CN203324186U - Laser induced breakdown spectroscopy system based on wavelength division multiplexing and time domain overlapping - Google Patents
Laser induced breakdown spectroscopy system based on wavelength division multiplexing and time domain overlapping Download PDFInfo
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- CN203324186U CN203324186U CN2013203602348U CN201320360234U CN203324186U CN 203324186 U CN203324186 U CN 203324186U CN 2013203602348 U CN2013203602348 U CN 2013203602348U CN 201320360234 U CN201320360234 U CN 201320360234U CN 203324186 U CN203324186 U CN 203324186U
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Abstract
The patent discloses a laser induced breakdown spectroscopy system based on wavelength division multiplexing and time domain overlapping. A laser pulse is divided into a plurality of laser pulses with different wavelengths and different time sequences, which are then combined, by a plurality of proportion spectroscopes, a plurality of time delay optical components, and a plurality of frequency doubling crystals or optical parametric oscillators; the plurality of laser pulses with different wavelengths stimulate the same point of a sample sequentially with certain time delay. As the stimulation effects of different types of atoms by the laser pulses with different wavelengths are different, the wavelength multiplexing LIBS (laser induced breakdown spectroscopy) method disclosed by the utility model can be used for improving the detection effect obviously; meanwhile, because of the time delay and overlapping in time domains of the laser pulses, a next laser pulse is injected when a plasma generated by the induction of a previous laser pulse is to be cooled down, and thus the detection signal to noise ratio can be improved obviously.
Description
Technical field
This patent relates to a kind of laser spectrum detection method, relates in particular to a kind of based on wavelength-division multiplex and overlapping Laser-induced Breakdown Spectroscopy (Laser-induced breakdown spectroscopy the is called for short LIBS) system of time domain.
Background technology
Laser-induced Breakdown Spectroscopy (LIBS) Detection Techniques are the laser pulses that utilize pulsed laser to send, focus on sample through condenser lens, obtain high-octane laser pulse on focus point, make the sample ablation, evaporate, excite with ionization after form the plasma spark of high temperature, high pressure, high electron density, give off the spectrum that comprises atom and ion characteristic spectral line, the element that can be used for detecting material forms.
The low repetition single-pulse laser of traditional LIBS detection method utilization is as driving source, when monopulse LIBS surveys, the shock wave that the sample target material surface produces makes that to be excited the plasma emission spectrum signal attenuation that produces larger, the signal therefore recorded a little less than, noise is smaller.In addition, because single-pulse laser centre wavelength is single, only for Partial Elements, have higher launching efficiency, the element that therefore can't obtain more all sidedly testing sample forms.
For improve noise that LIBS surveys when the element of Overall Acquisition testing sample form, this patent proposes a kind of based on wavelength-division multiplex and overlapping LIBS system and the detection method of time domain, the method is decomposed into some bundles to the beam of laser pulse to be had the laser pulse of different wave length, different sequential and is closed bundle, and the laser pulse of these different wave lengths passes through certain time delay and the same point of the overlapping excited sample of time domain successively.Can select different frequency-doubling crystals and OPO, obtain one group of suitable wavelength-division multiplex Wavelength distribution λ
1, λ
2, λ
3..., λ
N-1, λ
n(n represents wavelength-division multiplex wavelength sum), the element that the LIBS spectral analysis excited by the laser pulse with these Wavelength distribution obtains testing sample all sidedly forms.Simultaneously, due to each laser pulse, in the time delay of time domain and overlapping, at previous laser pulse, induce the grade of generation to be about to when cooling inject a rear laser pulse in vitro, can significantly improve the detection signal to noise ratio (S/N ratio).
Summary of the invention
It is a kind of based on wavelength-division multiplex and the overlapping LIBS system of time domain that the purpose of this patent is to provide, and overcomes the deficiency of traditional monopulse LIBS, and the noise that raising LIBS surveys the when element of Overall Acquisition testing sample forms.
As shown in Figure 1, comprise ratio spectroscope, high-energy solid pulse laser, time delay optical module, optical delay line, frequency-doubling crystal or optical parametric oscillator, total reflective mirror, half-reflecting half mirror, dichroic mirror, Multicolour mirror, catoptron with holes, optical fiber ICCD spectrometer, computing machine and condenser lens based on wavelength-division multiplex and the overlapping Laser-induced Breakdown Spectroscopy system of time domain.
Sending a branch of wavelength by high-energy solid pulse laser 2 is λ
1Nanosecond pulse laser, be divided into two-way through 1 than n-1 ratio spectroscope 1, seeing through 1 is λ than the wavelength of n-1 ratio spectroscope 1
1At first first laser pulse that accounts for the n of laser gross energy/mono-arrives condenser lens 19 through Multicolour mirror B20, after line focus, through the aperture at catoptron with holes 18 centers, arrives sample target 16 surfaces, and the sample target is induced the generation plasma through laser pulse; Laser pulse is induced the LIBS signal of generation, and through catoptron 18 reflections with holes, lens 17 focus on the subsidiary fibre-optical probe end face of optical fiber ICCD spectrometer 14, and what optical fiber ICCD spectrometer 14 will be accepted is λ by wavelength
1The LIBS signal data that produces of induced with laser be sent to computing machine 15;
Through 1, than the wavelength of n-1 ratio spectroscope 1 reflection, be λ
1The laser pulse that accounts for the n/n-1 of laser gross energy enter first group of time delay optical module 3 and see through first group of frequency-doubling crystal or optical parametric oscillator 6 to change wavelength into be λ
2Laser pulse, through n-2 than 1 ratio spectroscope 9 be divided into the reflection and the transmission two-way, the wavelength wherein obtained by reflection is λ
2Second laser pulse of one of n that energy is the laser total amount focused on by lens 19 after reflecting by Multicolour mirror A12 and Multicolour mirror B20, laser pulse after focusing is through the aperture at catoptron with holes 8 centers, arrive sample target 16 surfaces, the sample target is induced the generation plasma through laser pulse; Laser pulse is induced the LIBS signal of generation, and through catoptron 18 reflections with holes, lens 17 focus on the subsidiary fibre-optical probe end face of optical fiber ICCD spectrometer 14, and what optical fiber ICCD spectrometer 14 will be accepted is λ by wavelength
2The LIBS signal data that produces of induced with laser be sent to computing machine 15; Now because laser pulse has passed through time delay τ, guarantee that the sample target induces the plasma of generation to be about to when cooling be injected into second laser pulse at first laser pulse;
Through n-2, than the wavelength of 1 ratio spectroscope 9 transmissions, be λ
2The laser pulse of n/n-2 that energy is the laser total amount through second group of time delay optical module 3 and see through second group of frequency-doubling crystal or optical parametric oscillator 6 to change wavelength into be λ
3Laser pulse, the ratio spectroscope is divided into reflection and transmission two-way, and the wavelength wherein obtained by reflection is λ
3The 3rd laser pulse of one of n that energy is the laser total amount be for inducing the sample target to produce the LIBS signal, the transmitted light part by the 3rd group of time delay optical module 3 and see through the 3rd group of frequency-doubling crystal or optical parametric oscillator 6 to change wavelength into be λ
4Laser pulse and the sample of light splitting deexcitation again target; By mode work like this until system completes wavelength is λ
N-2Laser pulse conversion, being converted to wavelength through n-2 group time delay optical module 3 and n-2 group frequency-doubling crystal or optical parametric oscillator 6 is λ
N-1Laser pulse be divided into two tunnels through half-reflecting half mirror 11, take and provide corresponding wavelength as λ by excited sample in a road of reflection
N-1The LIBS signal of laser, it is λ that a route n-1 group time delay optical module 3 of transmission and n-1 group frequency-doubling crystal or optical parametric oscillator 6 are treated to wavelength
nLaser pulse, be used for inducing sample target generation-LIBS signal after total reflective mirror 10 reflection; Like this, system has obtained one group and has been respectively λ for the wavelength of inducing the sample target to produce the LIBS signal
1, λ
2, λ
3..., λ
N-1, λ
nLaser pulse, wherein n is the total number of wavelength-division multiplex wavelength that system is selected.
Described time delay optical module 3 is comprised of incidence reflection mirror 3.1, prism 3.2 and outgoing catoptron 3.3, n-1 prism 3.2 in all n-1 group time delay optical modules 3 all is arranged on unique optical delay line 4 by same support 5, the distance of prism 3.2 and incidence reflection mirror 3.1 and outgoing catoptron 3.3 in all time delay optical modules 3 of the meticulous adjusting of optical delay line 4, realize the identical time delay of all adjacent laser pulses by changing light path.
Induced the LIBS signal of generation by the laser pulse of the n with n wavelength, through mirror reflects with holes, lens focus is to the subsidiary fibre-optical probe end face of optical fiber ICCD spectrometer, and fibre-optical probe is arranged on structure of fiber_optic, conveniently adjusted for accurate focusing.Carry out the unlatching of ICCD and the accurate control of closing moment by the software on the computing machine connected with optical fiber ICCD spectrometer, can gather, store the LIBS signal of being induced generation by the laser pulse of the n with n wavelength, with the accurate analysis of the component that carries out the sample target.
Due to the laser pulse of the different wave length stimulation effect difference to dissimilar atom, can select different frequency-doubling crystals and OPO, obtain one group of suitable wavelength-division multiplex Wavelength distribution λ
1, λ
2, λ
3..., λ
N-1, λ
n(n represents wavelength-division multiplex wavelength sum), the element that the LIBS spectral analysis excited by the laser pulse with these Wavelength distribution obtains testing sample all sidedly forms.
The wavelength-division multiplex LIBS method that this patent proposes can obviously improve Effect on Detecting, simultaneously, due to each laser pulse, in the time delay of time domain and overlapping, at previous laser pulse, induce the grade of generation to be about to when cooling inject a rear laser pulse in vitro, can significantly survey signal to noise ratio (S/N ratio).
The accompanying drawing explanation
The schematic diagram that Fig. 1,2 is this patent, in figure: 1---1 than n-1 ratio spectroscope; 2---the high-energy solid pulse laser; 3---the time delay optical module; 3.1---the incidence reflection mirror; 3.2---prism; 3.3---the outgoing catoptron; 4---optical delay line; 5---support; 6---frequency-doubling crystal (or optical parametric oscillator OPO); 7---total reflective mirror A; 8---half-reflecting half mirror; 9---n-2 is than 1 ratio spectroscope; 10---total reflective mirror B; 11---dichroic mirror A; 12---Multicolour mirror A; 13---structure of fiber_optic; 14---optical fiber ICCD spectrometer; 15---computing machine; 16---the sample target; 17---lens; 18---catoptron with holes; 19---condenser lens; 20---Multicolour mirror B.
Annotate: n represents the total number of the wavelength of wavelength-division multiplex, and ICCD represents Intensified Charge Coupled Device.τ represents the time delay between adjacent laser pulse.
Embodiment
The principle of this patent as shown in Figure 1, 2, is selected n=4 in this specific embodiment, and the total number of wavelength-division multiplex wavelength is 4.
Sending a branch of wavelength by high-energy solid pulse laser 2 is λ
1The nanosecond pulse laser of=1064nm is divided into two-way through 1 to 3 ratio spectroscope 1:
The wavelength that sees through 1 to 3 ratio spectroscope 1 is λ
1First laser pulse (account for laser gross energy 1/4th) at first arrives condenser lens 19 through Multicolour mirror B20; line focus and through the aperture at catoptron with holes 18 centers; arrive sample target 16 surfaces; require sample target 16 surfaces to equal the focal length (being focus) of condenser lens 19 to the distance of condenser lens 19, induce the generation plasma;
Enter first group of time delay optical module 3 through the laser pulse of 1 to 3 ratio spectroscope 1 reflection (account for laser gross energy 3/4ths), time delay optical module 3 is comprised of incidence reflection mirror 3.1, prism 3.2, outgoing catoptron 3.3, all prisms 3.2 of respectively organizing time delay optical module 3 all are arranged on optical delay line 4 by same support 5, can be by optical delay line 4 every group of prisms 3.2 of meticulous adjusting simultaneously and incidence reflection mirror 3.1 and the distance of outgoing catoptron 3.3, reach and change the purpose that light path is realized time delay.After this laser pulse passes through first group of time delay optical module 3, changing wavelength into through first group of frequency-doubling crystal (or optical parametric oscillator OPO) 6 is λ
2Laser pulse, through 2 to 1 ratio spectroscopes 9 reflection and transmissions: (energy becomes 1/4th of laser total amount to second laser pulse wherein obtained by reflection, and wavelength is λ
2), by Multicolour mirror A12 reflection, then after Multicolour mirror B20 reflection, with first laser pulse similarly, arrive condenser lens 19, line focus and through the aperture at catoptron with holes 18 centers, arrive sample target 16 surfaces, because passed through time delay, so this wavelength is λ
2Laser pulse than wavelength, be λ
1First laser pulse arrives evening, can be by regulating two interpulse time delay τ (as Fig. 2) of optical delay line 4 fine adjustment, produce certain overlappingly in time domain, make first laser pulse induce the grade of generation to be about to when cooling inject second pulse in vitro;
The laser pulse produced through 2 to 1 ratio spectroscope 9 transmissions, its energy is 1/2nd of laser gross energy, after second group of time delay assembly 3 time delay, changing wavelength into through second group of frequency-doubling crystal (or optical parametric oscillator OPO) 6 is λ
3Laser pulse, through half-reflecting half mirror 8 reflection and transmissions: (energy becomes 1/4th of laser total amount to the 3rd laser pulse wherein obtained by reflection, and wavelength is λ
3), by dichroic mirror A11 reflection, Multicolour mirror A12 transmission, then after Multicolour mirror B20 reflection, with second laser pulse similarly, arrive condenser lens 19, line focus and through the aperture at catoptron with holes 18 centers, arrive sample target 16 surfaces, because passed through time delay, so this wavelength is λ
3Laser pulse than wavelength, be λ
2Second laser pulse arrive evening; because system is with a support 5, the prism 3.2 in all time delay optical modules 3 all to be fixed on an optical delay line 4 and due to the symmetry of light channel structure; so realized the time delay τ (as Fig. 2) identical to all adjacent laser pulses, made similarly second laser pulse induce the grade of generation to be about to when cooling inject the 3rd laser pulse in vitro;
The laser pulse produced through half-reflecting half mirror 8 transmissions, its energy is 1/4th of laser gross energy, after the 3rd group of time delay assembly 3 time delays, changing wavelength into through the 3rd group of frequency-doubling crystal (or optical parametric oscillator OPO) 6 is λ
4Laser pulse, through total reflective mirror A7 and total reflective mirror B10 reflection, transmission is by dichroic mirror A11 and Multicolour mirror A12, again after Multicolour mirror B20 reflection, with the 3rd laser pulse similarly, arrive condenser lens 19, line focus and through the aperture at catoptron with holes 18 centers, arrive sample target 16 surfaces, because passed through time delay τ, so this wavelength is λ
4Laser pulse than wavelength, be λ
3The 3rd laser pulse arrive evening, in time domain, produce certain overlapping, and the 3rd laser pulse induce generation etc. be about to the 4th pulse when cooling in vitro and just in time arrive.
Induced the LIBS signal of generation by the many laser pulses with multi-wavelength, through catoptron 18 reflections with holes, lens 17 focus on the subsidiary fibre-optical probe end face of optical fiber ICCD spectrometer 14, and fibre-optical probe is arranged on structure of fiber_optic 13, conveniently adjusted for accurate focusing.Carry out the unlatching of ICCD and the accurate control of closing moment by the software on the computing machine 15 connected with optical fiber ICCD spectrometer 14, can gather, store the LIBS signal of being induced generation by the many laser pulses with multi-wavelength, with the accurate analysis of the component that carries out sample target 16.
Due to the laser pulse of the different wave length stimulation effect difference to dissimilar atom, can select different frequency-doubling crystals and OPO, obtain one group of suitable wavelength-division multiplex Wavelength distribution λ
1, λ
2, λ
3..., λ
N-1, λ
n(n represents wavelength-division multiplex wavelength sum), the element that the LIBS spectral analysis excited by the laser pulse with these Wavelength distribution obtains testing sample all sidedly forms.
The wavelength-division multiplex LIBS method that this patent proposes can obviously improve Effect on Detecting, simultaneously, due to each laser pulse, in the time delay of time domain and overlapping, at previous laser pulse, induce the grade of generation to be about to when cooling inject a rear laser pulse in vitro, can significantly survey signal to noise ratio (S/N ratio).
Claims (2)
1. one kind based on wavelength-division multiplex and the overlapping Laser-induced Breakdown Spectroscopy system of time domain, it comprises ratio spectroscope, high-energy solid pulse laser, time delay optical module, optical delay line, frequency-doubling crystal or optical parametric oscillator, total reflective mirror, half-reflecting half mirror, dichroic mirror, Multicolour mirror, catoptron with holes, optical fiber ICCD spectrometer, computing machine and condenser lens, it is characterized in that:
Sending a branch of wavelength by high-energy solid pulse laser (2) is λ
1Nanosecond pulse laser, be divided into two-way through 1 than n-1 ratio spectroscope (1), seeing through 1 is λ than the wavelength of n-1 ratio spectroscope (1)
1Account for first laser pulse of the n of laser gross energy/mono-through Multicolour mirror B(20) at first arrive condenser lens (19), pass the aperture at catoptron with holes (18) center after line focus, arrive sample target (16) surface, the sample target is induced the generation plasma through laser pulse; Laser pulse is induced the LIBS signal of generation, and through catoptron with holes (18) reflection, lens (17) focus on the subsidiary fibre-optical probe end face of optical fiber ICCD spectrometer (14), and what optical fiber ICCD spectrometer (14) will be accepted is λ by wavelength
1The LIBS signal data that produces of induced with laser be sent to computing machine (15);
Through 1, than the wavelength of n-1 ratio spectroscope (1) reflection, be λ
1The laser pulse that accounts for the n/n-1 of laser gross energy enter first group of time delay optical module (3) and see through first group of frequency-doubling crystal or optical parametric oscillator (6) to change wavelength into be λ
2Laser pulse, through n-2 than 1 ratio spectroscope (9) be divided into the reflection and the transmission two-way, the wavelength wherein obtained by reflection is λ
2Second laser pulse of one of n that energy is the laser total amount is by Multicolour mirror A(12) and Multicolour mirror B(20) by lens (19), focused on after reflection, laser pulse after focusing is through the aperture at catoptron with holes (8) center, arrive sample target (16) surface, the sample target is induced the generation plasma through laser pulse; Laser pulse is induced the LIBS signal of generation, and through catoptron with holes (18) reflection, lens (17) focus on the subsidiary fibre-optical probe end face of optical fiber ICCD spectrometer (14), and what optical fiber ICCD spectrometer (14) will be accepted is λ by wavelength
2The LIBS signal data that produces of induced with laser be sent to computing machine (15); Now because laser pulse has passed through time delay τ, guarantee that the sample target induces the plasma of generation to be about to when cooling be injected into second laser pulse at first laser pulse;
Through n-2, than the wavelength of 1 ratio spectroscope (9) transmission, be λ
2The laser pulse of n/n-2 that energy is the laser total amount through second group of time delay optical module (3) and see through second group of frequency-doubling crystal or optical parametric oscillator (6) to change wavelength into be λ
3Laser pulse, the ratio spectroscope is divided into reflection and transmission two-way, and the wavelength wherein obtained by reflection is λ
3The 3rd laser pulse of one of n that energy is the laser total amount be for inducing the sample target to produce the LIBS signal, the transmitted light part by the 3rd group of time delay optical module (3) and see through the 3rd group of frequency-doubling crystal or optical parametric oscillator (6) to change wavelength into be λ
4Laser pulse and light splitting again; By mode work like this until system completes wavelength is λ
N-2Laser pulse conversion, being converted to wavelength through n-2 group time delay optical module (3) and n-2 group frequency-doubling crystal or optical parametric oscillator (6) is λ
N-1Laser pulse be divided into two tunnels through half-reflecting half mirror (11), a road of reflection is for to provide by wavelength be λ
N-1The LIBS signal of generation that laser is induced, it is λ that a route n-1 group time delay optical module (3) of transmission and n-1 group frequency-doubling crystal or optical parametric oscillator (6) are treated to wavelength
nLaser pulse, be used for inducing sample target generation-LIBS signal after total reflective mirror (10) reflection; Like this, system has obtained one group and has been respectively λ for the wavelength of inducing the sample target to produce the LIBS signal
1, λ
2, λ
3..., λ
N-1, λ
nLaser pulse, wherein n is the total number of wavelength-division multiplex wavelength that system is selected.
2. according to claim 1 a kind of based on wavelength-division multiplex and the overlapping Laser-induced Breakdown Spectroscopy system of time domain, it is characterized in that: described time delay optical module (3) is by incidence reflection mirror (3.1), prism (3.2) and outgoing catoptron (3.3) form, n-1 prism (3.2) in all n-1 group time delay optical modules (3) all passes through same support (5) and is arranged on unique optical delay line (4), the distance of prism (3.2) and incidence reflection mirror (3.1) and outgoing catoptron (3.3) in all time delay optical modules of the meticulous adjusting of optical delay line (4) (3), come to realize the identical time delay of all adjacent laser pulses by changing light path.
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| CN103335986A (en) * | 2013-06-21 | 2013-10-02 | 中国科学院上海技术物理研究所 | Laser-induced breakdown spectroscopy (LIBS) system and method based on wavelength division multiplexing and time domain overlapping |
| CN104181146A (en) * | 2013-05-22 | 2014-12-03 | 中国科学院光电研究院 | Multipulse laser-induced breakdown spectrum on-line detection system |
| CN104833665A (en) * | 2015-03-30 | 2015-08-12 | 天津大学 | Multicomponent simultaneous measurement device in optics engine cylinder combustion process |
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| CN104181146A (en) * | 2013-05-22 | 2014-12-03 | 中国科学院光电研究院 | Multipulse laser-induced breakdown spectrum on-line detection system |
| CN103335986A (en) * | 2013-06-21 | 2013-10-02 | 中国科学院上海技术物理研究所 | Laser-induced breakdown spectroscopy (LIBS) system and method based on wavelength division multiplexing and time domain overlapping |
| CN103335986B (en) * | 2013-06-21 | 2015-05-13 | 中国科学院上海技术物理研究所 | Laser-induced breakdown spectroscopy (LIBS) system and method based on wavelength division multiplexing and time domain overlapping |
| CN104833665A (en) * | 2015-03-30 | 2015-08-12 | 天津大学 | Multicomponent simultaneous measurement device in optics engine cylinder combustion process |
| CN104897625A (en) * | 2015-06-02 | 2015-09-09 | 中国科学院上海技术物理研究所 | Combined laser induced spectrum system for detecting Mars substance components |
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| CN108181711A (en) * | 2018-01-16 | 2018-06-19 | 北京工业大学 | Extend the method in chevilled silk service life using double laser beams breakdown spectral relaxation effect |
| CN108680559A (en) * | 2018-04-29 | 2018-10-19 | 天津大学 | Laser induced breakdown spectroscopy ICCD time discrimination measurement method and systems |
| CN110658633A (en) * | 2019-08-14 | 2020-01-07 | 武汉安扬激光技术有限责任公司 | Ultrafast laser of output multi-wavelength |
| CN113394651A (en) * | 2021-06-08 | 2021-09-14 | 中国科学院精密测量科学与技术创新研究院 | Multi-pulse laser delay adjustable combined transmitting device |
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