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.     

Effect of lens-to-sample distance on spatial uniformity and emission spectrum of flat-top laser-induced plasma

The optimal spectral excitation and acquisition scheme is explored by studying the effect of the lens-to-sample distance (LTSD) on the spatial homogeneity and emission spectra of flat-top laser converging spot induced plasma. The energy distribution characteristics before and after the convergence of the laser beam with quasi flat-top intensity profile used in this study are theoretically simulated and experimentally measured. For an aspheric converging mirror with a focal length of 100 mm, the LTSD (106 mm ≥ LTSD ≥ 96 mm) was changed by raising the stainless-steel sample height. The plasma images acquired by ICCD show that there is air breakdown when the sample is below the focal point, and a ring-like plasma is produced when the sample is above the focal point. When the sample is located near the focal point, the plasma shape resembles a hemisphere. Since the spectral acquisition region is confined to the plasma core and the image contains all the optical information of the plasma, it has a lower relative standard deviation (RSD) than the spectral lines. When the sample surface is slightly higher than the focal plane of the lens, the converging spot has a quasi flat-top distribution, the spatial distribution of the plasma is more uniform, and the spectral signal is more stable. Simultaneously, there is little difference between the RSD of the plasma image and the laser energy. In order to further improve the stability of the spectral signal, it is necessary to expand the spectral acquisition area.     

Image-based plasma morphology determination and LIBS spectra correction in combustion environments

Spectra correction is essential for the quantification of laser-induced breakdown spectroscopy (LIBS) due to the uncertainties in plasma morphology. In this work, we determined the plasma morphology using a charge-coupled device camera and introduced the spectral correction method based on plasma images to a combustion environment. The plasma length, width, volume, and location were extracted from the plasma images. Using a back-scattering setup, the contribution of plasma location fluctuation to the total spectral fluctuation was mitigated. The integral intensity of the plasma image was used as a proxy of the total number density to correct the spectra. Linear relationships were established between the integral intensities of the plasma images and the spectral intensities, under different laser energy levels and gas temperatures. The image-based correction method could significantly reduce the fluctuation of raw spectral intensities when the laser energy was below 240 mJ. Compared with the correction method based on total spectral areas, the proposed method offered significant improvements in the low energy region, which promises to reduce the signal fluctuations in combustion environments while preserving the spatial resolution and mitigating the flow disturbance.     

Self-absorption effects of laser-induced breakdown spectroscopy under different gases and gas pressures

The self-absorption effect is one of the main factors affecting the quantitative analysis accuracy of laser-induced breakdown spectroscopy. In this paper, the self-absorption effects of laserinduced 7050 Al alloy plasma under different pressures in air, Ar, and N₂ have been studied.Compared with air and N₂, Ar significantly enhances the spectral signal. Furthermore, the spectral self-absorption coefficient is calculated to quantify the degree of self-absorption, and the inf...     

Comparison of emission signals for different polarizations in femtosecond laser-induced breakdown spectroscopy

In this study, a femtosecond laser was focused to ablate brass target and generate plasma emission in air. The influence of lens to sample distance(LTSD) on spectral emission of brass plasma under linearly and circularly polarized pulses with different pulse energies was investigated. The results indicated that the position with the strongest spectral emission moved toward focusing lens with increasing the energy. At the same laser energy, the line emission under circularly polarized pulse was stronger compared with linearly polarized pulse for different LTSDs. Next, electron temperature and density of the plasma were obtained with Cu(Ⅰ) lines,indicating that the electron temperature and density under circularly polarized pulse were higher compared to that under linearly polarized pulse. Therefore, changing the laser polarization is a simple and effective way to improve the spectral emission intensity of femtosecond laserinduced plasma.     

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.     

Effect of cylindrical cavity height on laser-induced breakdown spectroscopy with spatial confinement

In this paper,we present a study on the spatial confinement effect of laser-induced plasma with a cylindrical cavity in laser-induced breakdown spectroscopy(LIBS).The emission intensity with the spatial confinement is dependent on the height of the confinement cavity.It is found that,by selecting the appropriate height of cylindrical cavity,the signal enhancement can be significantly increased.At the cylindrical cavity(diameter = 2 mm) with a height of 6 mm,the enhancement ratio has the maximum value(approximately 8.3),and the value of the relative standard deviation(RSD)(7.6%) is at a minimum,the repeatability of LIBS signal is best.The results indicate that the height of confinement cavity is very important for LIBS technique to reduce the limit of detection and improve the precision.     

Comparison of sample temperature effect on femtosecond and nanosecond laser-induced breakdown spectroscopy

In this paper, we investigated the emission spectra of plasmas produced from femtosecond and nanosecond laser ablations at different target temperatures in air. A brass was selected as ablated target of the experiment. The results indicated that spectral emission intensity and plasma temperature showed similar trend for femtosecond and nanosecond lasers, and the two parameters were improved by increasing the sample temperature in both cases. Moreover, the temperature of nanosecond laser-excited plasma was higher compared with that of femtosecond laser-excited plasma, and the increase of the plasma temperature in the case of nanosecond laser was more evident. In addition, there was a significant difference in electron density between femtosecond and nanosecond laser-induced plasmas. The electron density for femtosecond laser decreased with increasing the target temperature, while for nanosecond laser, the electron density was almost unchanged at different sample temperatures.     

Aqueous ruthenium detection by microwave-assisted laser-induced breakdown spectroscopy

Aqueous ruthenium was detected in real-time under ambient conditions using microwave-assisted laser-induced breakdown spectroscopy (MW-LIBS). A 10 mJ laser energy and 750 W microwave power were directed at an open liquid jet sample of ruthenium. It was observed that, for liquid flow, the coupling efficiency between the microwave and the laser-induced plasma was limited to 43%. The improvement in the ruthenium's signal-to-noise ratio with MW-LIBS, with respect to LIBS, was 76-fold. Based on MW-LIBS, the limit of detection for aqueous ruthenium was determined to be 957 ± 84 ppb.     

Influence of sample temperature on the expansion dynamics of laser-induced germanium plasma

In this paper, we investigated the influence of sample temperature on the expansion dynamics and the optical emission spectroscopy of laser-induced plasma, and Ge was selected as the test sample. The target was heated from room temperature(22 °C) to 300 °C, and excited in atmospheric environment by using a Q-Switched Nd:YAG pulse laser with the wavelength of 1064 nm. To study the plasma expansion dynamics, we observed the plasma plume at different laser energies(5.0, 7.4 and 9.4 mJ)and different sample temperatures by using time-resolved image. We found that the heated target temperature could accelerate the expansion of plasma plume. Moreover, we also measured the effect of target temperature on the optical emission spectroscopy and signal-to-noise ratio.     

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.     

Uranium measurements using laser-induced breakdown spectroscopy in lithium chloride-potassium chloride salt of pyroprocessing

In pyroprocessing,uranium(U) is recovered from molten LiCl-KCl salt,and,for safeguard purposes,it is important to analyze the U and Plutonium(Pu) concentrations in a timely manner.In the present work,salt samples containing U were fabricated.The laser used in the present work was an Nd:YAG laser with a wavelength of 532 nm,a laser energy on the sample of11.5 mJ,and a pulse repetition rate of 10 Hz.The plasma emission light was measured with an Echelle spectrometer.A total of 100 points on the sample surface were measured as the laser incident position was changed.The U and potassium(K) peaks in the spectrum were identified.Univariate and multivariate analyzes were conducted to determine the accuracy and limit of detection(LOD) of the laser-induced breakdown spectroscopy.     

Evaluation of gases'molecular abundance ratio by fiber-optic laser-induced breakdown spectroscopy with a metal-assisted method

A metal-assisted method is proposed for the evaluation of gases'molecular abundance ratio in fiber-optic laser-induced breakdown spectroscopy(FO-LIBS).This method can reduce the laser ablation energy and make gas composition identification possible.The principle comes from the collision between the detected gases and the plasma produced by the laser ablation of the metal substrate.The interparticle collision in the plasma plume leads to gas molecules dissociating and sparking,which can be used to determine the gas composition.The quantitative relationship between spectral line intensity and molecular abundance ratio was developed over a large molecular abundance ratio range.The influence of laser ablation energy and substrate material on gas quantitative calibration measurement is also analyzed.The proposed metal-assisted method makes the measurement of gases'molecular abundance ratios possible with an FO-LIBS system.     

Spectral characteristic of laser-induced plasma in soil

The spectral characteristic of laser-induced plasma in soil was studied in this work, laser-induced breakdown spectroscopy was used to analyze the spectral characteristic of plasma under the condition of different time delays and irradiances. Moreover, the time evolution characteristics of plasma temperature and electron density were discussed. Within the time delay range of 0-5 μs,the spectral intensity of the characteristic lines of Si I: 288.158 nm, Ti I: 336.126 nm, Al I:394.400 nm and Fe I: 438.354 nm of the four main elements in two kinds of national standard soil decayed exponentially with time. The average lifetime of the spectral lines was nearly 1.56 μs. Under the condition of different time delays, the spectral intensity of Pb I: 405.78 nm in soil increased linearly with laser energy. However, the slope between the spectral intensity and laser energy decreased exponentially with the increase in time delay, from 4.91 to 0.99 during 0-5 μs. The plasma temperature was calculated by the Boltzmann plot method and the electron density was obtained by inversion of the full width at half maximum of the spectrum. The plasma temperature decreased from 8900 K to 7800 K and the electron density decreased from 1.5 × 10~(17) cm~(-3) to 7.8 × 10~(16) cm~(-3) in the range of 0-5 μs.     

Enhancement of optical emission generated from femtosecond double-pulse laser-induced glass plasma at different sample temperatures in air

In double-pulse laser-induced breakdown spectroscopy(DP-LIBS), the collinear femtosecond double-pulse laser configuration is experimentally investigated with different initial sample temperatures using a Ti:sapphire laser. The glass sample is ablated to produce the plasma spectroscopy. During the experiment, the detected spectral lines include two Na(I) lines(589.0 nm and 589.6 nm) and one Ca(I) line at the wavelength of 585.7 nm. The emission lines are measured at room temperature(22 ℃) and three higher initial sample temperatures(T_s?=?100 ℃, 200 ℃, and 250 ℃). The inter-pulse delay time ranges from-250 ps to 250 ps.The inter-pulse delay time and the sample temperature strongly influence the spectral intensity,and the spectral intensity can be significantly enhanced by increasing the sample temperature and selecting the optimized inter-pulse time. For the same inter-pulse time of 0 ps(single-pulse LIBS), the enhancement ratio is approximately 2.5 at T_s?=?200 ℃ compared with that obtained at T_s?=?22 ℃. For the same inter-pulse time of 150 ps, the enhancement ratio can be up to 4 at T_s?=?200 ℃ compared with that obtained at T_s?=?22 ℃. The combined enhancement effects of the different initial sample temperatures and the double-pulse configuration in femtosecond LIBS are much stronger than that of the different initial sample temperatures or the double-pulse configuration only.     

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.     

Temporal and spatial evolution measurement of laser-induced breakdown spectroscopy on hydrogen retention in tantalum

Fuel retention measurement on plasma-facing components is an active field of study in magnetic confinement nuclear fusion devices.The laser-induced breakdown spectroscopy(LIBS)diagnostic method has been well demonstrated to detect the elemental distribution in PFCs.In this work,an upgraded co-axis LIBS system based on a linear fiber bundle collection system has been developed to measure the hydrogen(H) retention on a tantalum(Ta) sample under a vacuum condition.The spatial resolution measurement of the different positions of the LIBS plasma can be achieved simultaneously with varying delay times.The temporal and spatial evolution results of LIBS plasma emission show that the H plasma observably expands from the delay times of 0-200 ns.The diameter of Ta plasma is about 6 mm which is much less than the size of H plasma after 200 ns.The difference in the temporal and spatial evolution behaviors between H plasma and Ta plasma is due to the great difference in the atomic mass of H and Ta.The depth profile result shows that H retention mainly exists on the surface of the sample.The temporal and spatial evolution behaviors of the electron excited temperature are consistent with that of the Ta emission.The result will further improve the understanding of the evolution of the dynamics of LIBS plasma and optimize the current collection system of in situ LIBS in fusion devices.     

Spatio-temporal evaluation of Zr plasma parameters in a single-beam-splitting double-pulse laser-induced plasma

The plasma shielding effect is one of the major weaknesses of laser-induced breakdown spectroscopy(LIBS) as it causes non-linearity in signal strength. Although LIBS is typically carried out in constant laser energy, this non-linearity causes a reduction in sensitivity. In this work, we systematically examine laser-induced plasma, formed by two different excitation source modes, i.e. single pulse(SP)-excitation and single-beam-splitting double-pulse(SBSDP)-excitation over Zr-2.5% Nb alloy. The two most important plasma parameters influencing the emission line intensity, plasma temperature(T_e) and electron density(N_e) were studied and compared for both modes of laser excitation. Comparison of the results conclusively demonstrates that due to the splitting of the laser energy in the SBS-DP mode, the plasma shielding effect is significantly reduced. The reduced plasma shielding translates to an increased laser–sample coupling under SBS-DP mode. Temporal imaging of the total intensity of the laserinduced plasma in both excitation modes was also studied. The study shows how the plasma shielding effect can be reduced to improve the analytical quality of the LIBS methodology.     

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.     

Heavy Metal Detection in Soils by Laser Induced Breakdown Spectroscopy Using Hemispherical Spatial Confinement

Spatial confinement has great potential for Laser Induced Breakdown Spectroscopy(LIBS) instruments after it has been proven that it has the ability to enhance the LIBS signal strength and repeatability.In order to achieve in-situ measurement of heavy metals in farmland soils by LIBS,a hemispherical spatial confinement device is designed and used to collect plasma spectra,in which the optical fibers directly collect the breakdown spectroscopy of the soil samples.This device could effectively increase the stability of the spectrum intensity of soil.It also has other advantages,such as ease of installation,and its small and compact size.The relationship between the spectrum intensity and the laser pulse energy is studied for this device.It is found that the breakdown threshold is 160 cm~(-2),and when the laser fluence increases to 250 J/cm~2,the spectrum intensity reaches its maximum.Four different kinds of laser pulse energy were set up and in each case the limits of detection of Cd,Cu,Ni,Pb and Zn were calculated.The results show that when the laser pulse fluence was 2.12 GW/cm~2,we obtained the smallest limits of detection of these heavy metals,which are all under 10 mg/kg.This device can satisfy the needs of heavy metal in-situ detection,and in the next step it will be integrated into a portable LIBS instrument.