CN114544589B - A beam concentric dense multi-reversal cavity for gas Raman signal enhancement - Google Patents
A beam concentric dense multi-reversal cavity for gas Raman signal enhancement Download PDFInfo
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Abstract
一种光束共心密集多反腔，包括：首端腔镜与末端腔镜，首端腔镜、末端腔镜中间相对的区域构成增强腔，增强腔用于激光在首端腔镜与末端腔镜之间多次反射，首端腔镜开设多个通光孔，包括第一通光孔与第二通光孔，其中，多个通光孔距离首端腔镜中心的位置均不相同，且多个通光孔与首端腔镜的圆心共线；激光经由第一通光孔沿着光束共心方向进入增强腔；激光从第一通光孔射出增强腔，利用反射装置，经由第二通光孔沿着光束共心方向再次进入增强腔。本发明提出的光束共心密集多反腔，可使激光在腔内反射数百次，且腔内光束共心，大幅提升腔焦点处的激光强度。多组分气体拉曼光谱检测的检出限可达亚ppm量级。
A beam concentric dense multi-reflection cavity includes: a head end cavity mirror and a tail end cavity mirror, the opposite area between the head end cavity mirror and the tail end cavity mirror constitutes an enhancement cavity, the enhancement cavity is used for multiple reflections of laser between the head end cavity mirror and the tail end cavity mirror, the head end cavity mirror is provided with multiple light holes, including a first light hole and a second light hole, wherein the positions of the multiple light holes from the center of the head end cavity mirror are all different, and the multiple light holes are collinear with the center of the head end cavity mirror; the laser enters the enhancement cavity through the first light hole along the beam concentric direction; the laser is emitted from the enhancement cavity from the first light hole, and enters the enhancement cavity again through the second light hole along the beam concentric direction by using a reflection device. The beam concentric dense multi-reflection cavity proposed by the present invention can make the laser reflect hundreds of times in the cavity, and the beam in the cavity is concentric, which greatly improves the laser intensity at the focus of the cavity. The detection limit of multi-component gas Raman spectroscopy detection can reach the sub-ppm level.
Description
Technical Field
The invention belongs to the field of gas Raman spectrum detection, and particularly relates to a beam concentric dense multi-reflection cavity for gas Raman signal enhancement.
Background
The raman spectroscopy irradiates a gas with laser light to generate a raman effect, determines a gas composition by detecting a wavelength of raman scattered light, and determines a gas concentration by detecting an intensity of the scattered light. Compared with other spectrum gas detection methods (such as infrared absorption spectroscopy, photoacoustic spectroscopy and the like), the Raman spectroscopy can realize simultaneous measurement of multi-component mixed gas by utilizing a single-wavelength laser, compared with a method based on infrared absorption effect, the Raman spectroscopy can realize measurement of homonuclear diatomic gas (H 2、O2、N2 and the like), the Raman peak of water vapor is far away from other gases, and the influence of water vapor in a gas sample on the Raman spectroscopy is small. Therefore, the Raman spectroscopy has good application prospect in the field of gas detection.
However, since the raman scattering cross-sectional area of the gas molecules is extremely small, the detection limit of the raman spectroscopy gas detection is high. Therefore, if raman spectroscopy is used for detecting a trace amount of gas, an appropriate signal enhancement method must be employed.
The multi-cavity enhancement method is one of the commonly used gas Raman signal enhancement methods. The multi-reflection cavity utilizes the laser to reflect in the cavity for multiple times and pass through the same point (the focus of the cavity) approximately, so that the beams in the cavity are concentric, the laser intensity at the focus is improved, and the gas Raman signal intensity collected laterally is enhanced. However, in the prior art, the utilization rate of the reflecting mirror of the multi-reflecting cavity capable of enabling the light beams in the cavity to be concentric is low, the reflecting mirror only uses the edge area to reflect laser, the central area is an ineffective area, the reflection times of the laser in the cavity are less, the laser intensity at the focus is low, and the gas Raman signal intensity needs to be further improved.
In summary, the existing multi-reflection cavity capable of enabling the light beams in the cavity to be concentric cannot realize intensive multi-reflection of the light beams in the cavity, and when raman scattered light is collected laterally, the signal enhancement amplitude is low, and the gas detection limit is still high.
The prior art document 1 (CN 108535192A) discloses a laser Raman gas detection device based on multipath quantitative detection, wherein two concave reflectors are arranged in a gas chamber, a first reflector, a triple prism and a high-pressure helium neon tube are coaxially and sequentially arranged on an outer light path on one side of the gas chamber, a second reflector opposite to an opening of the gas chamber is arranged on the other side of the gas chamber, laser output by the high-pressure helium neon tube is reflected by the triple prism to the first reflector of a vertical light path and vertically enters the gas chamber from a window on one side of the gas chamber through the triple prism and the high-pressure helium neon tube, the laser is repeatedly refracted between the two concave reflectors, and is emitted from a window on the other side of the gas chamber to the second reflector opposite to the opening of the gas chamber outside the gas chamber, the laser is reflected by the reflectors and repeatedly refracted between the two concave reflectors again, multipath gas enters the gas chamber through an air inlet on the gas chamber and reacts with the laser to generate Raman signals, and mixed light is collected through a detector module on the gas chamber, and the prior art document 1 has the defects that the reflector forming the cavity has no light through holes, the laser can only enter the cavity from the outside one reflector, and can form at least a larger incident mode. Conversely, if the laser light is incident into the cavity from the light passing hole, a larger number of reflections can be formed. Under the same conditions (same mirror, etc.), even if the mirror has only a single light-passing hole, the multiple reflecting cavities formed by the holed mirror have at least twice as many reflections as those of the non-holed mirror. Furthermore, the technique described in this document does not direct the laser light into the cavity multiple times to further increase the number of reflections of the laser light within the cavity.
The invention has the biggest innovation point that a multi-reflection cavity formed by a multi-pass light hole reflecting mirror is provided, so that laser can enter the cavity for multiple times and be reflected for multiple times. Compared with a multiple reflecting cavity formed by a traditional single-pass unthreaded hole reflecting mirror, the laser reflection cavity can realize more laser reflection times.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the beam concentric dense multi-reflection cavity for enhancing the gas Raman signal, so that laser in the cavity is intensively reflected for multiple times, and the beam passes through the focal point of the cavity during each reflection, thereby improving the laser intensity at the focal point of the cavity, enhancing the gas Raman signal intensity collected laterally, and realizing the detection of the trace gas with low detection limit Raman spectrum.
The invention adopts the following technical scheme.
The beam concentric dense multi-reflection cavity comprises a head end cavity mirror and a tail end cavity mirror, wherein an enhancement cavity is formed in the opposite area between the head end cavity mirror and the tail end cavity mirror, and the enhancement cavity is used for reflecting laser between the head end cavity mirror and the tail end cavity mirror for multiple times;
The head end cavity mirror is provided with a plurality of light through holes, wherein the light through holes comprise a first light through hole and a second light through hole, and the positions of the light through holes from the center of the head end cavity mirror are different;
laser enters the enhancement cavity along the beam concentric direction through the first light-passing hole;
the laser is emitted out of the enhancement cavity from the first light-passing hole, and enters the enhancement cavity again along the beam concentric direction through the second light-passing hole by utilizing a plane reflector.
Further, the head end cavity mirror and the tail end cavity mirror are concave reflectors with the same focal length and the same size, and the distance between the head end cavity mirror and the tail end cavity mirror is 4 times of the focal length.
Further, the light through holes are round light through holes, and the distances from the centers of the light through holes to the centers of the head end cavity mirrors are in an arithmetic progression.
A beam concentric dense multi-reflecting cavity for gas Raman signal enhancement, comprising a beam concentric dense multi-reflecting cavity, a laser, a gas chamber, a Raman light collimating lens, a long-pass filter, a Raman light focusing lens, a spectrometer and a CCD according to any one of claims 1 to 3;
the gas chamber is arranged in the enhancement cavity and is used for filling the gas;
the laser is used for emitting laser light, wherein the laser light is used for exciting gas to generate Raman signals;
the Raman light collimating lens is used for collecting Raman signals and focusing the Raman signals at the beam concentric point;
The long-pass filter, the Raman light focusing lens, the spectrometer and the CCD are sequentially positioned on an extension line from the beam concentric point to the center of the Raman light collimating lens, wherein the long-pass filter is used for filtering interference signals, the Raman light focusing lens is used for focusing Raman light to the spectrometer, and the spectrometer and the CCD are used for detecting Raman signals of the gas to be detected.
Further, the diameters of the head end endoscope and the tail end endoscope are 100mm, and the focal lengths are 200mm.
Further, the light passing hole is round, and the diameter is 3.5mm.
Further, the wavelength of the laser is 532nm, and the power is 1.5W.
Further, the cut-off wavelength of the long-pass filter is 533nm.
Further, the Raman light collimating lens is a spherical lens with a focal length of 50mm, and the Raman light focusing lens is a spherical lens with a focal length of 50mm.
A method for beam-concentric dense multi-reflection cavity for gas raman signal enhancement, comprising the steps of:
step 1, laser enters an enhancement cavity along the beam concentric direction through a first light through hole, and is reflected between a head end cavity mirror and a tail end cavity mirror for multiple times;
And 2, the laser is emitted out of the enhancement cavity from the first light through hole, and enters the enhancement cavity again along the beam concentric direction through the second light through hole by using the plane reflector, so as to enhance the Raman signal of the gas at the beam concentric position.
Compared with the prior art, the invention has the following advantages:
(1) The existing multi-reflecting cavity with concentric beams in the cavity can reflect laser light tens times, and at most 100 times. The laser beam provided by the invention is concentric, dense and multi-reflecting cavity, so that the laser is reflected hundreds of times in the cavity, and the laser intensity at the focus of the cavity is greatly improved. The detection limit of the multi-component gas Raman spectrum detection can reach the sub ppm level.
Drawings
Fig. 1 is a schematic diagram of a beam-centered multi-reflecting cavity according to an embodiment of the present disclosure.
Fig. 2 is a front view of a spot distribution on a head end endoscope provided by an embodiment of the present disclosure.
Fig. 3 is a schematic diagram of a structure of a beam-concentric dense multi-reflective cavity for gas raman signal enhancement provided by an embodiment of the present disclosure.
FIG. 4 is a Raman spectrum of a multicomponent gas according to an embodiment of the present disclosure.
The reference numerals in the figure are 101, a head end cavity mirror, 102, a tail end cavity mirror, 103, a laser, 104, an air chamber, 105, a Raman light collimating lens, 106, a long-pass filter, 107, a Raman light focusing lens, 108, a spectrometer, 109, a CCD, 201, a first light through hole, 202, a second light through hole, 203, a third light through hole, 204, a fourth light through hole, 301 and a light beam concentric point.
Detailed Description
The application is further described below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present application, and are not intended to limit the scope of the present application.
As shown in fig. 1, embodiment 1 of the present invention provides a beam-concentric dense multi-reflecting cavity comprising a head end cavity mirror 101, a tail end cavity mirror 102 and planar mirrors.
The head-end cavity mirror 101 is a concave mirror with a first focal length toRepresentation having a first diameter toIn the illustration, a plurality of light-passing holes (for example, a first light-passing hole 201, a second light-passing hole 202, a third light-passing hole 203 and a fourth light-passing hole 204 in fig. 1) are provided to pass the lightThe representation is made of a combination of a first and a second color,,Indicating the number of light-passing holesThe distance between the center and the center of the head-end endoscope 101 is set to beThe representation, wherein,I.e. different light passing holes are at different distances from the centre of the lens, as shown in fig. 1.
In a preferred but non-limiting embodiment of the present invention, the light passing holes are circular light passing holes having a third diameterLight-transmitting holeDistance between center and center of the head end scope 101For the arithmetic series, it is further preferable that the plurality of light passing holes are arranged in a straight line with the center of the head end cavity mirror 101.
The end mirror 102 is a concave mirror with a second focal length toIs shown to have a second diameter ofAnd (3) representing.
In a preferred but non-limiting embodiment of the invention, the focal length of the head end endoscope 101Focal length with the end mirror 102Equal, expressed by the following formula,
The head end endoscope 101 and the tail end endoscope 102 are arranged opposite to each other, the focuses coincide, and the distance between the head end endoscope 101 and the tail end endoscope 102 isThe relationship between the distance between the head end endoscope 101 and the end endoscope 102 and the focal length is expressed by the following formula,
Wherein:
Represents the distance adjustment factor, and further preferably, 。
As shown in fig. 1, the plane mirror is disposed on a side of the head end cavity mirror 101 away from the end cavity mirror 102, laser is injected into the enhancement cavity from a light-passing hole of the head end cavity mirror 101, reflected between the two cavity mirrors for multiple times, and then emitted from the light-passing hole of the head end cavity mirror, the emitted laser is guided by the plane mirror, enters the enhancement cavity again from the next light-passing hole, is emitted from the light-passing hole of the head end cavity mirror after multiple reflections, and the above processes are repeated until the laser is emitted from the last light-passing hole. In this process, the laser light reflected multiple times within the cavity and the incident light will both approximately center the beam within the cavity by enhancing the same point within the cavity, i.e., beam center point 301 in fig. 2. The enhancement cavity is the region of the head end endoscope 101 that is opposite the middle of the end endoscope 102.
As shown in fig. 2, in the process of multiple reflection of laser in the cavity, the laser is distributed in light spots formed on the head end cavity mirror 101 and the tail end cavity mirror 102, so that the utilization rate of the lens by the beam concentric dense multiple reflection cavities is high, and dense multiple reflection is formed, and the reflection times are high.
As shown in fig. 3, embodiment 2 of the present invention provides a multi-component gas raman spectrum detection system based on a beam-centered dense multi-reflecting cavity, which comprises a laser 103, a beam-centered dense multi-reflecting cavity, a raman light collimating lens 105, a long-pass filter 106, a raman light focusing lens 107, a spectrometer 108, a CCD109 and a gas cell 104. The raman light collimating lens 105 is focused at a beam centerpoint 301. The long-pass filter 106, the raman light focusing lens 107, the spectrometer 108 and the CCD109 are sequentially positioned on an extension line from the beam concentric point 301 to the center of the raman light collimating lens 105.
In a preferred but non-limiting embodiment of the present invention, the head end endoscope 101 and the end endoscope 102 used in this example are both 100mm in diameter and 200mm in focal length.
In a preferred but non-limiting embodiment of the invention, the laser 103 used in this example has a wavelength of 532 nm and a power of 1.5W for exciting gas raman signals. Correspondingly, the cut-off wavelength of the long-pass filter 106 used in the embodiment is 533 nm, which is used for filtering interference signals such as laser light, rayleigh scattered light and the like in the raman signal.
The beam concentric dense multi-reflecting cavity used in this embodiment comprises 2 concave mirrors (head end mirror 101 and end mirror 102) and several plane mirrors. The diameters of the head end endoscope 101 and the tail end endoscope 102 are 100 mm, and the focal lengths are 200 mm. The head end cavity mirror 101 is provided with 5 circular light through holes, the diameter is 3.5 mm, and the distances from the center of the light through holes to the center of the head end cavity mirror 101 are 45, 40, 35, 30 and 25 mm respectively. The number of reflections of the laser light within the cavity amounts to about 600 or more and all pass approximately the same point (focal point).
The raman light collimating lens 105 used in this embodiment is a spherical lens with a focal length of 50 mm, and is used for collimating the raman scattered light laterally propagating at the focal point, so as to improve the collection efficiency of raman signals.
The raman light focusing lens 107 used in this embodiment is a spherical lens with a focal length of 50 mm, which is used to focus the raman light into the slit of the spectrometer 108.
The spectrometer 108 and the CCD109 used in this embodiment are used to detect the Raman signal of the gas to be measured and generate a Raman spectrum.
The gas chamber 104 used in this embodiment is disposed in the enhancement cavity (e.g., at the beam-concentric point 301 in fig. 3) between the head end mirror 101 and the end mirror 102, and is used for filling the gas to be measured.
The embodiment utilizes the system pair、、The raman spectrum of the gas mixture was measured, and the raman spectrum was shown in fig. 4 (integration time: 1 minute). Wherein the concentration of each gas is 2000 ppm, and the detection limit obtained according to the three-time signal-to-noise ratio principle is:0.8 ppm、:0.7 ppm;:0.4 ppm。
A method for beam-concentric dense multi-reflection cavity for gas raman signal enhancement, comprising the steps of:
step 1, laser enters an enhancement cavity along the beam concentric direction through a first light through hole, and is reflected between a head end cavity mirror and a tail end cavity mirror for multiple times;
And 2, emitting laser from the first light through hole to the enhancement cavity, and re-entering the enhancement cavity along the beam concentric direction by using a plane reflector through the second light through hole for enhancing the Raman signal of the gas at the beam concentric position.
While the applicant has described and illustrated the embodiments of the present invention in detail with reference to the drawings, it should be understood by those skilled in the art that the above embodiments are only preferred embodiments of the present invention, and the detailed description is only for the purpose of helping the reader to better understand the spirit of the present invention, and not to limit the scope of the present invention, but any improvements or modifications based on the spirit of the present invention should fall within the scope of the present invention.
Claims (9)
1. The light beam concentric dense multi-reflection cavity comprises a head end cavity mirror and a tail end cavity mirror, wherein an enhancement cavity is formed in the middle of the head end cavity mirror and the tail end cavity mirror in an opposite area, and is used for reflecting laser between the head end cavity mirror and the tail end cavity mirror for multiple times, and the light beam concentric dense multi-reflection cavity is characterized in that:
The head end cavity mirror is provided with a plurality of light through holes, each light through hole comprises a first light through hole, a second light through hole, a third light through hole and a fourth light through hole, wherein the positions of the light through holes from the center of the head end cavity mirror are different, the light through holes are round light through holes, the distances from the center of the light through holes to the center of the head end cavity mirror are in an arithmetic progression, and the light through holes and the center of the head end cavity mirror are in linear arrangement;
The beam concentric dense multi-reflecting cavity further comprises a plane reflecting mirror, and the plane reflecting mirror is positioned at one side of the head end cavity mirror, which is far away from the tail end cavity mirror;
laser enters the enhancement cavity along the beam concentric direction through the first light-passing hole;
the laser is emitted out of the enhancement cavity from the first light-passing hole, and enters the enhancement cavity again along the beam concentric direction through the second light-passing hole by utilizing a plane reflector.
2. The beam-concentric dense multi-reflecting cavity of claim 1, wherein the head end cavity mirror and the tail end cavity mirror are concave reflectors with equal focal lengths and same sizes, and the distance between the head end cavity mirror and the tail end cavity mirror is 4 times of the focal length.
3. A beam concentric dense multi-reflection cavity for enhancing a gas Raman signal is characterized by comprising the beam concentric dense multi-reflection cavity, a laser, a gas chamber, a Raman light collimating lens, a long-pass filter, a Raman light focusing lens, a spectrometer and a CCD according to any one of claims 1 to 2;
the gas chamber is arranged in the enhancement cavity and is used for filling the gas;
the laser is used for emitting laser light, wherein the laser light is used for exciting gas to generate Raman signals;
the Raman light collimating lens is used for collecting Raman signals and focusing the Raman signals at the beam concentric point;
The long-pass filter, the Raman light focusing lens, the spectrometer and the CCD are sequentially positioned on an extension line from the beam concentric point to the center of the Raman light collimating lens, wherein the long-pass filter is used for filtering interference signals, the Raman light focusing lens is used for focusing Raman light to the spectrometer, and the spectrometer and the CCD are used for detecting Raman signals of the gas to be detected.
4. A beam concentric dense multi-reflection cavity for gas raman signal enhancement according to claim 3, wherein the diameters of the head end cavity mirror and the tail end cavity mirror are 100mm, and the focal lengths are 200mm.
5. A beam-concentric dense multi-reflecting cavity for gas raman signal enhancement according to claim 3 wherein said light passing aperture is circular with a diameter of 3.5mm.
6. A beam-concentric dense multi-reflecting cavity for gas raman signal enhancement according to claim 3 wherein said laser has a wavelength of 532nm and a power of 1.5W.
7. A beam-concentric dense multi-reflecting cavity for gas raman signal enhancement according to claim 6, wherein said long pass filter cutoff wavelength is 533nm.
8. A beam-concentric dense multi-reflecting cavity for gas raman signal enhancement according to claim 3 wherein said raman light collimating lens is a spherical lens having a focal length of 50mm, said raman light focusing lens is a spherical lens having a focal length of 50mm.
9. A method for beam-concentric dense multi-reflecting cavities for gas raman signal enhancement, for use on the beam-concentric dense multi-reflecting cavities of claim 1, the method comprising the steps of:
step 1, laser enters an enhancement cavity along the beam concentric direction through a first light through hole, and is reflected between a head end cavity mirror and a tail end cavity mirror for multiple times;
And 2, the laser is emitted out of the enhancement cavity from the first light through hole, and enters the enhancement cavity again along the beam concentric direction through the second light through hole by using the plane reflector, so as to enhance the Raman signal of the gas at the beam concentric position.
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| CN208013077U (en) * | 2018-03-21 | 2018-10-26 | 黄保坤 | Transparent sample light scattering signal collection device and corresponding signal analysis device |
| CN110715909A (en) * | 2019-10-30 | 2020-01-21 | 山东大学 | Multi-channel multi-reflection gas detection device |
| CN113295669B (en) * | 2021-05-14 | 2023-10-24 | 重庆大学 | Folding type multi-reflecting cavity for enhancing gas Raman signal |
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| JPH1126840A (en) * | 1997-06-27 | 1999-01-29 | Shibuya Kogyo Co Ltd | Laser device |
| CN112414992A (en) * | 2020-11-13 | 2021-02-26 | 苏州灵析精密仪器有限公司 | Raman spectrum excitation enhancement module |
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