CN117288741A - Target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy high-sensitivity element analysis method - Google Patents
Target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy high-sensitivity element analysis method Download PDFInfo
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- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 title claims abstract description 43
- 238000004458 analytical method Methods 0.000 title claims abstract description 24
- 238000001228 spectrum Methods 0.000 claims abstract description 28
- 238000002679 ablation Methods 0.000 claims abstract description 20
- 239000010453 quartz Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003287 optical effect Effects 0.000 claims abstract description 10
- 230000005855 radiation Effects 0.000 claims abstract description 10
- 239000013307 optical fiber Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 23
- 230000006378 damage Effects 0.000 claims description 11
- 239000012212 insulator Substances 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- 238000000921 elemental analysis Methods 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 3
- 239000000523 sample Substances 0.000 description 73
- 238000005516 engineering process Methods 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000003303 reheating Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000010183 spectrum analysis Methods 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 238000010206 sensitivity analysis Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001299 laser-induced shock wave plasma spectroscopy Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241001226615 Asphodelus albus Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
Abstract
The invention discloses a target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy high-sensitivity element analysis method, which comprises the following steps of: the first step, a first pulse laser emits pre-ablation laser, and the pre-ablation laser is reflected by a first reflecting sheet and a semi-reflecting sheet and focused on the surface of a target by a first focusing lens to generate pre-ablation plasma; the second step, the second pulse laser emits laser with lower energy, and the laser is reflected by the second reflecting sheet and focused on the surface of the sample by the second focusing lens to generate sample plasma; the third step, the third pulse laser emits laser, the laser is focused on the surface of the target through the first focusing lens after passing through the semi-reflecting sheet to generate target plasma, and the sample plasma is heated by the target plasma to emit obviously enhanced optical radiation; and fourthly, collecting optical radiation of the composite plasma by the first quartz lens and the second quartz lens to the incident end of the optical fiber, recording a spectrum by a spectrometer, and transmitting the spectrum data to a computer for subsequent processing and analysis.
Description
Technical Field
The invention belongs to the technical fields of photoelectric detection, application spectrum technology, spectrum analysis and the like, and is particularly suitable for the field of high-sensitivity analysis of material elements developed based on laser-induced breakdown spectroscopy, in particular to a target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy high-sensitivity element analysis method.
Background
The laser-induced breakdown spectroscopy is a novel qualitative and quantitative analysis technique for the spectrum of a substance element. It focuses a short pulse laser on a sample (which may be solid, liquid or gas), and due to the high laser power density at the focus, a laser-induced plasma is generated, during which the ablated sample is broken down and atomized and emits a characteristic line of each element. And carrying out spectral analysis on the spectrum of the plasma to qualitatively or quantitatively obtain the element concentration information in the sample. A technique called single pulse laser induced breakdown spectroscopy in which only one laser pulse is used to generate plasma and to perform spectroscopic analysis.
The laser-induced breakdown spectroscopy technology has the advantages of no need of complex sample preparation process, high analysis speed, field analysis and field or remote analysis when analyzing sample elements, and the like. However, compared with the mature element analysis technology, such as atomic absorption spectrum, inductively coupled plasma-atomic emission spectrum, inductively coupled plasma-mass spectrum technology and X-ray fluorescence spectrum technology, the method has the defects of low sensitivity, poor stability and the like. Moreover, the single pulse laser induced breakdown spectroscopy technique also presents an inherent contradiction between low sample damage and high spectral analysis sensitivity when analyzing solid samples.
The use of orthogonal double-pulse or triple-pulse excitation has the potential to resolve the above contradictions. A significant signal enhancement can be achieved without further destruction of the sample by ablating a small sample with a low energy laser pulse incident perpendicular to the sample surface, and using a second (and third) laser parallel to the sample surface to improve the gas environment and excite the sample plasma. Orthogonal double-pulse laser-induced breakdown spectroscopy can be classified into pre-ablation and reheating according to the time sequence of arrival of two laser pulses, and many related literature reports exist. Regarding the orthogonal three-pulse laser-induced breakdown spectroscopy, there is only one English literature (David Prochazka, pavel Poriizka, jan Novotny et al, triple-pulse LIBS: laser-induced breakdown spectroscopy signal enhancement by combination of pre-absorption and re-heating laser pulses, journal of Analytical Atomic Spectrometry,2020,35,293-300), the technique adopted in this literature is excited by three lasers from three directions perpendicular to each other, which combines two types of orthogonal two-pulse laser-induced breakdown spectroscopy techniques of pre-ablation and reheating together, and a better signal enhancement effect than the orthogonal two-pulse laser-induced breakdown spectroscopy technique is obtained. Because of the introduction of the pre-etched laser, the signal enhancement effect is about 5 times based on the original reheating orthogonal double-pulse laser-induced breakdown spectroscopy technology.
Disclosure of Invention
The invention aims to establish an orthogonal three-pulse laser-induced breakdown spectroscopy method, wherein a solid target is added at the side of a sample to be analyzed, and pre-ablation and reheating laser acts on the solid target from the direction parallel to the surface of the sample, so that the effects of changing the gas environment and exciting the plasma of the sample are achieved; the laser ablating the sample ablates the sample from a direction perpendicular to the surface of the sample. Due to various physical mechanisms (including improving the utilization rate of reheat laser energy and introducing a collision mechanism), the signal intensity of the sample with the solid target has a remarkable enhancement effect compared with that without the solid target, which is beneficial to carrying out high-sensitivity analysis of solid sample elements on the premise of micro-damage.
The invention is realized by at least one of the following technical schemes.
The target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy high-sensitivity element analysis method comprises the following steps:
the first step, a first pulse laser emits pre-ablation laser, and after being reflected by a first reflecting sheet and a semi-reflecting sheet, the pre-ablation laser is focused on the surface of a target by a first focusing lens to generate pre-ablation plasma, so that an instantaneous, high-temperature and low-pressure gas environment is formed;
the second step, the second pulse laser emits laser, and the laser is reflected by the second reflecting sheet and focused on the surface of the sample by the second focusing lens to generate sample plasma;
the third step, the third pulse laser emits laser, the laser is focused on the surface of the target through the first focusing lens after passing through the semi-reflecting sheet to generate target plasma, and the sample plasma is heated by the target plasma to emit obviously enhanced optical radiation;
and fourthly, collecting optical radiation of the composite plasma by the first quartz lens and the second quartz lens to the incident end of the optical fiber, recording a spectrum by a spectrometer, and transmitting the spectrum data to a computer for subsequent processing and analysis.
Further, the laser beams of the first pulse laser and the third pulse laser are transmitted in a line and act on the target, and the laser beams of the second pulse laser are transmitted in a direction orthogonal to the laser beams of the first pulse laser and the third pulse laser and act on the sample.
Further, the pulse delay controller is responsible for synchronously controlling the time sequence of the three pulse lasers and the delay of signal acquisition of the spectrometer.
Further, the laser pulse of the first pulse laser precedes the laser pulse of the second pulse laser by 4-10 microseconds; the laser pulse of the third pulse laser is 4-10 microseconds later than the laser pulse of the second pulse laser.
Further, the spectrum acquisition is 1.0-4.0 microseconds after the laser pulse of the third pulse laser, and the sampling gate width is 0.2 microseconds-2.0 milliseconds.
Further, the sample is driven by the two-dimensional motion platform to do uniform motion at a speed of 0.5-3.0 mm/s.
Further, the target is placed against the sample and is rotated by the motor at a rotational speed of 1-10 revolutions per minute.
Further, the target contains all solids including conductors, semiconductors and insulators, and the target is in the shape of a sheet or rod.
Further, the samples analyzed are solid samples, including conductors, semiconductors, and insulators.
Further, the laser energy of the second pulse laser is lower than the laser energy of the first and third pulse lasers to ensure that the sample is damaged as little as possible.
Compared with the prior art, the invention has the following advantages and effects compared with the prior art:
the ablation of the first and the samples is completed by the laser (namely, the second laser) emitted by the second pulse laser, and the damage degree of the sample can be reduced by reducing the energy of the laser, or pits with small diameters can be ablated on the surface of the sample. This is of great value for reducing sample damage and improving image resolution in developing surface element distribution imaging analysis;
secondly, as the target is added and two paths of lasers are adopted to sequentially act on the surface of the target, the signal enhancement factor is obviously improved. Under the condition of low ablation laser energy, the signal enhancement factor can reach 2-3 orders of magnitude, so that the method is favorable for high-sensitivity material element analysis; when the target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy is used for analyzing a solid sample, the damage degree to the sample can be reduced to the minimum, and meanwhile, higher spectral analysis sensitivity can be obtained, so that the inherent contradiction between low sample damage and high spectral analysis sensitivity existing in the process of analyzing the solid sample by adopting the single-pulse laser-induced breakdown spectroscopy is better solved. The invention is also helpful for the high-resolution imaging analysis technology of the element distribution on the surface of the solid sample. Since the signal of the sample element is enhanced, the ablation amount of the sample can be further reduced under the condition of the same detection sensitivity, which is equivalent to reducing the ablation pit diameter and improving the resolution of the image.
Thirdly, by optimizing the material and surface structure of the target, the method also has considerable technical potential for further improving the signal enhancement factor, so that newer technologies are derived.
Drawings
FIG. 1 is a schematic diagram of a target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy system according to the present embodiment;
FIG. 2 is a spectrum contrast chart of the present embodiment;
FIG. 3 is a spectrum chart recorded for evaluating the detection limit of lithium in this example;
wherein 1-a first pulsed laser; 2-a first reflective sheet; 3-semi-reflecting sheet; 4-a first focusing lens; 5-target and rotating platform; 6-a second pulsed laser; 7-a second reflective sheet; 8-a second focusing lens; 9-a sample and a two-dimensional motion platform; 10-a third pulse laser; 11-a first quartz lens, 12-a second quartz lens; 13-an optical fiber; 14-spectrometer; 15-a computer; 16-pulse delay controller.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The invention provides an instrument system of a target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy technology and an analysis method for carrying out micro-ablation high-sensitivity element analysis on a solid sample based on the technology. The technique employs three pulsed lasers, a solid target and a solid sample to be analyzed. One path of low-energy laser is focused on the sample from the direction vertical to the surface of the sample to ablate the sample and generate sample plasma; the other two paths of laser with higher energy are in a collinear mode, respectively precede and lag the laser for ablating the sample in time, are focused on the surface of the solid target, and sequentially generate pre-etching plasma and target plasma. The sample plasma interacts with the target plasma to emit significantly enhanced optical radiation. Qualitative or quantitative analysis of the sample elements can be performed by observing their spectra.
The target enhanced orthogonal three-pulse laser induced breakdown spectroscopy analysis system shown in fig. 1 comprises a first pulse laser 1, a first reflecting sheet 2, a semi-reflecting sheet 3, a first focusing lens 4, a solid target 5, a second pulse laser 6, a second reflecting sheet 7 for reflection, a second focusing lens 8, a third pulse laser 10, a first quartz lens 11, a second quartz lens 12, an optical fiber 13, a spectrometer 14, a computer 15 and the like.
The first pulse laser 1 emits a first path of pre-etched laser, after being reflected by the first reflecting sheet 2 and the semi-reflecting sheet 3, the first focusing lens 4 is used for weakly focusing on the surface of the solid target 5 to generate a pre-etched plasma, so that an instantaneous, high-temperature and low-pressure gas environment is formed; the second pulse laser 6 emits a second path of laser light, and the second path of laser light is reflected by the second reflecting sheet 7 and focused on the surface of the sample 9 by the second focusing lens 8 to generate sample plasma; the third pulse laser 10 finally emits a third laser beam, the third laser beam is focused on the surface of the target 5 by the first focusing lens 4 after passing through the semi-reflecting sheet 3 to generate target plasma, and the sample plasma emits obviously enhanced optical radiation after being heated by the target plasma; the incident end of the optical fiber 13 is collected by the first quartz lens 11 and the second quartz lens 12, and the spectrum is recorded by the spectrometer 14. A computer 15 for recording and storing the spectral data; the pulse delay controller 16 is used to control the relative delay between the three laser pulses and the sample gate delay of the spectrometer 14. The target 5 is rotated by a motor and the sample 9 is mounted on a two-dimensional motion platform. During the spectroscopic analysis both the sample and the target are in motion.
The target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy high-sensitivity elemental analysis method can analyze any solid sample, and the solid target can also be any solid including conductors, semiconductors and insulators, and different targets can be selected according to different analysis objects.
As an example, the sample of this example was a chip pre-doped with trace lithium elements and the target was brass. As shown in figure 1, the target enhanced orthogonal three-pulse laser induced breakdown spectroscopy high-sensitivity element analysis method comprises the following steps:
in the first step, the first pulse laser 1 emits a first path of pre-etched laser light, and after the pre-etched laser light is reflected by the first reflecting sheet 2 and the semi-reflecting sheet 3, the pre-etched laser light is weakly focused on the surface of the target 5 by the first focusing lens 4 to generate a pre-etched plasma. The plasma has the main functions of forming a transient, high-temperature and low-pressure gas environment on the surfaces of the sample and the target, and laying a foundation for the reheat laser to better interact with the target;
a second step, the second pulse laser 6 emits a second path of laser light, and the second path of laser light is reflected by the second reflecting sheet 7 and focused on the surface of the sample 9 by the second focusing lens 8 to generate sample plasma; the energy of the laser can be as low as possible, so that the damage or damage degree to the sample can be reduced;
and thirdly, finally, a third pulse laser 10 emits a third laser path, and the third laser path is focused on the surface of the target 5 by the first focusing lens 4 after passing through the semi-reflecting sheet 3 to generate target plasma. The sample plasma emits significantly enhanced optical radiation after being heated by the target plasma;
and fourthly, collecting optical radiation of the composite plasma by the first quartz lens 11 and the second quartz lens 12 at the incident end of the optical fiber 13, recording a spectrum by the spectrometer 14, and transmitting the spectrum data to the computer 15 for subsequent processing and analysis. The composite plasma is a plasma formed by the interaction of the pre-etch plasma, the sample plasma, and the target plasma.
The pulse delay controller 16 is responsible for synchronously controlling the time sequence of the three pulse lasers and the delay of signal acquisition of the spectrometer, and the time width of the signal acquisition window is set by the spectrometer.
As a preferred embodiment, the laser pulse of the pulsed laser 1 precedes the laser pulse of the pulsed laser 6 by about 5 microseconds; whereas the laser pulse of the pulsed laser 10 is about 5 microseconds later than the laser pulse of the pulsed laser 6. The spectrum acquisition is then 1.5 microseconds later than the laser pulse of the pulsed laser 10, with a sampling gate width of 2 milliseconds.
During analysis, the sample 9 is driven by a two-dimensional motion platform to do uniform motion at a speed of 1.0mm/s, and the target 5 is driven by a motor to rotate at a speed of 5 revolutions per minute. During the spectroscopic analysis both the sample and the target are in motion.
The obtained spectrum is shown in figure 2, and comprises the measurement result of the target enhanced orthogonal three-pulse laser induced breakdown spectroscopy technology and the measurement result of the single-pulse laser induced breakdown spectroscopy technology. The results of the single pulse laser induced breakdown spectroscopy measurement in fig. 2 are plotted at 10 x magnification, with the laser energy of the ablated sample being 10mJ; the pre-ablation and reheating laser energies were 45mJ; the concentration of lithium was 3.2ppm. Under the current experimental conditions, when the pulse laser 6 adopts 10mJ of laser energy, the spectrum signal intensity of lithium is enhanced by about 80 times compared with the spectrum of single pulse laser induced breakdown by the target enhanced orthogonal three-pulse laser induced breakdown spectrum. Due to the orthogonal spatial arrangement, the damage (or destruction) to the sample is exactly the same in both cases.
Figure 3 demonstrates the improvement in sensitivity when measured using the target enhanced orthogonal three pulse laser induced breakdown spectroscopy technique in the presence of elemental lithium in the wood chips under the foregoing experimental conditions as compared to the sensitivity measured using the 10mJ laser energy single pulse laser induced breakdown spectroscopy technique. The upper part of fig. 3 shows the spectrum obtained when the chip with the lithium concentration of 0.4ppm is analyzed by using the target enhanced orthogonal three pulse laser induced breakdown spectroscopy, the signal intensity of lithium atoms is significantly higher than the background noise; the lower part of fig. 3 shows the spectrum obtained when the chip with a lithium concentration of 8.0ppm was analyzed by single pulse laser induced breakdown spectroscopy, where the signal of lithium atoms could just be measured. The detection limit of lithium element was evaluated by the commonly employed 3 sigma rule (that is, the concentration of the element corresponding to a net signal intensity of 3 times the background standard deviation, i.e., the detection limit of the element), with an improvement of about 30 times as measured using the target enhanced orthogonal three pulse laser-induced breakdown spectroscopy technique compared to that measured using the single pulse laser-induced breakdown spectroscopy technique.
Potassium bicarbonate (insulator) was used as a signal enhancement target and the sample to be analyzed was brass. In this example, the potassium bicarbonate target was prepared by placing dried potassium bicarbonate particles in a tablet press and pressing the particles under a pressure of 21 Mpa. The target was a 3 cm diameter disc, approximately 3 mm thick. The brass sample is a round bar with a diameter of 6 mm. When the laser energy of the second path of ablated sample is 4mJ, the energy of the first path of pre-ablation laser and the energy of the third path of reheating laser are both 30mJ, the relative delay condition between laser pulses and the spectrum data acquisition condition are the same as those of the previous embodiment, and compared with the single pulse laser induced breakdown spectrum adopting the same sample ablation laser energy (4 mJ), the signal intensity of copper and zinc in the sample can obtain the enhancement effect which is higher than 100 times.
And carrying out high-sensitivity analysis on harmful heavy metal element lead in water based on a target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy technology. In this analysis, a lead-free wood chip was used to absorb water and then allowed to dry before being mounted on a sample motion platform, with the target being a pure silver rod. The three paths of laser energy are selected to be 20+10+20mJ, and the relative delay condition among laser pulses and the spectrum data acquisition condition are kept unchanged. In this example, the target enhanced orthogonal three pulse laser induced breakdown spectroscopy can achieve a 60-fold enhancement in the signal intensity of lead in a sample compared to a single pulse laser induced breakdown spectroscopy using the same sample ablative laser energy (10 mJ).
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The target enhanced orthogonal three-pulse laser-induced breakdown spectroscopy high-sensitivity element analysis method is characterized by comprising the following steps of:
the first step, a first pulse laser emits pre-ablation laser, and after being reflected by a first reflecting sheet and a semi-reflecting sheet, the pre-ablation laser is focused on the surface of a target by a first focusing lens to generate pre-ablation plasma, so that an instantaneous, high-temperature and low-pressure gas environment is formed;
the second step, the second pulse laser emits laser, and the laser is reflected by the second reflecting sheet and focused on the surface of the sample by the second focusing lens to generate sample plasma;
the third step, the third pulse laser emits laser, the laser is focused on the surface of the target through the first focusing lens after passing through the semi-reflecting sheet to generate target plasma, and the sample plasma is heated by the target plasma to emit obviously enhanced optical radiation;
and fourthly, collecting optical radiation of the composite plasma by the first quartz lens and the second quartz lens to the incident end of the optical fiber, recording a spectrum by a spectrometer, and transmitting the spectrum data to a computer for subsequent processing and analysis.
2. The method for analyzing the high-sensitivity element of the target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy according to claim 1, wherein the laser beams of the first pulse laser and the third pulse laser are transmitted in a line and act on the target, and the laser beams of the second pulse laser are transmitted in a direction orthogonal to the laser beams of the first pulse laser and the third pulse laser and act on the sample.
3. The method for analyzing the high-sensitivity element of the target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy according to claim 1, wherein the pulse delay controller is responsible for synchronously controlling the time sequence of the three pulse lasers and the delay of signal acquisition of the spectrometer.
4. The method for high-sensitivity elemental analysis of a target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy according to claim 1, wherein the laser pulse of the first pulse laser is 4-10 microseconds before the laser pulse of the second pulse laser; the laser pulse of the third pulse laser is 4-10 microseconds later than the laser pulse of the second pulse laser.
5. The method for high-sensitivity elemental analysis of target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy according to claim 1, wherein the spectrum acquisition is 1.0-4.0 microseconds after the laser pulse of the third pulse laser, and the sampling gate width is 0.2 microseconds-2.0 milliseconds.
6. The method for analyzing the target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy high-sensitivity element according to claim 1, wherein the sample is driven by the two-dimensional motion platform to do uniform motion at a speed of 0.5-3.0 mm/s.
7. The method for target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy (OTA) high-sensitivity elemental analysis according to claim 1, wherein the target is placed in close proximity to the sample and is rotated by a motor at a rotational speed of 1-10 rpm.
8. The method for high-sensitivity elemental analysis of target-enhanced orthogonal three-pulse laser-induced breakdown spectroscopy according to claim 1, wherein the target contains all solids including conductors, semiconductors and insulators, and the target is in the shape of a sheet or a rod.
9. The method of claim 1, wherein the sample is a solid sample including conductors, semiconductors, and insulators.
10. The method of any one of claims 1 to 9, wherein the second pulse laser emits laser energy that is lower than the first and third pulse lasers to ensure as little damage as possible to the sample.
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