CN113899728A - Dual-wavelength light source Raman spectrometer system - Google Patents
Dual-wavelength light source Raman spectrometer system Download PDFInfo
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- CN113899728A CN113899728A CN202111322623.7A CN202111322623A CN113899728A CN 113899728 A CN113899728 A CN 113899728A CN 202111322623 A CN202111322623 A CN 202111322623A CN 113899728 A CN113899728 A CN 113899728A
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- 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
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/061—Sources
- G01N2201/06113—Coherent sources; lasers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/08—Optical fibres; light guides
Abstract
The invention discloses a dual-wavelength light source Raman spectrometer system, which comprises: the laser light source group is provided with laser light sources with two wavelengths, and the laser light sources with the two wavelengths respectively excite two material samples with different properties; the volume holographic transmission grating group comprises two independent volume holographic transmission gratings which respectively receive Raman scattered light generated after two samples are excited by light sources with two wavelengths; and different areas of the CCD detector receive the parallel light beams after the Raman scattered light from the two volume holographic transmission gratings is split. According to the multichannel Raman spectrometer for detecting the laser light sources with the two wavelengths, two samples with different types and properties can be detected by the same equipment through the dual-wavelength light source, and a plurality of samples can be simultaneously detected by the same type through multichannel arrangement, so that the multichannel Raman spectrometer is convenient and quick.
Description
Technical Field
The invention relates to the technical field of optical detection, in particular to a dual-wavelength light source Raman spectrometer system.
Background
Raman spectroscopy is a method in which when a laser beam of a certain frequency is irradiated onto a sample, molecules of a substance and photons are subjected to energy conversion, so that the vibration of chemical bonds between atoms in the molecules changes in different ways and degrees, and then light of different frequencies is scattered, the frequency change depends on the characteristics of a scattering substance, and the vibration of chemical bonds between different kinds of atoms is unique in way, so that scattered light having a specific difference from the frequency of the incident light can be generated, and the difference spectrum is called "raman spectrum". The raman spectrometer is an instrument that irradiates a sample with laser and collects raman scattering light to perform signal analysis to obtain a raman spectrum.
The raman spectrometer has the advantages of wide detection range (capable of detecting transparent gas, liquid and solid), short detection time (from several seconds to several minutes), less sample consumption, no damage to the sample, rich spectral information, strong characteristics, small volume, remote detection, easy system maintenance and the like, and is widely applied to process analysis at present. The detection efficiency can be greatly improved by simultaneously detecting multiple materials and multiple channels, and materials in different states sometimes need to use laser light sources with different wavelengths. However, in the prior art, although there is a multi-channel raman spectrometer which can detect samples of a plurality of materials at the same time, it is difficult to detect materials of different properties, such as one liquid and one gas, by using a light source with one wavelength, and therefore, in this case, two different raman spectrometers are often required to detect the materials respectively.
The Chinese patent application CN109085152A discloses a multichannel optical fiber type gas Raman scattering measurement system, in the scheme, a laser system, a Raman spectrum imaging system, a 10-channel optical fiber coupling system, a measurement and control system, a 45-degree laser reflector, a laser focusing mirror and a laser collector are arranged on the same optical platform, the scheme can realize laser spontaneous vibration Raman spectrum line imaging of gaseous species in a dynamic combustion field, and can realize high-precision quantitative measurement of the mole fraction and the region temperature of the gaseous species in the dynamic combustion field. This prior art technique collects raman scattered light passing through a sample by a multi-channel fiber optic sensor, but can only be used for detection by a single wavelength light source.
In process analysis, such as analysis of materials controlled in an oil refining process, the materials are related to gas and liquid, at present, different instruments are often adopted for analysis aiming at different materials or materials with different shapes, such as near infrared spectrum and nuclear magnetic resonance for liquid phase materials, and gas chromatography for gas phase materials. Therefore, need for an instrument that can detect two kinds of different property materials simultaneously, based on dual wavelength laser light source's multichannel raman spectroscopy, can realize that same platform equipment detects the sample of different properties, and the sample of same property can also detect a plurality ofly simultaneously, convenient and fast.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a multichannel Raman spectrometer system capable of detecting two wavelength laser light sources, which can detect two samples with different types and properties by using the same equipment through the dual wavelength light sources, and can detect a plurality of samples with the same type at the same time through the multichannel arrangement, thereby being convenient and fast.
To achieve the above object, the present invention provides a dual wavelength light source raman spectrometer system, comprising: the laser light source group is provided with laser light sources with two wavelengths, and the laser light sources with the two wavelengths respectively excite two material samples with different properties; the volume holographic transmission grating group comprises two independent volume holographic transmission gratings which respectively receive Raman scattered light generated after two samples are excited by light sources with two wavelengths; and different areas of the CCD detector receive the parallel light beams after the Raman scattered light from the two volume holographic transmission gratings is split.
Further, in the above technical scheme, in the same raman spectrometer, the laser light sources with two wavelengths may be respectively provided with a plurality of light sources, and each light source corresponds to a different sampling point, so as to form multi-channel detection.
Further, in the above technical solution, each of the multiple channels is connected in series with the incident optical fiber, the probe, the sample cell, and the collection optical fiber in a unidirectional manner.
Further, in the above technical solution, the raman spectrometer may further include: an entrance slit that receives the multiple Raman scattered light from the collection fiber; and the relay lens receives the multiple paths of Raman scattered light passing through the entrance slit and sequences the Raman scattered light according to different excitation wavelengths.
Further, in the above technical solution, the sequenced raman scattered light with different excitation wavelengths may enter the corresponding volume holographic transmission gratings respectively.
Further, in the above technical solution, the two volume holographic transmission gratings may correspond to a single CCD detector.
Further, in the above technical solution, collimating lenses corresponding to the number of the light sources are disposed between the volume holographic transmission grating and the CCD detector, and the collimating lenses receive the raman scattered light split by the volume holographic transmission grating and irradiate different detection regions of the CCD detector in parallel.
Further, in the above technical solution, the two laser light sources with the wavelengths may be 532nm laser and 785nm laser, respectively; the two materials with different properties can be respectively gas and liquid.
Further, in the above technical solution, the direction of the slits of the two volume hologram transmission gratings is perpendicular to the direction of the raman scattering light from the front collimator, and the slits of the two volume hologram transmission gratings are parallel. This effectively prevents the beams from crossing.
Further, in the above technical solution, the CCD detector may be connected to a signal processing system for converting the photoelectric signal into a digital signal and acquiring a spectrum of the raman scattered light.
Compared with the prior art, the invention has the following beneficial effects:
1) the Raman spectrometer system adopting the dual-wavelength light source can simultaneously detect material samples with two properties by utilizing the light sources with two wavelengths in the same equipment respectively, adopts the dual-grating light splitting corresponding to the dual-wavelength light source, expands the detection object range of the Raman spectrometer, has stronger practicability, and can be applied to the fields of chemical industry, petroleum refining, biological medicine, environmental monitoring and the like, wherein gas phase and liquid phase materials need to be detected simultaneously;
2) by adopting the multi-channel system, each sampling point can be excited by selecting one light source, and the intensity of the light source can be adjusted according to the requirement of each sampling point, so that the detection sensitivity and the detection precision are improved;
3) the multi-channel system of the invention shares one CCD detector, so that the Raman spectrometer system is more compact, the instrument volume is smaller, and the invention is more beneficial to portability and selection of the placing position of an application site;
4) the slits of the two independent volume holographic transmission gratings are kept in a parallel state, and the directions of the slits of the two volume holographic transmission gratings are kept perpendicular to the direction of Raman scattering light entering through the front collimator, so that the Raman scattering light obtained by different light sources through light splitting can be effectively ensured to be irradiated on different detection areas of the CCD detector in parallel, the light beam crossing is avoided, multiple channels can be detected simultaneously, and the detection efficiency is improved;
5) the light source placing position of the invention can be flexibly selected, and the longer the optical fiber is, the more serious the light attenuation is, the light source placing position can be selected to be beneficial to controlling the using length of the optical fiber, thereby increasing the detection capability.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood and to make the technical means implementable in accordance with the contents of the description, and to make the above and other objects, technical features, and advantages of the present invention more comprehensible, one or more preferred embodiments are described below in detail with reference to the accompanying drawings.
Drawings
Fig. 1 is a schematic structural diagram (in a multi-channel arrangement) of a dual wavelength light source raman spectrometer system of the present invention.
Fig. 2 is a light splitting schematic diagram of embodiment 1 (four-channel) of the dual-wavelength light source raman spectrometer system of the present invention.
Description of the main reference numerals:
1-laser light source, 2-incident optical fiber, 3-probe, 4-sample cell, 5-collecting optical fiber, 6-entrance slit, 7-relay lens, 8-collimator, 9-volume holographic transmission grating, 9A-first volume holographic transmission grating, 9B-second volume holographic transmission grating, 10-collimating lens, 11-CCD detector and 12-signal processing system.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Spatially relative terms, such as "below," "lower," "upper," "above," "upper," and the like, may be used herein for ease of description to describe one element or feature's relationship to another element or feature in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the object in use or operation in addition to the orientation depicted in the figures. For example, if the items in the figures are turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the elements or features. Thus, the exemplary term "below" can encompass both an orientation of below and above. The article may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative terms used herein should be interpreted accordingly.
In this document, the terms "first", "second", etc. are used to distinguish two different elements or portions, and are not used to define a particular position or relative relationship. In other words, the terms "first," "second," and the like may also be interchanged with one another in some embodiments.
The dual-wavelength light source Raman spectrometer system adopts light sources with two wavelengths, and the light source with one wavelength adopts a plurality of light sources to carry out multi-channel detection. In order to ensure the detection precision, one light source detects one sampling point, one device uses a plurality of light sources to detect a plurality of sampling points, under the condition that the conditions are met, a double grating is arranged in the spectrometer and used for splitting Raman scattered light after two light sources excite a sample, each light source can be provided with a plurality of light sources, one grating can support splitting of the light sources with the same wavelength, and different pixel positions are selected according to different light sources through the same CCD detector.
As shown in fig. 1, fig. 1 illustrates a six-channel raman spectrometer with a dual-wavelength light source. The raman spectrometer in fig. 1 may include a laser light source 1, an incident fiber 2, a probe 3, a sample cell 4, a collection fiber 5, an entrance slit 6, a relay lens 7, a collimator 8, a first volume holographic transmission grating 9A, a second volume holographic transmission grating 9B, a collimating lens 10, a CCD detector 11, and a signal processing system 12.
As further shown in fig. 1, six laser light sources 1 constitute a laser light source group, the laser light source group has two wavelength laser light sources, and the two wavelength laser light sources respectively excite two material samples with different properties. Preferably, but not limitatively, the laser light sources of two wavelengths can respectively adopt 532nm laser and 785nm laser; the two materials with different properties can be respectively gas and liquid. The light sources with the two wavelengths are used for respectively detecting gas and liquid in the same Raman spectrometer, so that the detection precision is higher, and the detection effect is better.
As further shown in fig. 1, a laser light source group composed of six laser light sources 1, an incident optical fiber group composed of six incident optical fibers 2, a probe group composed of six probes 3, a sample cell group composed of six sample cells 4, and a collection optical fiber group composed of six collection optical fibers 5 are respectively in one-to-one correspondence and connected in a unidirectional serial connection manner. Laser emitted by the laser source 1 is transmitted to the probe 3 through the incident optical fiber 2, the probe 3 irradiates the light of the laser source on a sampling point in the sample cell 4, and corresponding Raman scattering light on the sampling point is collected by the corresponding collecting optical fiber 5.
As further shown in fig. 1, the raman scattered light collected by each collection fiber 5 enters an entrance slit 6, and the multiple paths of raman scattered light from the collection fibers enter corresponding collimators 8 respectively according to different corresponding excitation wavelengths through relay lenses 7. In the same raman spectrometer, the laser light sources with two wavelengths are respectively provided with a plurality of light sources, namely, in fig. 1, three channels in six channels use laser with the same wavelength (for example, 532nm), the other three channels use laser with the other wavelength (for example, 785nm), and each light source corresponds to different sampling points, so that multi-channel detection is formed. The entrance slit 6 of the present invention receives the multiple raman scattered light from the collection fiber set, and the relay lens 7 is used to receive the multiple raman scattered light passing through the entrance slit 6 and sort the raman scattered light according to different excitation wavelengths. The light with different excitation wavelengths respectively enters the corresponding volume holographic transmission gratings in sequence, for example, the raman scattering light formed after the laser with the wavelength of 532nm excites the sample enters the first volume holographic transmission grating 9A, and the raman scattering light formed after the laser with the wavelength of 785nm excites the sample enters the second volume holographic transmission grating 9B. The first volume holographic transmission grating 9A and the second volume holographic transmission grating 9B are two independent volume holographic transmission gratings, and can respectively receive the raman scattered light after the two samples are excited by the light sources with two wavelengths. The Raman scattering light enters the corresponding collimating lenses 10 after being split by the volume holographic transmission grating and is detected by the same CCD detector 11, and the parallel beams of the Raman scattering light split by the two volume holographic transmission gratings are received by different areas of the CCD detector 11. Further, the photoelectric signal is converted into a digital signal by the signal processing system 12, and a required raman spectrum can be obtained.
In order to ensure that the multichannel Raman scattering light can be incident to the CCD detector 11 in sequence after being split, namely parallel light beams are obtained, and the light beams are prevented from being crossed, slits of the first volume holographic transmission grating 9A and the second volume holographic transmission grating 9B are set to be in a parallel state, and the directions of the slits of the two volume holographic transmission gratings are perpendicular to the direction of the Raman scattering light entering through the collimator 8. In this way, beam crossover is effectively avoided. The parallel light beam further enters a collimating lens 10 corresponding to the number of light sources between the volume holographic transmission grating and the CCD detector 11, and the collimating lens 10 receives the raman scattered light split from the volume holographic transmission grating and can irradiate different detection areas of the CCD detector 11 in parallel (refer to fig. 2).
By adopting the Raman spectrometer, the light sources with two wavelengths can be used for simultaneously detecting material samples with two properties in the same equipment, and the double-grating light splitting corresponding to the light sources with two wavelengths is adopted, so that the detection object range of the Raman spectrometer is expanded, the practicability is higher, and the Raman spectrometer can be applied to the fields of chemical industry, petroleum refining, biological medicine, environmental monitoring and the like, in which gas-phase and liquid-phase materials need to be detected simultaneously; each sampling point in the multi-channel is excited by selecting one light source, and the intensity of the light source can be adjusted according to the requirement of each sampling point, so that the detection sensitivity and the detection precision are improved; the multiple channels share one CCD detector, so that the Raman spectrometer system is more compact, the instrument volume is smaller, and portability and selection of the placing position of an application site are facilitated; by adopting the Raman spectrometer, Raman scattered light obtained by irradiation of different light sources can be irradiated in parallel to different detection areas of the CCD detector through the light beams after light splitting, so that multiple channels can be detected simultaneously, and the detection efficiency is improved; the light source placing position of the invention can be flexibly selected, and the longer the optical fiber is, the more serious the light attenuation is, the light source placing position can be selected to be beneficial to controlling the using length of the optical fiber, thereby increasing the detection capability.
Example 1
A four-channel raman spectrometer is arranged in a connection manner shown in fig. 1, wherein two channels are 532nm light sources, raman scattering light obtained by irradiation is finally projected on a CCD detector 11, and corresponding pixel positions are [10,45] and [60,95] respectively; the raman scattered light obtained by 785nm light source irradiation of the other two channels is finally projected on the same CCD detector 11, and the corresponding pixel positions are [105,140] and [155,190], respectively.
Selection of two independent volume holographic transmission gratings:
532nm laser grating: the Raman shift is set to 200-4000 cm-1532nm converted to 1/532 nm-18796.99 cm-1The range of Raman scattered light is [18796.99-4000,18796.99-200 ]]cm-1Converting the converted wavelength into 537.7-675.8 nm, determining the spectral range of the system to be 530-670 and the central wavelength to be 600nm, and selecting the linear density of the grating to be 600l/mm by considering the size of the system and the size of a dispersion angle.
785nm laser grating: raman positionThe distance is set to be 250-3000 cm-1785nm converted to 1/785 nm-12738.85 cm-1The range of Raman scattered light is [12738.85-2800,12738.85-250 ]]cm-1Converting the wavelength into 800.7-1026.8 nm, determining the spectral range of the system to be 800-1000 nm, determining the central wavelength to be 900nm, and selecting the linear density of the grating to be 1200l/mm by considering the size of the system and the size of a dispersion angle.
Selection of a CCD detector:
the detector selects 1650 × 200active pixels (16 × 16 μm pixel size), the light is imaged on the detector through the optical system via the slit, the image of one spectral channel is dispersed on the detector by 2 pixels, the two spectral channels are separated by one pixel, the number of spectral channels is 1650/3-550, the resolution is (1000-800)/550-0.36 nm for 785nm light source, and the frequency is converted to 4.44cm-1(ii) a For 532nm light source, the resolution is (670-) -530)/550-0.25 nm, and the converted wave number is 6.95cm-1。
The light splitting principle of this embodiment is as shown in fig. 2, in this embodiment, the slits of two independent volume holographic transmission gratings are set to be in a parallel state, and the directions of the slits of the two volume holographic transmission gratings are both perpendicular to the direction of the raman scattering light entering through the front collimator, so as to ensure that the light beams impinging on the CCD detector are parallel light beams in a certain order.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. Any simple modifications, equivalent changes and modifications made to the above exemplary embodiments shall fall within the scope of the present invention.
Claims (10)
1. A dual wavelength light source raman spectrometer system, comprising:
the laser light source group is provided with laser light sources with two wavelengths, and the laser light sources with the two wavelengths respectively excite two material samples with different properties;
the volume holographic transmission grating group comprises two independent volume holographic transmission gratings which respectively receive Raman scattering light after the two samples are excited by the light sources with the two wavelengths;
and different areas of the CCD detector receive the parallel light beams after the Raman scattered light from the two volume holographic transmission gratings is split.
2. The dual wavelength light source raman spectrometer system of claim 1, wherein a plurality of light sources are respectively disposed for the two wavelength laser light sources in the same raman spectrometer, each light source corresponding to a different sampling point, forming a multi-channel detection.
3. The dual wavelength light source raman spectrometer system of claim 2, wherein each of the multiple channels is unidirectionally connected in series with an incident optical fiber, a probe, a sample cell, and a collection optical fiber, respectively.
4. The dual wavelength light source raman spectrometer system of claim 3, wherein the raman spectrometer further comprises:
an entrance slit that receives the multiple Raman scattered light from the collection fiber;
a relay lens that receives the multiple Raman scattered light passing through the entrance slit and orders the Raman scattered light according to different excitation wavelengths.
5. The dual wavelength light source raman spectrometer system of claim 4, wherein the sequenced raman scattered light of different excitation wavelengths enter the corresponding volume holographic transmission gratings respectively.
6. The dual wavelength light source raman spectrometer system of claim 5, wherein two of the volume holographic transmission gratings correspond to one of the CCD detectors.
7. The dual wavelength light source raman spectrometer system according to claim 6, wherein a number of collimating lenses corresponding to the number of light sources are provided between the volume holographic transmission grating and the CCD detector, and the collimating lenses receive raman scattered light split from the volume holographic transmission grating and irradiate different detection regions of the CCD detector in parallel.
8. The dual wavelength light source raman spectrometer system of claim 1, wherein the two wavelength laser light sources are 532nm laser and 785nm laser, respectively; the two materials with different properties are respectively gas and liquid.
9. The dual wavelength light source raman spectrometer system of claim 1, wherein the direction of the slits of the two volume holographic transmission gratings is perpendicular to the direction of the raman scattered light from the front end collimator, and wherein the slits of the two volume holographic transmission gratings are parallel.
10. The dual wavelength light source raman spectrometer system of claim 1, wherein the CCD detector is connected to a signal processing system for converting the photoelectric signal into a digital signal and acquiring a spectral spectrum of the raman scattered light.
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| CN114923892A (en) * | 2022-05-24 | 2022-08-19 | 中国工程物理研究院材料研究所 | Dual-wavelength near-infrared portable Raman spectrum device |
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| CN114923892A (en) * | 2022-05-24 | 2022-08-19 | 中国工程物理研究院材料研究所 | Dual-wavelength near-infrared portable Raman spectrum device |
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