Plasma-grating-induced breakdown spectroscopy Download: 756次
1 Introduction
Laser-induced breakdown spectroscopy (LIBS) is one of the most effective tools used to study the interaction between lasers and matter. Compared with other techniques, like atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy, LIBS has some unique advantages including the capacity of direct analysis without a complex pretreatment of the sample, rapid response, and multiple elemental analysis ability. LIBS is suitable for special requirements of practical solid,1
For traditional LIBS systems, nanosecond (ns) pulse lasers are widely used. But due to some adverse impacts like laser emission intensity, long pulse duration, and plasma shielding effect,11 the ns-LIBS has drawbacks, including low reproducibility and repeatability, low signal-to-noise ratios, and difficult molecular measurements. In contrast, the pulse duration of femtosecond lasers is much shorter, such that there is no plasma shielding effect and the interaction time of laser and matter is very short. Therefore, signal-to-background ratios and resolutions of spectral lines are higher.12,13 Meanwhile, because of the high power density, materials could be ionized and dissociated quickly, and thus the ions and molecular fragments could be stimulated effectively.14
Filament-induced breakdown spectroscopy (FIBS) combines the LIBS technique and a femtosecond laser filament. 17 When a high-intensity femtosecond laser pulse transmits in the air, due to the dynamic balance between the self-focusing of the Kerr effect and the defocusing of the plasma formed by multiphoton ionization, a long and stable laser plasma channel forms, i.e., a femtosecond (fs) laser filament.18
In this work, we propose and demonstrate the plasma-grating-induced breakdown spectroscopy (GIBS) technique. The plasma grating is generated by two noncollinear femtosecond filaments. GIBS is proven to be useful to overcome the drawbacks of ns-LIBS, fs-LIBS, and FIBS. With GIBS, the signal intensity enhancement is greater than 3 times that obtained by FIBS with the same initial pulse. The plasma evolution is studied, and the lifetime of plasma-grating-induced plasma is found to be about twice that of filament-induced plasma. Due to the absence of plasma shielding effects, the high power, and electron density of the femtosecond plasma grating, materials could be ionized and dissociated in a more uniform manner so that the matrix effect is reduced and quantitative analyses are feasible.
2 Experimental Details
2.1 Experimental Setup
Our experimental schematic is shown in
Fig. 1. Experimental schematic. Top view of the noncollinear interaction area where two filaments interfere and create a plasma grating, with a focus lens collecting the plasma emission into the spectrometer from the side direction after plasma grating ablating the sample pellet.
2.2 Sample Preparation
Five standard reference soil samples (GSS-08, GSS-04, GSS-03, GSS-20, and GSF-03) were used for the present study. All soil samples were ground carefully in a mortar to become homogeneous. Then 0.5 g of the obtained mixture powder was filled into a steel dye of 13 mm diameter. A hydraulic press was applied on the powder to obtain a pellet. The pressure of 4 MPa and time of 1 min were used for all pellets. Prepared pellets were then put on the motorized stage so that fresh materials could be irradiated and ablated continuously.
3 Results and Discussion
3.1 Signal Enhancement of GIBS
Plasma gratings are generated due to the nonlinear interaction of two filaments.30,32 The power density and electron density are higher than a single fs filament with the same pulse energy due to the constructive interference in the two-beam overlapping area. In this section, the exposure time of the spectrometer is set as 0.05 s, considering the pulse interval of 0.001 s of the 1 kHz repetitive femtosecond pulses, which means that each spectrum obtained under the integrate-on-chip mode is accumulated with 50 shots. Soil sample GSS-08 was used here.
Fig. 2. (a) Intensity of the Si 288.2 nm line as a function of the laser pulse energy detected with the FIBS and GIBS systems. (b) Intensity of the Si 288.2 nm line obtained by interaction of two beams with different polarizations.
3.2 Time Evolution of Induced Plasma
Based on the results described above, in order to better understand the signal enhancement of the GIBS, we analyzed the time evolution of the plasma emission from filament and plasma grating ablation, respectively. Soil sample GSS-08 was used. The time evolutions of the intensities of four spectral lines (Al 394.5 nm, Ca 393.4 nm, Mg 517.3 nm, and Si 288.2 nm) are shown in
Fig. 3. Time evolution for intensities of four spectral lines (Al 394.5 nm, Ca 393.4 nm, Mg 517.3 nm, and Si 288.2 nm) detected with (a) an FIBS and (b) a GIBS system.
3.3 Reduction of Matrix Effect
In order to study the matrix effect, soil samples doped with a Cr element of different concentrations were used as target samples. The target elemental concentrations of these soil samples are given in
Table 1. Element concentrations of soil samples in the experiment.
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First, we used the previous ns-LIBS experimental system described in Refs. 8 and 34 to detect these soil samples.
Fig. 4. Intensity of the Cr 425.43 nm line as a function of the prepared Cr concentration detected with (a) ns-LIBS, (b) fs-LIBS, (c) FIBS, and (d) GIBS systems.
In order to quantitatively assess the matrix effect among different samples, we calculated the average relative error of prediction (REP) for other soil samples with respect to the calibration curve of S3, as defined by
For ns-LIBS, due to long pulse durations, there is a plasma shielding effect,11 which refers to the fact that laser-induced plasma absorbs part of incident laser energy and prevents the efficient coupling between laser and matter, resulting in a low utilization rate of laser energy. For different samples, the constituents and opacity of plasma are different, so that plasma of different samples will shield postpulse and subsequently ablate the sample surface with different efficiencies and to different extents. Therefore, the spectral line intensity of the same element in different samples would exhibit an inconsistent relationship with respect to elemental concentrations. But for fs laser pulse, before the plasma formation and other thermal response, the interaction between the laser and matter has finished and all the laser energy has already been deposited on the sample surface. There are no further effects or processes that impact the plasma formation. Power density and electron density are very high inside the fs filaments, and especially higher in the fs plasma grating so that the sample pellets could be ablated. As a result, FIBS and especially GIBS could overcome the matrix effect effectively.
4 Conclusions
We used a plasma grating from the interference of two noncollinear fs filaments to ablate and detect sample pellets. The interaction of two filaments leads to more intense electron acceleration and collision so that the local electron density inside the plasma grating is higher than that obtained with a single fs filament. The signal intensity of spectral lines detected by GIBS is enhanced by more than 3 times that obtained from a single FIBS system. The lifetime of grating-induced plasma is apparently extended. Finally, we demonstrate that using the GIBS technique, materials could be ionized and dissociated, effectively leading to reduction of the matrix effect. The GIBS technique could be a promising tool to detect samples hard to melt, ionize, or dissociate, and samples with a complex matrix.
Article Outline
Mengyun Hu, Junsong Peng, Sheng Niu, Heping Zeng. Plasma-grating-induced breakdown spectroscopy[J]. Advanced Photonics, 2020, 2(6): 065001.