CN116124756A - Spectrometer device based on combination of Raman spectrum and near infrared spectrum - Google Patents
Spectrometer device based on combination of Raman spectrum and near infrared spectrum Download PDFInfo
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- CN116124756A CN116124756A CN202211334008.2A CN202211334008A CN116124756A CN 116124756 A CN116124756 A CN 116124756A CN 202211334008 A CN202211334008 A CN 202211334008A CN 116124756 A CN116124756 A CN 116124756A
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- 238000002329 infrared spectrum Methods 0.000 title claims abstract description 23
- 238000001237 Raman spectrum Methods 0.000 title claims abstract description 22
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 49
- 230000003287 optical effect Effects 0.000 claims abstract description 29
- 238000013519 translation Methods 0.000 claims abstract description 15
- 238000004497 NIR spectroscopy Methods 0.000 claims 6
- 230000000149 penetrating effect Effects 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 10
- 238000004458 analytical method Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 230000001678 irradiating effect Effects 0.000 abstract 1
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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
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
Abstract
The invention provides a spectrometer device based on combination of Raman spectrum and near infrared spectrum, comprising: the device comprises a first light source device, a second light source device, a light beam deflection device, a switchable reflector, a near infrared spectrometer, a Raman spectrometer and a translation device; the first light source device and the second light source device are respectively used for emitting Raman light beams and near infrared light beams to be incident to the light beam deflection device; irradiating the sample to be detected by using a Raman beam and a near infrared beam; the method comprises the steps of emitting near infrared light signals and Raman light signals with sample information to be detected to be incident on a switchable reflector; when the switchable reflector cuts into the light path, the near infrared light signals are focused to the near infrared spectrometer, and the near infrared reflected light signals are collected; when the switchable reflector cuts out the light path, the Raman optical signal is focused to the Raman spectrometer after the fluorescence interference is eliminated by the optical rotation sheet, and the Raman optical signal is collected. The invention improves the detection precision and the data reliability and solves the problem of inaccurate analysis of small batches of samples.
Description
Technical Field
The invention relates to the technical field of spectroscopic instruments, in particular to a spectrometer device based on combination of Raman spectrum and near infrared spectrum.
Background
Spectroscopic methods are methods for identifying a substance and determining its chemical composition and relative content based on the measurement of the wavelength and intensity of emitted, absorbed or scattered radiation resulting from energy level transitions occurring within the substance as it reacts with the radiation. With the continued development of spectroscopy, various new spectra were discovered, and different spectroscopic analysis methods were successively established, with the advent of corresponding spectroscopic analysis instrumentation. Spectral analysis has been studied for a long time in principle, has been approaching to perfection in theory, and has become one of the most modern analytical chemistry means, the most widely used and the most powerful analytical methods. The spectrum analysis method has excellent performance in qualitative, quantitative and structural analysis, and the spectrum detection has the advantages of good transmissibility, simple structure, high real-time performance, nondestructive detection, strong applicability and the like, and is widely applied to the fields of life science, medicine, food, chemical industry, medicine, environment, business inspection, space exploration and the like. Has very wide application space in scientific research, teaching and industrial production. The performance of the spectrometer directly influences the accuracy and applicability of the test as a basis for spectrum detection.
The near infrared spectrum analysis technology realizes the unique advantages of non-contact and non-damage, no need of sample pretreatment, quick, high-flux, qualitative and quantitative detection of solid, liquid and gas substance components and contents through a near infrared spectrometer, has important and wide application in the fields of biological medicine, food safety, environmental monitoring, industrial and agricultural production, aerospace, national safety and the like, and is one of the most rapid developed new technologies in modern detection analysis technologies. Raman spectroscopy is a molecular spectral characterization means, known as "fingerprint" spectroscopy. In recent years, the Raman spectrum technology is mature, and the Raman spectrometer is widely applied to the fields of biomedical science, precious stone identification, petrochemical explosives and the like, and becomes one of the effective analysis tools commonly used by people.
However, in the prior art, aiming at the fact that the detection precision of Raman spectrum is limited by fluorescence interference, a near infrared spectrum model needs a large number of representative samples with known chemical values to build a model, and the near infrared spectrum model is greatly influenced by a calibration sample, so that the problem of inaccurate analysis of small batches of samples exists.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a spectrometer device based on the combination of raman spectrum and near infrared spectrum, which improves the detection accuracy and data reliability by developing an optical path system combining raman spectrum and near infrared spectrum to collect near infrared spectrum and raman spectrum data of a sample at the same time and performing interactive analysis processing.
In order to achieve the above purpose, the present invention adopts the following specific technical scheme:
the invention provides a spectrometer device based on combination of Raman spectrum and near infrared spectrum, comprising: the device comprises a first light source device, a second light source device, a light beam deflection device, a switchable reflector, a near infrared spectrometer, a gyrometer, a Raman spectrometer and a translation device;
the first light source device and the second light source device are respectively used for emitting Raman light beams and near infrared light beams to be incident to the light beam deflection device;
the beam deflection device comprises a first reflecting element, a second reflecting element and a third reflecting element;
the Raman light beam and the near infrared light beam irradiate the sample to be detected after being reflected by the first reflecting element and the second reflecting element in sequence;
placing a sample to be measured on a translation stage;
the sample to be measured emits a near infrared light signal and a Raman light signal with the information of the sample to be measured after irradiation, and the near infrared light signal and the Raman light signal are transmitted by the second refraction element and then are incident to the switchable reflector after being emitted by the third reflection element;
when the switchable reflector cuts into the light path, the near infrared light signals are focused to the near infrared spectrometer, and the near infrared reflected light signals are collected;
when the switchable reflector cuts out the light path, the Raman optical signal is focused to the Raman spectrometer after the fluorescence interference is eliminated by the optical rotation sheet, and the Raman optical signal is collected.
Preferably, the first light source device includes: the laser, the first attenuation sheet and the beam expander;
the laser is used for emitting a monochromatic light beam with stable light intensity, and the monochromatic light beam is incident to the light beam deflection device after being sequentially expanded by the first attenuation sheet and the beam expander.
Preferably, the second light source device includes: a near infrared light source and a second attenuation sheet;
the near infrared light source is used for emitting a near infrared light beam, and the near infrared light beam is transmitted by the second attenuation sheet and then enters the light beam deflection device.
Preferably, the first light reflecting element is a first concave mirror;
the second light-refracting element is a dichroic mirror;
the third reflecting element is a second concave reflecting mirror;
the single-color light beam and the near-infrared light beam firstly enter a first concave reflector, and irradiate a sample to be detected after being reflected by the first concave reflector and the dichroic mirror in sequence; the near infrared light signal and the Raman light signal which are emitted and provided with the information of the sample to be detected are transmitted by the dichroic mirror and reflected by the second concave reflecting mirror, and then are incident to the switchable reflecting mirror.
Preferably, the switchable mirror is a filter wheel structure;
when the optical filter rotates to the reflecting mirror, the near infrared light signals are focused to the near infrared spectrometer, and the near infrared reflected light signals are collected;
when the optical filter rotates to the through hole, the Raman optical signal is focused to the Raman spectrometer after passing through the optical rotary sheet, and the Raman optical signal is collected.
Preferably, during the acquisition of near infrared spectral data and raman spectral data:
firstly, controlling a translation stage to move along an X or Y direction, collecting near infrared spectrum data, and simultaneously recording position information of the collected data;
and secondly, controlling the translation stage to move in the opposite direction, and collecting Raman spectrum information at the same position.
Compared with the prior art, the invention has the advantages that by developing the optical path system combining the Raman spectrum and the near infrared spectrum and collecting the near infrared spectrum and the Raman spectrum data of the sample, the detection precision and the data reliability are improved by the interactive analysis processing, and the problems that the Raman spectrum detection precision is limited by fluorescence interference, a near infrared spectrum model needs a large number of representative samples with known chemical values to build a model, is greatly influenced by a calibration sample, and is inaccurate in analyzing small batches of samples are solved.
Drawings
Fig. 1 is a schematic structural diagram of a spectrometer device based on the combination of raman spectrum and near infrared spectrum according to an embodiment of the present invention.
Wherein reference numerals include: the device comprises a laser 1, a first attenuation sheet 2, a beam expander 3, a near infrared light source 4, a second attenuation sheet 5, a first concave reflecting mirror 6, a dichroic mirror 7, a second concave reflecting mirror 8, a switchable reflecting mirror 9, a near infrared spectrometer 10, an optical rotation sheet 11, a Raman spectrometer 12 and a translation stage 13.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, like modules are denoted by like reference numerals. In the case of the same reference numerals, their names and functions are also the same. Therefore, a detailed description thereof will not be repeated.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limiting the invention.
Fig. 1 is a schematic structural diagram of a spectrometer device based on the combination of raman spectrum and near infrared spectrum according to an embodiment of the present invention.
As shown in fig. 1, a spectrometer device based on combination of raman spectrum and near infrared spectrum provided by an embodiment of the present invention includes: a first light source device, a second light source device, a beam deflector, a switchable mirror 9, a near infrared spectrometer 10, an optical rotation sheet 11, a raman spectrometer 12 and a translation stage 13.
The first light source device and the second light source device are respectively used for emitting Raman light beams and near infrared light beams to be incident into the light beam deflection device.
Because the surfaces of the samples to be tested have height differences, the first light source device, the second light source device and the light beam deflection device can move in the z direction, so that the system can modulate different focusing positions on the samples to be tested, the position of the laser incident on the surfaces of the samples is accurate, and the Raman excitation signal is maximized.
The first light source device includes: a laser 1, a first attenuation sheet 2 and a beam expander 3; the laser 1 is used for emitting a monochromatic light beam with stable light intensity; the first attenuation sheet 2 is used for modulating the energy of a monochromatic light beam emitted by the laser, so that damage caused by supersaturation of the detector is avoided. The beams which pass through the first attenuation sheet 2 and the beam expander 3 in turn are incident into the beam deflector.
The second light source device includes: a near infrared light source 4 and a second attenuation sheet 5; the near infrared light source 4 is used for emitting a near infrared light beam, and the near infrared light beam is transmitted by the second attenuation sheet 5 and then is incident into the light beam deflection device.
The beam deflection device includes: a first concave mirror 6, a dichroic mirror 7 and a second concave mirror 8. The dichroic mirror 7 is used to realize spectral separation by selectively transmitting or reflecting light according to wavelength. In the device provided by the invention, the dichroic mirror 7 is selectively transmissive for raman scattered light and selectively reflective for light beams of other wavelengths.
The monochromatic light beam and the near infrared light beam firstly enter the first concave reflector 6, and irradiate the sample to be measured placed on the translation stage 13 after being reflected by the first concave reflector 6 and the dichroic mirror 7 in sequence; the near infrared light signal and the raman light signal which are transmitted and provided with the information of the sample to be detected are transmitted by the dichroic mirror 7 and then are incident to the second concave reflecting mirror 8, and then are reflected by the second concave reflecting mirror 8 and then are incident to the switchable reflecting mirror 9.
The switchable reflector 9 is of a filter wheel structure;
when the optical filter rotates to the reflecting mirror, the near infrared light signals are focused to the near infrared spectrometer 10, and the near infrared reflected light signals are collected;
when the optical filter rotates to the through hole, the Raman optical signal is focused to the Raman spectrometer 12 after the interference of the excitation light source and fluorescence is eliminated by the rear-end optical rotation sheet 11, and the Raman optical signal is collected.
In the process of collecting near infrared spectrum data and Raman spectrum data:
firstly, the translation stage 13 is controlled to move along the X or Y direction and collect near infrared spectrum data, meanwhile, the position information (X, Y, 0) of the collected data is recorded, the translation stage is controlled X, Y to move in the opposite direction, and corresponding Raman spectrum information is collected at the same position (X, Y, 0).
Near infrared spectrum data and Raman spectrum data of a sample to be detected at the position (X, Y, 0) on the translation stage 13 can be obtained simultaneously by combining a data splicing technology, and qualitative and quantitative analysis can be performed through subsequent data processing.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
The above embodiments of the present invention do not limit the scope of the present invention. Any of various other corresponding changes and modifications made according to the technical idea of the present invention should be included in the scope of the claims of the present invention.
Claims (6)
1. A spectrometer device based on a combination of raman spectroscopy and near infrared spectroscopy, comprising: the device comprises a first light source device, a second light source device, a light beam deflection device, a switchable reflector, a near infrared spectrometer, a gyrometer, a Raman spectrometer and a translation device;
the first light source device and the second light source device are respectively used for emitting Raman light beams and near infrared light beams to be incident to the light beam deflection device;
the light beam deflection device comprises a first reflecting element, a second reflecting element and a third reflecting element;
the Raman light beam and the near-infrared light beam irradiate the sample to be detected after being reflected by the first reflecting element and the second reflecting element in sequence;
the sample to be measured is placed on the translation stage;
the sample to be measured emits a near infrared light signal and a Raman light signal with sample information to be measured after irradiation, and the near infrared light signal and the Raman light signal are transmitted by the second light refraction element and are incident to the switchable reflector after being emitted by the third light reflection element;
when the switchable reflector cuts into an optical path, the near infrared light signals are focused to the near infrared spectrometer to collect near infrared reflected light signals;
when the switchable reflector cuts out the light path, the Raman optical signal is focused to the Raman spectrometer after the fluorescence interference is eliminated by the optical rotation sheet, and the Raman optical signal is collected.
2. The spectrometer arrangement based on the combination of raman spectroscopy and near infrared spectroscopy according to claim 1, wherein the first light source arrangement comprises: the laser, the first attenuation sheet and the beam expander;
the laser is used for emitting a monochromatic light beam with stable light intensity, and the monochromatic light beam is incident to the light beam deflection device after passing through the first attenuation sheet and the beam expansion of the beam expansion lens in sequence.
3. The spectrometer arrangement based on the combination of raman spectroscopy and near infrared spectroscopy according to claim 2, wherein the second light source arrangement comprises: a near infrared light source and a second attenuation sheet;
the near infrared light source is used for emitting a near infrared light beam, and the near infrared light beam is transmitted by the second attenuation sheet and then enters the light beam deflection device.
4. A spectrometer arrangement based on the combination of raman spectroscopy and near infrared spectroscopy according to claim 3, wherein the first light reflecting element is a first concave mirror;
the second light refracting element is a dichroic mirror;
the third reflecting element is a second concave reflecting mirror;
the monochromatic light beam and the near infrared light beam firstly enter the first concave reflecting mirror, and irradiate the sample to be detected after being reflected by the first concave reflecting mirror and the dichroic mirror in sequence; the near infrared light signal and the Raman light signal which are emitted and provided with the information of the sample to be detected are transmitted by the dichroic mirror and reflected by the second concave reflecting mirror and then are incident to the switchable reflecting mirror.
5. The spectrometer device based on the combination of raman spectroscopy and near infrared spectroscopy according to claim 4, wherein the switchable mirror is a filter wheel structure;
when the optical filter rotates to the reflecting mirror, the near infrared light signals are focused to a near infrared spectrometer, and the near infrared reflected light signals are collected;
when the optical filter rotates to the through hole, the Raman optical signal is focused to the Raman spectrometer after penetrating through the optical rotation sheet, and the Raman optical signal is collected.
6. The spectrometer device based on the combination of Raman spectroscopy and near infrared spectroscopy according to claim 5,
during the acquisition of the near infrared spectrum data and the raman spectrum data:
firstly, controlling the translation stage to move along the X or Y direction, collecting the near infrared spectrum data, and simultaneously recording the position information of the collected data;
and secondly, controlling the translation stage to move in the opposite direction, and collecting the Raman spectrum information at the same position.
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