技术领域technical field
本发明涉及一种激光诱导击穿光谱和光腔衰荡光谱同位素成像仪，尤其涉及一种可分辨碳同位素的增强型激光诱导击穿光谱仪。The invention relates to a laser-induced breakdown spectrum and optical cavity ring-down spectrum isotope imager, in particular to an enhanced laser-induced breakdown spectrometer capable of resolving carbon isotopes.
背景技术Background technique
激光诱导击穿光谱（Laser-induced Breakdown Spectroscopy，LIBS技术）是一种激光烧蚀光谱分析技术，激光聚焦在测试位点，当激光脉冲的能量密度大于击穿阈值时，即可产生等离子体。基于这种特殊的等离子体剥蚀技术，通常在原子发射光谱技术中分别独立的取样、原子化、激发三个步骤均可由脉冲激光激发源一次实现。等离子体能量衰退过程中产生连续的轫致辐射以及内部元素的离子发射线，通过光纤光谱仪采集光谱发射信号，分析谱图中元素对应的特征峰强度即可以用于样品的定性以及定量分析，但该技术中待测样品一般为大气样品，其特点为待测物质含量稀薄，单次测得的LIBS信号微弱。Laser-induced breakdown spectroscopy (LIBS technology) is a laser ablation spectroscopy analysis technique. The laser is focused on the test site. When the energy density of the laser pulse is greater than the breakdown threshold, plasma can be generated. Based on this special plasma ablation technology, the three independent steps of sampling, atomization and excitation in atomic emission spectroscopy can be realized by a pulsed laser excitation source at one time. Continuous bremsstrahlung and ion emission lines of internal elements are generated during the energy decay of the plasma, and the spectral emission signals are collected by a fiber optic spectrometer, and the characteristic peak intensities corresponding to the elements in the analysis spectrum can be used for qualitative and quantitative analysis of the sample, but In this technique, the sample to be tested is generally an atmospheric sample, which is characterized by a thin content of the substance to be tested, and a single measured LIBS signal is weak.
光腔衰荡光谱技术（Cavity Ring Down Spectroscopy, CRDS技术）是近几年迅速发展起来的一种吸收光谱检测技术。其原理是利用脉冲激光在由两个反射率为99%以上的反射镜组成的衰荡腔内来回反射，衰荡腔中为被测气体，腔外采用高响应速率的探测器接收随时间变化的光强。测量结果部署脉冲激光涨落的影响，具有灵敏度高、信噪比、高抗干扰能力强等优点。Cavity Ring Down Spectroscopy (CRDS technology) is an absorption spectrum detection technology developed rapidly in recent years. The principle is to use the pulsed laser to reflect back and forth in the ring-down cavity composed of two mirrors with a reflectivity of more than 99%. of light intensity. The measurement results are influenced by pulsed laser fluctuations, and have the advantages of high sensitivity, signal-to-noise ratio, and high anti-interference ability.
发明内容Contents of the invention
本发明为了解决现有技术中存在的问题，提供一种将LIBS技术和CRDS技术相结合的，可以区分同位素并且可以增强LIBS成像效果的增强型激光诱导击穿光谱仪。In order to solve the problems in the prior art, the present invention provides an enhanced laser-induced breakdown spectrometer that combines LIBS technology and CRDS technology, can distinguish isotopes and can enhance LIBS imaging effect.
为了达到上述目的，本发明提出的技术方案为：一种可分辨碳同位素的增强型激光诱导击穿光谱仪，包括光腔、激光器和探测器，所述光腔内设有衰荡反射镜和光线聚焦反射镜，所述衰荡反射镜设置于光腔的两侧且相对设置，光线聚焦反射镜位于光腔的底部，光腔的一侧壁设有激光口，所述激光器位于激光口处，光腔另一侧壁和顶部分别设有第一探测口和第二探测口，所述第二探测口与光线聚焦反射镜相对设置，第一、第二探测口处均设有一探测器。In order to achieve the above object, the technical solution proposed by the present invention is: an enhanced laser-induced breakdown spectrometer capable of resolving carbon isotopes, including an optical cavity, a laser, and a detector, and the optical cavity is provided with a ring-down mirror and light Focusing mirrors, the ring-down mirrors are arranged on both sides of the optical cavity and oppositely arranged, the light focusing mirrors are located at the bottom of the optical cavity, a side wall of the optical cavity is provided with a laser port, and the laser is located at the laser port, The other side wall and the top of the optical cavity are respectively provided with a first detection port and a second detection port. The second detection port is arranged opposite to the light focusing reflector, and a detector is provided at the first and second detection ports.
对上述技术方案得劲进一步设计为：所述激光口处设有凸透镜，激光器发射的激光经过凸透镜后进入光腔。The above-mentioned technical solution is further designed as follows: the laser port is provided with a convex lens, and the laser light emitted by the laser enters the optical cavity after passing through the convex lens.
所述衰荡反射镜和光线聚焦反射镜均为凹面镜，两个衰荡反射镜和光线聚焦反射镜中间形成光线聚焦室，所述衰荡反射镜和光线聚焦反射镜的凹面均面向光线聚焦室。Both the ring-down reflector and the light focusing reflector are concave mirrors, and a light focusing chamber is formed between the two ring-down reflectors and the light focusing reflector, and the concave surfaces of the ring-down reflector and the light focusing reflector both face the light focusing room.
所述衰荡反射镜为反射率为99%以上的高反射镜片。The ring-down mirror is a highly reflective mirror with a reflectivity above 99%.
所述光腔上设有进气口。An air inlet is provided on the optical cavity.
本发明的有益效果为：The beneficial effects of the present invention are:
1、本发明的装置通过激光在光腔内的多次反射聚焦，每次激光聚焦都可以击穿待测大气样品，因此，每个焦点可以得到一个LIBS信号，多个焦点可以得到多个LIBS信号，这样在大气颗粒物的探测中，可以提高LIBS信号强度。1. The device of the present invention focuses through multiple reflections of the laser in the optical cavity, and each time the laser is focused, the atmospheric sample to be measured can be broken down. Therefore, one LIBS signal can be obtained for each focus, and multiple LIBS can be obtained for multiple focuses signal, so that in the detection of atmospheric particulate matter, the LIBS signal strength can be improved.
2、由于大气样品具有不稳定性，信号会有波动，而本技术方案中多个焦点会产生多个LIBS信号，可以测取数据的平均值，提高稳定度，同时增强信噪比，减少失真。2. Due to the instability of atmospheric samples, the signal will fluctuate, but in this technical solution, multiple focal points will generate multiple LIBS signals, which can measure the average value of the data, improve stability, and at the same time enhance the signal-to-noise ratio and reduce distortion .
3、由于LIBS光谱的局限性，无法区分同位素，从而不能追本溯源，了解碳的来源。本技术方案将LIBS光谱与CRDS光谱进行结合，可以探测大气CO2振动相关的CRDS光谱，通过光谱的吸收峰来区分同位素12C和13C，使装置更具实用性。3. Due to the limitations of LIBS spectrum, it is impossible to distinguish isotopes, so it is impossible to trace the source and understand the source of carbon. This technical solution combines LIBS spectrum with CRDS spectrum, can detect atmospheric CO2 vibration-related CRDS spectrum, and distinguish isotopes12 C and13 C through the absorption peak of the spectrum, making the device more practical.
附图说明Description of drawings
图1为本发明的结构示意图。Fig. 1 is a structural schematic diagram of the present invention.
图2为激光在光腔内的多次反射示意图。Fig. 2 is a schematic diagram of multiple reflections of laser light in the optical cavity.
图3为光腔内聚焦点示意图。Fig. 3 is a schematic diagram of the focal point in the optical cavity.
上述附图中：1-光腔，11-激光口，12-进气口，13-第一探测口，14-第二探测口，2-衰荡反射镜，3-光线聚焦反射镜，4-激光器，5-第一探测器，6-第二探测器，7-凸透镜，8-聚焦点。In the above drawings: 1-optical cavity, 11-laser port, 12-inlet port, 13-first detection port, 14-second detection port, 2-ringdown mirror, 3-ray focusing mirror, 4 -laser, 5-first detector, 6-second detector, 7-convex lens, 8-focus point.
具体实施方式Detailed ways
下面结合附图以及具体实施例对本发明进行详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.
本发明的可分辨碳同位素的增强型激光诱导击穿光谱仪结构图1所示，包括光腔1、激光器4、第一探测器5和第二探测器6，光腔1内设有衰荡反射镜2和光线聚焦反射镜3，衰荡反射镜2设有两个，为反射率为99%以上的高反射镜片，分别设置于光腔1的两侧且相对设置，光线聚焦反射镜3位于光腔1的底部，两个衰荡反射镜2和光线聚焦反射镜3中间形成光线聚焦室，衰荡反射镜2和光线聚焦反射镜3均为凹面镜，且凹面均面向光线聚焦室；光腔1的一侧壁设有激光口11，另一侧壁设有司第一探测口13，顶部设有第二探测口14，激光口11处设有凸透镜7，激光器2位于激光口处，且发射的激光经过凸透镜后进入光腔1，第二探测口14与光线聚焦反射镜3相对设置，第一、第二探测口处分别设有第一探测器5和第二探测器6。The structure of the enhanced laser-induced breakdown spectrometer capable of resolving carbon isotopes of the present invention is shown in Figure 1, including an optical cavity 1, a laser 4, a first detector 5 and a second detector 6, and the optical cavity 1 is provided with a ring-down reflection mirror 2 and light focusing reflector 3, the ring-down reflector 2 is provided with two, which are high reflective mirrors with a reflectivity of more than 99%, and are respectively arranged on both sides of the optical cavity 1 and are relatively arranged, and the light focusing reflector 3 is located at At the bottom of the optical cavity 1, a light focusing chamber is formed between the two ring-down reflectors 2 and the light focusing reflector 3, the ring-down reflector 2 and the light focusing reflector 3 are concave mirrors, and the concave surfaces all face the light focusing chamber; One side wall of the cavity 1 is provided with a laser port 11, the other side wall is provided with a first detection port 13, the top is provided with a second detection port 14, the laser port 11 is provided with a convex lens 7, the laser device 2 is located at the laser port, and The emitted laser light enters the optical cavity 1 after passing through the convex lens. The second detection port 14 is set opposite to the light focusing mirror 3. The first and second detection ports are respectively provided with a first detector 5 and a second detector 6 .
光腔1上还设有进气口12，进气口可设置于光腔壁上的任何不遮挡光路的位置。An air inlet 12 is also provided on the optical cavity 1, and the air inlet can be arranged at any position on the wall of the optical cavity that does not block the light path.
实施例Example
上述增强型激光诱导击穿光谱仪具体如何对同位素分辨成像，本实施例以二氧化碳中的同位素12CO2和13CO2为例进行说明，如果实验中要探测二氧化碳中13CO2离子的信息，区分出同位素12CO2。首先在光腔内泵浦入待测样品，在其进入探测系统后，选取合适脉宽的激光进行实验。二氧化碳分子的红外光谱有两个吸收谱带，一个对应反对称伸缩振动，一个对应变形振动，12CO2反对称伸缩振动的波数是2369cm-1，而变形振动波数是667cm-1，13CO2反对称伸缩振动的波数是2283cm-1。因此本实施例采用激光泵浦染料产生可调谐激光，得到输出波长为4380nm的激光束(13CO2红外光谱的吸收谱带），在脉冲激光器产生的4380nm激光束1聚焦作用下，使得样品颗粒物呈现等离子体状态，与此同时，激光在经过设有两个反射率为99%以上的衰荡反射镜的光腔后，在光腔内来回反射（如图2所示），多次聚焦后形成多个聚焦点8由光线聚焦反射镜3收集信号被第二探测器6所接收（如图3所示）。How the above-mentioned enhanced laser-induced breakdown spectrometer specifically performs isotope resolution imaging, this embodiment takes the isotopes12 CO2 and13 CO2 in carbon dioxide as an example to illustrate, if the experiment is to detect the information of13 CO2 ions in carbon dioxide, distinguish out isotope12 CO2 . First, the sample to be tested is pumped into the optical cavity, and after it enters the detection system, a laser with a suitable pulse width is selected for the experiment. The infrared spectrum of carbon dioxide molecules has two absorption bands, one corresponds to the antisymmetric stretching vibration, and the other corresponds to the deformation vibration. The wave number of the antisymmetric stretching vibration of12 CO2 is 2369cm-1 , while the wave number of the deformation vibration is 667cm-1 ,13 CO2 The wavenumber of the antisymmetric stretching vibration is 2283cm-1 . Therefore, in this embodiment, laser pumping dyes are used to generate tunable laser light to obtain a laser beam with an output wavelength of 4380nm (the absorption band of13 CO2 infrared spectrum). At the same time, after passing through the optical cavity with two ring-down mirrors with a reflectivity of more than 99%, the laser is reflected back and forth in the optical cavity (as shown in Figure 2), and after multiple focusing A plurality of focusing points 8 are formed, and the light-focusing mirror 3 collects signals to be received by the second detector 6 (as shown in FIG. 3 ).
再调谐激光泵浦得到输出波长为4220nm(12CO2红外光谱的吸收谱带）的激光束，同样进行上一步的步骤，然后采用高响应速率的第一探测器5接收随时间变化的光强，数据传入数据处理系统，可以快速判别所测得的样品同位素信息。Then tune the laser pump to obtain a laser beam with an output wavelength of 4220nm (the absorption band ofthe 12 CO2 infrared spectrum), perform the same steps as in the previous step, and then use the first detector 5 with a high response rate to receive the light intensity varying with time , the data is transmitted to the data processing system, which can quickly identify the measured sample isotope information.
激光在光腔内来回反射聚焦作用，多次击穿样品产生的等离子体，第二探测器6收集得到的LIBS光谱，可以在所含13CO2浓度极低情况下实现对颗粒物中的元素进行准确的定性和定量分析。而由第一探测器5所收集到的信息为激光脉冲的衰减过程，记录激光在腔内的衰荡时间，辨别同位素。The laser beam reflects and focuses back and forth in the optical cavity, and breaks down the plasma generated by the sample multiple times. The LIBS spectrum collected by the second detector 6 can realize the analysis of the elements in the particles when the concentration of13 CO2 is extremely low. Accurate qualitative and quantitative analysis. The information collected by the first detector 5 is the attenuation process of the laser pulse, which records the ring-down time of the laser in the cavity and identifies isotopes.
本发明的技术方案不局限于上述各实施例，凡采用等同替换方式得到的技术方案均落在本发明要求保护的范围内。The technical solutions of the present invention are not limited to the above-mentioned embodiments, and all technical solutions obtained by adopting equivalent replacement methods fall within the protection scope of the present invention.
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| CN201810437422.3ACN108398421A (en) | 2018-05-09 | 2018-05-09 | A kind of enhanced laser induced breakdown spectrograph of distinguishable carbon isotope |
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| CN201810437422.3ACN108398421A (en) | 2018-05-09 | 2018-05-09 | A kind of enhanced laser induced breakdown spectrograph of distinguishable carbon isotope |
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| CN108398421Atrue CN108398421A (en) | 2018-08-14 |
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| CN201810437422.3APendingCN108398421A (en) | 2018-05-09 | 2018-05-09 | A kind of enhanced laser induced breakdown spectrograph of distinguishable carbon isotope |
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| RJ01 | Rejection of invention patent application after publication | Application publication date:20180814 | |
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