NPP. In a feasible study conducted by using simulated debris, which was a mixture of CeO₂ (surrogate of UO₂), ZrO₂ and Fe, we selected atomic lines suitable for the analysis of materials, and prepared calibration curves for the component elements. The feasible study has guaranteed that the developed fiber-coupled LIBS system is applicable for analyzing the debris materials in the F1-NPP.     

Temporal and spatial dynamics of optical emission from laser ablation of the first wall materials of fusion device

Laser-induced breakdown spectroscopy(LIBS) has been developed to in situ diagnose the chemical compositions of the first wall in the EAST tokamak. However, the dynamics of optical emission of the key plasma-facing materials, such as tungsten, molybdenum and graphite have not been investigated in a laser produced plasma(LPP) under vacuum. In this work, the temporal and spatial dynamics of optical emission were investigated using the spectrometer with ICCD.Plasma was produced by an Nd:YAG laser(1064 nm) with pulse duration of 6 ns. The results showed that the typical lifetime of LPP is less than 1.4 μs, and the lifetime of ions is shorter than atoms at ~10~(-6)mbar. Temporal features of optical emission showed that the optimized delay times for collecting spectra are from 100 to 400 ns which depended on the corresponding species. For spatial distribution, the maximum LIBS spectral intensity in plasma plume is obtained in the region from 1.5 to 3.0 mm above the sample surface. Moreover, the plasma expansion velocity involving the different species in a multicomponent system was measured for obtaining the proper timing(gate delay time and gate width) of the maximum emission intensity and for understanding the plasma expansion mechanism. The order of expansion velocities for various species is V_C~+ V_H V_(Si)~+ V_(Li) V_(Mo) V_W.These results could be attributed to the plasma sheath acceleration and mass effect. In addition, an optimum signal-to-background ratio was investigated by varying both delay time and detecting position.     

A systematic study of the initial electrical and radiation hardnessproperties of reoxidized nitrided oxides by rapid thermalprocessing

The initial electrical and radiation hardness properties of MOS capacitors with reoxidized nitrided oxides (RNO) structures are systematically investigated by changing the pressure, temperature, and times of nitridation and reoxidation in rapid thermal processes. It was found that the initial flat-band voltage (V_fb) and midgap interface trap density (D_itm) are strongly dependent on the growth conditions and show concave or convex “turnaround” dependency on some process parameters. This may be explained by the hydrogen evaporation and oxygen passivation mechanisms. The radiation induced flat-band voltage shift (ΔV_fb) and midgap interface trap density shift (ΔD_itm) are also growth-condition dependent and show different “turnaround” dependencies on some process parameters from those observed in initial properties. This may be explained by the variations of the amount of hydrogen-related species such as Si-NH, Si-H, or Si-OH, and nitrogen-related species, such as Si-N, in the oxide bulk and at the Si/SiO₂ interface. Finally, the sample with a reoxidation pressure of 250 torr, a reoxidation temperature of 1050°C, and a reoxidation time of 100 s is suggested to be the most radiation-hard together with good initial properties for RNO devices     

Spectral Enhancement of Laser-Induced Breakdown Spectroscopy in External Magnetic Field

In this paper the spectral enhancement of laser-induced breakdown spectroscopy (LIBS) for copper plasma in the presence of a magnetic field is investigated and the temporal-and spatial-resolved plasma emission spectra are analyzed. Experimental results show that the copper plasma atomic and ion spectra have been enhanced in the presence of the external magnetic field. In addition, the Cu I 521.82 nm spectral intensity evolution with delay time appears to have a double peak around the delay time of 2 μs, but that of Cu II 507.57 nm has a sharp decrease because of the electron-atom three body recombination process. The plasma temperature with magnetic confinement is lower than that of the case in the absence of magnetic fields. Finally, the spectral enhancement mechanisms of laser induced breakdown spectroscopy with magnetic confinement are analyzed.     

Simultaneous Determination of Trace Lead and Chromium in Water Using Laser-Induced Breakdown Spectroscopy and Paper Substrate

Toxic metals such as lead and chromium in aqueous solutions have been analyzed simultaneously by laser-induced breakdown spectroscopy(LIBS), in which the ordinary printing paper is used as a liquid absorber which was immerged into Pb(NO3)2and Cr(NO3)3aqueous solution to enrich the heavy metals. This method overcomes the drawbacks of splashing and low sensitivity in ordinary LIBS analysis of water, in which a laser beam is directly focused on a liquid surface. A good signal intensity and reproducibility has been demonstrated. The Pb 405.78 nm and Cr 427.48 nm spectral lines are used as the analytical lines. The variation of line intensity with immersion time was investigated. The calibration curve for quantitative measurement of Pb and Cr in water was established, and the detection limits are 0.033 mg/L and 0.026 mg/L respectively,which is about 2-3 orders of magnitude better than that in the ordinary LIBS analysis of heavy metal in solution.