CN112505016A - Compact portable multi-wavelength in-situ Raman detector and detection method thereof - Google Patents
Compact portable multi-wavelength in-situ Raman detector and detection method thereof Download PDFInfo
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Abstract
The invention relates to a compact portable multi-wavelength in-situ Raman detector, which comprises a micro control system, a laser and spectrometer module and a multi-wavelength Raman front-end light path module, wherein the compact portable multi-wavelength in-situ Raman detector comprises: the multi-wavelength Raman front-end light path module comprises a plurality of Raman front-end light path modules and a light path coupling module, wherein the Raman front-end light path modules correspond to different wavelength ranges respectively and share the light path coupling module; the light path coupling module is provided with a long-wave-pass dichroic mirror and a short-wave-pass dichroic mirror which selectively transmit and/or reflect light beams with different wavelengths respectively. According to the invention, detection modules in three wavelength ranges are organically combined on the premise of not increasing a mobile device and ensuring the stability of an instrument, so that the in-situ and simultaneous detection requirements of Raman of three wavelengths are met. Aiming at the characteristics of the sample, the method can effectively reduce fluorescence background signals and improve the accuracy, reliability and application range of detection in a characteristic wavelength Raman precise detection mode and a multi-wavelength fluorescence quenching precise detection mode.
Description
Technical Field
The invention belongs to the field of photoelectric detection, relates to an in-situ spectrum detector with multiple laser light sources and a detection method thereof, and particularly relates to a compact portable in-situ Raman spectrum simultaneous detection device with multiple laser wavelengths, which is suitable for molecular structure analysis of substances with different characteristics.
Background
In raman spectroscopy, the characteristics of the test sample are different, and it is usually necessary to select a specific raman excitation wavelength, for example: inorganic compound samples are generally subjected to Raman testing by selecting laser with ultraviolet wavelength or visible wavelength, and biological sample substrates are complex and generally generate strong fluorescence background interference, so near-infrared band laser is selected to reduce the generation of fluorescence signals of the samples.
Conventional portable raman spectroscopy is generally configured with only one laser, for example, chinese patent application No.201610634478.9 discloses a 'portable raman spectrometer' comprising a single laser, an external optical path system, a single spectrometer and a control system; in practical application, the prior art is difficult to meet the detection requirements of various samples; a large-scale multi-wavelength Raman spectrum system usually adopts a mechanical switching device, and the mechanical switching device not only increases the volume of an instrument, but also influences the stability of the whole machine. Therefore, how to efficiently couple the multi-wavelength raman spectrum detection system is a problem to be solved urgently, and a portable multi-wavelength in-situ raman detection system is provided.
Disclosure of Invention
In view of the above technical problems, an object of the present invention is to provide a compact portable multi-wavelength in-situ raman detector and a method thereof, wherein a group of long-wavelength-pass dichroic mirrors and short-wavelength-pass dichroic mirrors are commonly used in a multi-wavelength in-situ raman spectrum detection system, so as to realize organic combination of ultraviolet raman, visible raman and near-infrared raman, and meet simultaneous testing of in-situ raman detection modules with three wavelengths.
In order to achieve the purpose, the invention provides the following technical scheme:
a compact portable multi-wavelength in-situ Raman detector comprises a micro main control system 1, a laser and spectrometer module 2 and a multi-wavelength Raman front-end light path module 42.
The multi-wavelength raman front optical path module 42 includes a plurality of raman front optical path modules and an optical path coupling module 37, where the plurality of raman front optical path modules respectively correspond to different wavelength ranges and share the optical path coupling module 37; the optical path coupling module 37 is provided with a long-wave-pass dichroic mirror 38 and a short-wave-pass dichroic mirror 39, which selectively transmit and/or reflect light beams with different wavelengths, respectively.
The laser and spectrometer module 2 comprises a laser and a Raman spectrometer corresponding to different wavelengths; the micro control system 1 is respectively connected with the laser with each wavelength and the Raman spectrometer, sets the wavelength and the power of each laser, sets the integration time and the integration times of each spectrometer, and collects and outputs Raman spectrum signals.
The detector is used for realizing Raman in-situ and simultaneous detection of multiple wavelengths.
The detector has various wavelengths of ultraviolet, visible light and near infrared wave bands.
In the optical path coupling module 37, a long-wave pass dichroic mirror 38 transmits a near-infrared band spectrum and reflects a visible band spectrum; the short wave pass dichroic mirror 39 transmits the ultraviolet band spectrum, reflects the visible and near infrared band spectrum, and the achromatic objective lens 40 focuses on the sample test point 41.
The multi-wavelength Raman front-end optical path module 42 comprises an ultraviolet Raman front-end optical path module 15, a visible Raman front-end optical path module 22, a near infrared Raman front-end optical path module 29 and an optical path coupling module 37; wherein:
the ultraviolet raman front-end optical path module 15 comprises an ultraviolet laser collimating mirror 16, an ultraviolet laser light filter 17, an ultraviolet plane reflecting mirror 18, an ultraviolet laser dichromatic mirror 19, an ultraviolet raman spectrum cut-off filter 20 and an ultraviolet spectrometer fiber coupling mirror 21.
The visible raman front optical path module 22 includes a visible laser collimating mirror 23, a visible laser line filter 24, a visible plane reflecting mirror 25, a visible laser dichromatic mirror 26, a visible raman spectrum cut-off filter 27 and a visible spectrometer fiber coupling mirror 28.
The near-infrared raman front optical path module 29 comprises a near-infrared laser collimating mirror 30, a near-infrared laser ray filter 31, a first near-infrared plane reflector 32, a near-infrared laser dichromatic mirror 33, a second near-infrared plane reflector 34, a near-infrared raman spectrum cut-off filter 35 and a near-infrared spectrometer optical fiber coupling mirror 36.
The detector has independent light paths in ultraviolet, visible and near-infrared wavelength ranges, wherein:
the ultraviolet laser collimating lens 16, the ultraviolet laser light filter 17, the ultraviolet plane reflecting mirror 18, the ultraviolet laser dichroscope 19, the short wave-pass dichroscope 39 and the achromatic objective lens 40 are sequentially arranged along the light path direction to form an ultraviolet emission light path; the achromatic objective lens 40, the short wave-pass dichroic mirror 39, the ultraviolet laser dichromatic mirror 19, the ultraviolet Raman spectrum cut-off filter 20 and the ultraviolet spectrometer optical fiber coupling mirror 21 are sequentially arranged along the optical path direction to form an ultraviolet receiving optical path.
The visible laser collimating lens 23, the visible laser line filter 24, the visible plane reflecting mirror 25, the visible laser dichroscope 26, the long-wave-pass dichroscope 38, the short-wave-pass dichroscope 39 and the achromatic objective lens 40 are sequentially arranged along the light path direction to form a visible emission light path; the achromatic objective lens 40, the short-wave-pass dichroic mirror 39, the long-wave-pass dichroic mirror 38, the visible laser dichromatic mirror 26, the visible Raman spectrum cut-off filter 27 and the visible spectrometer fiber coupling mirror 28 are sequentially arranged along the light path direction to form a visible receiving light path.
The near-infrared laser collimating mirror 30, the near-infrared laser ray filter 31, the first near-infrared plane reflecting mirror 32, the near-infrared laser dichromatic mirror 33, the second near-infrared plane reflecting mirror 34, the long-wave pass dichroic mirror 38, the short-wave pass dichroic mirror 39 and the achromatic objective lens 40 are sequentially arranged along the light path direction to form a near-infrared emission light path; the achromatic objective lens 40, the short-wave-pass dichroic mirror 39, the long-wave-pass dichroic mirror 38, the second near-infrared plane reflecting mirror 34, the near-infrared laser dichromatic mirror 33, the near-infrared Raman spectrum cut-off filter 35 and the near-infrared spectrometer optical fiber coupling mirror 36 are sequentially arranged along the optical path direction to form a near-infrared receiving optical path.
The laser and spectrometer module 2 comprises an ultraviolet laser 3, an ultraviolet Raman spectrometer 4, a visible laser 5, a visible Raman spectrometer 6, a near infrared laser 7 and a near infrared Raman spectrometer 8.
The ultraviolet laser 3 and the ultraviolet Raman spectrometer 4 are respectively connected with the ultraviolet Raman preposed optical path module 15 through an ultraviolet laser transmitting optical fiber 9 and an ultraviolet spectrum receiving optical fiber 10.
The visible laser 5 and the visible raman spectrometer 6 are respectively connected with the visible raman front optical path module 22 through a visible laser emitting fiber 11 and a visible spectrum receiving fiber 12.
The near-infrared laser 7 and the near-infrared Raman spectrometer 8 are respectively connected with a near-infrared Raman front-end light path module 29 through a near-infrared laser transmitting optical fiber 13 and a near-infrared spectrum receiving optical fiber 14.
The micro control system 1 is respectively connected with the ultraviolet laser 3, the ultraviolet Raman spectrometer 4, the visible laser 5, the visible Raman spectrometer 6, the near infrared laser 7 and the near infrared Raman spectrometer 8, and can be used for setting the wavelength and the power of each laser, setting the integration time and the integration times of each spectrometer, and collecting and outputting Raman spectrum signals.
The ultraviolet laser 3 is a semiconductor laser, and the wavelength lambda 1 is more than or equal to 200 nm; the ultraviolet Raman spectrometer 4 is a micro optical fiber spectrometer.
The visible laser 5 is a semiconductor laser, the wavelength lambda 2 corresponds to the wave number sigma 2, the wavelength lambda 1 of the ultraviolet laser corresponds to the wave number sigma 1, and the wavelength lambda 2 and the wave number sigma 1 satisfy the following conditions: sigma 1-sigma 2 is more than 6000cm-1(ii) a The visible Raman spectrometer 6 is a micro fiber spectrometer.
The near-infrared laser 7 is a semiconductor laser, the wavelength lambda 3 corresponds to the wave number sigma 3, the wavelength lambda 2 of the visible laser 5 corresponds to the wave number sigma 2, and the wavelength lambda 2 and the wave number sigma 2 meet the following conditions: sigma 3-sigma 2 is more than 6000cm-1(ii) a The near-infrared Raman spectrometer 8 is a micro optical fiberA spectrometer.
A detection method based on a compact portable multi-wavelength Raman detector comprises the following steps:
the micro control system 1 sends instructions to the ultraviolet laser 3, the ultraviolet Raman spectrometer 4, the visible laser 5, the visible Raman spectrometer 6, the near-infrared laser 7 and the near-infrared Raman spectrometer 8, and simultaneously performs ultraviolet Raman spectrum detection, visible Raman spectrum detection and near-infrared Raman spectrum detection, so as to simultaneously acquire multi-wavelength in-situ Raman spectrum information of the sample.
The micro-control system 1 performs database comparison analysis on the ultraviolet Raman spectrum, the visible Raman spectrum and the near-infrared Raman spectrum which simultaneously receive the in-situ information of the sample, performs database comparison identification on the three types of Raman spectra, and can determine that the identification is correct when the three types of Raman spectra identify the substances consistently; otherwise, entering a characteristic wavelength Raman accurate detection step.
The method further comprises the following characteristic wavelength Raman accurate detection steps: based on the multi-wavelength in-situ Raman spectrum information of the sample, the micro-control system 1 selects the characteristic laser wavelength of the sample to accurately detect the characteristic wavelength Raman, and then the high signal-to-back ratio Raman spectrum information of the sample is obtained.
The micro control system 1 sends a control instruction and starts the characteristic laser wavelength at the same time to carry out the accurate detection of the characteristic wavelength Raman, the micro control system 1 carries out database comparison analysis on the received characteristic wavelength Raman spectrum information, and when the identification degree of the characteristic Raman spectrum of the sample is higher than or equal to 80%, the identification is correct; and when the concentration is less than 80%, entering a multi-wavelength fluorescence quenching fine detection step.
The method further comprises the following multi-wavelength fluorescence quenching fine inspection steps: the micro-control system 1 selects a Raman spectrum area in a certain range, calculates the signal-to-back ratios of the ultraviolet Raman spectrum, the visible Raman spectrum and the near-infrared Raman spectrum, selects the characteristic laser wavelength with the highest signal-to-back ratio and performs the Raman accurate detection of the characteristic wavelength.
The micro control system 1 sets the other one or two laser beams as a fluorescence quenching light source, the optimized characteristic laser wavelength is used as a Raman test light source, and the micro control system 1 performs Raman test of the optimized characteristic laser wavelength after the sample is irradiated for a long time by the fluorescence quenching light source until the identification degree of the characteristic Raman spectrum of the sample is equal to or higher than 80%; t is 1 to 600 minutes.
The multi-wavelength fluorescence quenching fine inspection step comprises the following steps: based on the characteristic laser wavelength of the sample, the micro control system 1 sets the other one or two of the three lasers of ultraviolet, visible and near infrared as a fluorescence quenching light source, so as to effectively reduce the fluorescence background signal interference of the sample.
Compared with the prior art, the invention has the beneficial effects that:
according to the compact multi-wavelength in-situ Raman spectrum detection system, the group of long-wave-pass dichroic mirrors and the group of short-wave-pass dichroic mirrors are commonly used in the multi-wavelength in-situ Raman spectrum detection system, so that organic combination of ultraviolet Raman, visible Raman and near infrared Raman is realized, and simultaneous testing of in-situ Raman detection modules with three wavelengths is met. The detection system does not need to be additionally provided with a mobile device, can ensure the stability of the instrument and meets the requirement of portable Raman on a laser Raman spectrum system with various wavelengths. The detection system has a multi-wavelength Raman in-situ detection working mode, a characteristic wavelength Raman accurate detection working mode and a multi-wavelength fluorescence quenching accurate detection working mode, can effectively reduce fluorescence background signals aiming at high fluorescence background samples, and improves the accuracy and reliability of detection.
Drawings
Fig. 1 is a schematic structural diagram of the compact multi-wavelength in-situ raman spectroscopy detector of the present invention.
Wherein the reference numerals are:
1 micro control system 2 laser and spectrometer module
3 ultraviolet laser 4 ultraviolet Raman spectrometer
5 visible laser 6 visible Raman spectrometer
7 near-infrared laser 8 near-infrared Raman spectrometer
9 ultraviolet laser transmitting optical fiber 10 ultraviolet spectrum receiving optical fiber
11 visible laser emission optical fiber 12 visible spectrum receiving optical fiber
13 near-infrared laser emission optical fiber 14 near-infrared spectrum receiving optical fiber
15 ultraviolet Raman front light path module 16 ultraviolet laser collimating lens
17 ultraviolet laser light filter 18 ultraviolet plane reflector
19 ultraviolet laser diphase color mirror 20 ultraviolet Raman spectrum cut-off filter
21 ultraviolet spectrometer optical fiber coupling mirror 22 visible Raman front-end optical path module
23 visible laser collimating mirror 24 visible laser line filter
25 visible plane reflector 26 visible laser diphase mirror
27 visible Raman spectrum cut-off filter 28 visible spectrometer optical fiber coupling mirror
29 near-infrared Raman front-mounted light path module 30 near-infrared laser collimating mirror
31 near-infrared laser ray filter 32 first near-infrared plane mirror
33 near-infrared laser diphase mirror 34 second near-infrared plane reflector
35 near-infrared Raman spectrum cut-off filter 36 near-infrared spectrometer optical fiber coupling mirror
37 optical path coupling module 38 long wave pass dichroic mirror
39 short wave pass dichroic mirror 40 achromatic objective lens
41 sample test point 42 multi-wavelength Raman front-end optical path module
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
As shown in fig. 1, a compact portable multi-wavelength in-situ raman detector includes a micro control system 1, a laser and spectrometer module 2, and a multi-wavelength raman front-end optical path module 42. Wherein:
the multi-wavelength Raman front-end optical path module 42 comprises an ultraviolet Raman front-end optical path module 15, a visible Raman front-end optical path module 22, a near infrared Raman front-end optical path module 29 and an optical path coupling module 37;
the ultraviolet Raman preposed optical path module 15 comprises an ultraviolet laser collimating mirror 16, an ultraviolet laser light filter 17, an ultraviolet plane reflecting mirror 18, an ultraviolet laser dichromatic mirror 19, an ultraviolet Raman spectrum cut-off filter 20 and an ultraviolet spectrometer fiber coupling mirror 21;
the visible Raman preposed optical path module 22 comprises a visible laser collimating mirror 23, a visible laser line optical filter 24, a visible plane reflecting mirror 25, a visible laser dichroscope, a visible Raman spectrum cut-off optical filter 27 and a visible spectrometer optical fiber coupling mirror 28;
the near-infrared raman front optical path module 29 comprises a near-infrared laser collimating mirror 30, a near-infrared laser ray filter 31, a first near-infrared plane reflector 32, a near-infrared laser dichromatic mirror 33, a second near-infrared plane reflector 34, a near-infrared raman spectrum cut-off filter 35 and a near-infrared spectrometer optical fiber coupling mirror 36;
the optical path coupling module 37 comprises a long-wave-pass dichroic mirror 38, a short-wave-pass dichroic mirror 39 and an achromatic objective lens 40;
the long-wavelength-pass dichroic mirror 38 transmits the infrared band spectrum and reflects the visible band spectrum;
the short wave pass dichroic mirror 39 transmits the ultraviolet band spectrum and reflects the visible and near infrared band spectra;
the micro control system 1 is internally provided with main control software which can set the wavelength and power of an output laser, set the integration time and integration times of a spectrometer, and collect and output Raman spectrum signals;
the laser and spectrometer module 2 comprises an ultraviolet laser 3, an ultraviolet Raman spectrometer 4, a visible laser 5, a visible Raman spectrometer 6, a near-infrared laser 7 and a near-infrared Raman spectrometer 8;
the laser 3 is a semiconductor laser, and the wavelength lambda 1 is more than or equal to 200 nm;
the laser 3 is connected with the multi-wavelength Raman front-end optical path module 42 through an ultraviolet laser transmitting optical fiber 9;
the ultraviolet Raman spectrometer 4 is a micro optical fiber spectrometer;
the ultraviolet Raman spectrometer 4 is connected with the multi-wavelength Raman preposed optical path module 42 through the ultraviolet spectrum receiving optical fiber 10;
the visible laser 5 is a semiconductor laser, the wavelength lambda 2 corresponds to the wave number sigma 2, and the wave number sigma 1 corresponds to the wavelength lambda 1 of the laser ultraviolet laser 3, and the wavelength lambda 2 and the wave number sigma 1 satisfy the following conditions: sigma 1-sigma 2 is more than 6000cm-1；
The visible laser 5 is connected with the multi-wavelength Raman front-end optical path module 42 through the visible laser transmitting optical fiber 11;
the visible Raman spectrometer 6 is a micro optical fiber spectrometer;
the visible Raman spectrometer 6 is connected with the multi-wavelength Raman front-end optical path module 42 through the visible spectrum receiving optical fiber 12;
the near-infrared laser 7 is a semiconductor laser, the wave number sigma 3 corresponding to the wavelength lambda 3 and the wave number sigma 2 corresponding to the wavelength lambda 2 of the visible laser 5 satisfy the following conditions: sigma 3-sigma 2 is more than 6000cm-1；
The near-infrared laser 7 is connected with the multi-wavelength Raman front-end optical path module 42 through a near-infrared laser transmitting optical fiber 13;
the near infrared Raman spectrometer 8 is a micro optical fiber spectrometer;
the near-infrared Raman spectrometer 8 is connected with the multi-wavelength Raman front-end optical path module 42 through the near-infrared spectrum receiving optical fiber 14.
The detection method and the mode of the multi-wavelength portable Raman detector are as follows:
(1) multi-wavelength Raman in-situ detection working mode
Under the accurate detection mode of characteristic wavelength raman, the micro control system 1 sends out an instruction to simultaneously perform ultraviolet raman spectrum detection, visible raman spectrum detection and near-infrared raman spectrum detection, under the working mode, the in-situ multi-wavelength raman spectrum information of the sample can be simultaneously obtained, and the specific working flow is as follows:
the micro control system 1 sends out a control instruction to simultaneously start the ultraviolet laser 3, the visible laser 5 and the near-infrared laser 7, wherein:
light beams generated by an ultraviolet laser 3 are transmitted through an ultraviolet laser transmitting optical fiber 9 to enter a Raman preposed light path module, are subjected to laser beam expansion and collimation through an ultraviolet laser collimating mirror 16, are filtered to remove plasma rays through an ultraviolet laser ray filter 17, are subjected to 90-degree light path conversion through an ultraviolet plane reflecting mirror 18, are reflected through an ultraviolet laser two-phase color mirror 19, couple ultraviolet laser and an ultraviolet Raman scattering light path, penetrate through a short-wave transmission dichroic mirror 39 and are focused to a sample test point 41 through an achromatic objective lens 40;
light beams generated by a visible laser 5 are transmitted through a visible laser transmitting optical fiber 11 to enter a Raman preposed light path module, are subjected to laser beam expansion and collimation through a visible laser collimating mirror 23, are filtered to remove plasma rays through a visible laser line optical filter 24, are subjected to 90-degree light path deflection through a visible plane reflecting mirror 25, are reflected through a visible laser dichroscope, couple visible laser and a visible Raman scattering light path, are reflected through a long-wave-pass dichroscope 38, are reflected by a short-wave-pass dichroscope 39, and finally enter an achromatic objective 40 to be focused to a sample test point 41;
light beams generated by a near-infrared laser 7 are transmitted through a near-infrared laser transmitting optical fiber 13 to enter a Raman preposed light path module, are expanded and collimated by a near-infrared laser collimating mirror 30, are filtered to remove plasma rays through a near-infrared laser line optical filter 31, are subjected to 90-degree light path conversion through a first near-infrared plane reflector 32, are reflected by a near-infrared laser two-phase color mirror 33, couple near-infrared laser and a near-infrared Raman scattering light path, are subjected to 90-degree light path conversion through a second near-infrared plane reflector 34, are reflected through a long-wave dichroic mirror 38, are reflected through a short-wave dichroic mirror 39, and finally enter an achromatic objective 40 to be focused to a sample test point 41;
the sample test point 41 is excited by the ultraviolet laser, the visible laser and the near-infrared laser to simultaneously generate an ultraviolet raman spectrum, a visible raman spectrum and a near-infrared raman spectrum, wherein: the ultraviolet Raman spectrum passes through the achromatic objective lens 40, the short wave pass dichroic mirror 39 and the ultraviolet laser two-phase color mirror 19, then is filtered by the ultraviolet Raman spectrum cut-off filter 20 to remove the ultraviolet laser Rayleigh scattering spectrum, is converged and collected into the ultraviolet spectrum receiving optical fiber 10 by the ultraviolet spectrometer optical fiber coupling mirror 21, then enters the ultraviolet Raman spectrometer 4 for light splitting detection, and transmits the detected ultraviolet Raman spectrum to the micro-control system 1 for analysis.
The visible Raman spectrum penetrates through the achromatic objective lens 40, is reflected by the short wave pass dichroic mirror 39 and the long wave pass dichroic mirror 38, penetrates through the visible laser dichroism mirror 26, is filtered by the visible Raman spectrum cut-off filter 27 to remove the visible laser Rayleigh scattering spectrum, is converged and collected into the visible spectrum receiving optical fiber 12 by the visible spectrometer optical fiber coupling mirror 28, then enters the visible Raman spectrometer 6 to be subjected to light splitting detection, and the detected visible Raman spectrum is transmitted to the micro-control system 1 to be analyzed.
The near-infrared Raman spectrum penetrates through an achromatic objective lens 40, is reflected by a short-wave-pass dichroic mirror 39, is transmitted by a long-wave-pass dichroic mirror 38, is reflected by a second near-infrared plane reflecting mirror 34, penetrates through a near-infrared laser dichroic mirror 33, is filtered by a near-infrared Raman spectrum cut-off filter 35 to remove a near-infrared laser Rayleigh scattering spectrum, is converged and collected into a near-infrared spectrum receiving optical fiber 14 by a near-infrared spectrometer optical fiber coupling mirror 36, enters a near-infrared Raman spectrometer 8, is subjected to light splitting detection, and is transmitted to a micro control system 1 for analysis.
The micro-control system 1 performs database comparison analysis on the ultraviolet Raman spectrum, the visible Raman spectrum and the near-infrared Raman spectrum which simultaneously receive the in-situ information of the sample, performs database comparison identification on the three types of Raman spectra, and can determine that the identification is correct when the three types of Raman spectra identify the substances consistently; otherwise, the next step of characteristic wavelength Raman accurate detection is carried out:
(2) characteristic wavelength Raman accurate detection working mode
Under the characteristic wavelength Raman accurate detection working mode, based on the multi-wavelength Raman spectrum information acquired by the multi-wavelength Raman in-situ detection working mode, the micro control system 1 preferably selects the characteristic laser wavelength of the sample to perform the characteristic wavelength Raman accurate detection, and under the working mode, the high signal-to-back ratio Raman spectrum information of the sample can be acquired, and the specific working process is as follows:
the micro-control system 1 selects a Raman spectrum region in a specific range, calculates the signal-to-back ratios of the ultraviolet Raman spectrum, the visible Raman spectrum and the near-infrared Raman spectrum, and preferably selects the characteristic laser wavelength with the highest signal-to-back ratio.
The micro control system 1 sends a control instruction and starts the characteristic laser wavelength to accurately detect the characteristic wavelength Raman, the micro control system 1 performs database comparison analysis on the received characteristic wavelength Raman spectrum information, and when the identification degree of the characteristic Raman spectrum of the sample is higher than 80%, the identification is correct; and conversely, the next step of multi-wavelength fluorescence quenching fine inspection is carried out.
(3) Multi-wavelength fluorescence quenching fine inspection working mode
Under the multi-wavelength fluorescence quenching accurate detection working mode, based on the characteristic laser wavelength of the sample obtained under the characteristic wavelength Raman accurate detection working mode, the micro control system 1 sets one or two other lasers as a fluorescence quenching light source, under the working mode, the fluorescence background signal interference of the sample can be effectively reduced, and the specific working process is as follows:
the micro-control system 1 is provided with one or two laser beams as a fluorescence quenching light source, and the preferred characteristic laser wavelength is used as a Raman test light source. The micro-control system 1 performs the Raman test of the optimized characteristic laser wavelength after the sample is subjected to long-time t irradiation by arranging the fluorescence quenching light source until the identification degree of the characteristic Raman spectrum of the sample is higher than 80%.
Claims (12)
1. A compact portable multi-wavelength in-situ Raman detector comprises a micro main control system (1), a laser and spectrometer module (2) and a multi-wavelength Raman front-end light path module (42), and is characterized in that the multi-wavelength Raman front-end light path module (42) comprises a plurality of Raman front-end light path modules and a light path coupling module (37), wherein the Raman front-end light path modules respectively correspond to different wavelength ranges and share the light path coupling module (37); the light path coupling module (37) is provided with a long-wave-pass dichroic mirror (38) and a short-wave-pass dichroic mirror (39) which selectively transmit and/or reflect light beams with different wavelengths respectively;
the laser and spectrometer module (2) comprises a laser and a Raman spectrometer corresponding to different wavelengths; the micro control system (1) is respectively connected with the laser with each wavelength and the Raman spectrometer, the wavelength and the power of each laser are set, the integration time and the integration times of each spectrometer are set, and Raman spectrum signals are collected and output;
the detector is used for realizing Raman in-situ and simultaneous detection of multiple wavelengths.
2. The compact portable multi-wavelength in situ Raman detector according to claim 1, wherein the plurality of wavelengths of the detector are in the ultraviolet, visible, and near infrared bands.
3. The compact portable multi-wavelength in situ Raman detector according to claim 2, wherein in said optical path coupling module (37) a long-wave pass dichroic mirror (38) transmits the near infrared band spectrum and reflects the visible band spectrum; the short wave-pass dichroic mirror (39) transmits the ultraviolet band spectrum, reflects the visible and near infrared band spectrum, and the achromatic objective lens (40) focuses on the sample test point (41).
4. The compact portable multi-wavelength in situ Raman detector according to claim 1, wherein the multi-wavelength Raman front-end optical path module (42) comprises an ultraviolet Raman front-end optical path module (15), a visible Raman front-end optical path module (22), a near infrared Raman front-end optical path module (29), and an optical path coupling module (37); wherein:
the ultraviolet Raman preposed optical path module (15) comprises an ultraviolet laser collimating mirror (16), an ultraviolet laser ray filter (17), an ultraviolet plane reflector (18), an ultraviolet laser dichromatic mirror (19), an ultraviolet Raman spectrum cut-off filter (20) and an ultraviolet spectrometer optical fiber coupling mirror (21);
the visible Raman preposed optical path module (22) comprises a visible laser collimating mirror (23), a visible laser line optical filter (24), a visible plane reflecting mirror (25), a visible laser dichroscope (26), a visible Raman spectrum cut-off optical filter (27) and a visible spectrometer optical fiber coupling mirror (28);
the near-infrared Raman preposed optical path module (29) comprises a near-infrared laser collimating mirror (30), a near-infrared laser ray optical filter (31), a first near-infrared plane reflecting mirror (32), a near-infrared laser dichromatic mirror (33), a second near-infrared plane reflecting mirror (34), a near-infrared Raman spectrum cut-off optical filter (35) and a near-infrared spectrometer optical fiber coupling mirror (36).
5. The compact portable multi-wavelength in situ Raman detector according to claim 4, having independent optical paths in the ultraviolet, visible, and near infrared wavelength ranges, wherein:
the ultraviolet laser collimator (16), the ultraviolet laser light filter (17), the ultraviolet plane reflector (18), the ultraviolet laser dichroscope (19), the short-wave-pass dichroic mirror (39) and the achromatic objective (40) are sequentially arranged along the light path direction to form an ultraviolet emission light path; the achromatic objective lens (40), the short wave pass dichroic mirror (39), the ultraviolet laser dichromatic mirror (19), the ultraviolet Raman spectrum cut-off filter (20) and the ultraviolet spectrometer optical fiber coupling mirror (21) are sequentially arranged along the optical path direction to form an ultraviolet receiving optical path;
the visible emission light path is formed by sequentially arranging a visible laser collimating mirror (23), a visible laser line optical filter (24), a visible plane reflecting mirror (25), a visible laser dichroscope (26), a long-wave-pass dichroic mirror (38), a short-wave-pass dichroic mirror (39) and an achromatic objective lens (40) along the light path direction; the achromatic objective lens (40), the short-wave pass dichroic mirror (39), the long-wave pass dichroic mirror (38), the visible laser dichroscope (26), the visible Raman spectrum cut-off filter (27) and the visible spectrometer optical fiber coupling mirror (28) are sequentially arranged along the optical path direction to form a visible receiving optical path;
the near-infrared emission optical path comprises a near-infrared laser collimating mirror (30), a near-infrared laser line optical filter (31), a first near-infrared plane reflecting mirror (32), a near-infrared laser dichromatic mirror (33), a second near-infrared plane reflecting mirror (34), a long-wave-pass dichroic mirror (38), a short-wave-pass dichroic mirror (39) and an achromatic objective lens (40) which are sequentially arranged along the optical path direction to form a near-infrared emission optical path; the achromatic objective lens (40), the short-wave pass dichroic mirror (39), the long-wave pass dichroic mirror (38), the second near-infrared plane reflecting mirror (34), the near-infrared laser dichromatic mirror (33), the near-infrared Raman spectrum cut-off filter (35) and the near-infrared spectrometer optical fiber coupling mirror (36) are sequentially arranged along the optical path direction to form a near-infrared receiving optical path.
6. The compact portable multi-wavelength in situ Raman detector according to claim 1, wherein the laser and spectrometer module (2) comprises an ultraviolet laser (3), an ultraviolet Raman spectrometer (4), a visible laser (5), a visible Raman spectrometer (6), a near infrared laser (7) and a near infrared Raman spectrometer (8);
the ultraviolet laser (3) and the ultraviolet Raman spectrometer (4) are respectively connected with an ultraviolet Raman preposed optical path module (15) through an ultraviolet laser transmitting optical fiber (9) and an ultraviolet spectrum receiving optical fiber (10);
the visible laser (5) and the visible Raman spectrometer (6) are respectively connected with the visible Raman front-mounted optical path module (22) through a visible laser transmitting optical fiber (11) and a visible spectrum receiving optical fiber (12);
the near-infrared laser (7) and the near-infrared Raman spectrometer (8) are respectively connected with a near-infrared Raman front-mounted optical path module (29) through a near-infrared laser transmitting optical fiber (13) and a near-infrared spectrum receiving optical fiber (14).
7. The compact portable multi-wavelength in-situ Raman detector according to claim 6, wherein the micro-control system (1) is respectively connected with the ultraviolet laser (3), the ultraviolet Raman spectrometer (4), the visible laser (5), the visible Raman spectrometer (6), the near infrared laser (7) and the near infrared Raman spectrometer (8), and is capable of setting the wavelength and power of each laser, setting the integration time and integration times of each spectrometer, and collecting and outputting Raman spectrum signals.
8. The compact portable multi-wavelength in-situ Raman detector according to claim 6, wherein said UV laser (3) is a semiconductor laser with a wavelength λ 1 ≥ 200 nm; the ultraviolet Raman spectrometer (4) is a micro optical fiber spectrometer;
the visible laser (5) is a semiconductor laser, the wavelength lambda 2 corresponds to the wave number sigma 2, the wavelength lambda 1 of the ultraviolet laser corresponds to the wave number sigma 1, and the wavelength lambda 2 and the wave number sigma 1 meet the following conditions: sigma 1-sigma 2 is more than 6000cm-1(ii) a The visible Raman spectrometer (6) is a micro optical fiber spectrometer;
the near-infrared laser (7) is a semiconductor laser, the wavelength lambda 3 corresponds to the wave number sigma 3, the wavelength lambda 2 of the visible laser (5) corresponds to the wave number sigma 2, and the wavelength lambda 2 and the wave number sigma 2 meet the following conditions: sigma 3-sigma 2 is more than 6000cm-1(ii) a The near-infrared Raman spectrometer (8) is a micro optical fiber spectrometer.
9. A method of detecting a compact portable multi-wavelength raman detector according to claim 1, characterized in that it comprises the steps of:
the micro control system (1) sends instructions to the ultraviolet laser (3), the ultraviolet Raman spectrometer (4), the visible laser (5), the visible Raman spectrometer (6), the near-infrared laser (7) and the near-infrared Raman spectrometer (8), and simultaneously performs ultraviolet Raman spectrum detection, visible Raman spectrum detection and near-infrared Raman spectrum detection, so as to simultaneously acquire multi-wavelength in-situ Raman spectrum information of the sample;
the micro control system (1) performs database comparison analysis on the ultraviolet Raman spectrum, the visible Raman spectrum and the near infrared Raman spectrum which simultaneously receive the in-situ information of the sample, performs database comparison identification on the three types of Raman spectra, and can determine that the identification is correct when the three types of Raman spectra identify the substances consistently; otherwise, entering a characteristic wavelength Raman accurate detection step.
10. The detection method according to claim 9, further comprising the following characteristic wavelength raman accurate detection step: based on the multi-wavelength in-situ Raman spectrum information of the sample, the micro control system (1) selects the characteristic laser wavelength of the sample to perform accurate detection of characteristic wavelength Raman so as to obtain the high signal-to-back ratio Raman spectrum information of the sample;
the micro control system (1) sends a control instruction and starts the characteristic laser wavelength at the same time to accurately detect the characteristic wavelength Raman, the micro control system (1) performs database comparison analysis on the received characteristic wavelength Raman spectrum information, and when the identification degree of the characteristic Raman spectrum of the sample is higher than or equal to 80%, the identification is correct; and when the concentration is less than 80%, entering a multi-wavelength fluorescence quenching fine detection step.
11. The detection method according to claim 10, further comprising the following multi-wavelength fluorescence quenching fine detection steps: the micro control system (1) selects a Raman spectrum area in a certain range, calculates the signal-to-back ratios of an ultraviolet Raman spectrum, a visible Raman spectrum and a near-infrared Raman spectrum, selects the characteristic laser wavelength with the highest signal-to-back ratio and carries out accurate detection on Raman of the characteristic wavelength;
the micro control system (1) sets one or two other lasers as a fluorescence quenching light source, the preferable characteristic laser wavelength is used as a Raman test light source, and the micro control system (1) performs Raman test of the preferable characteristic laser wavelength after the sample is irradiated for a long time by setting the fluorescence quenching light source until the identification degree of the characteristic Raman spectrum of the sample is equal to or higher than 80%; t is 1 to 600 minutes.
12. The detection method according to claim 10, wherein the multi-wavelength fluorescence quenching fine detection step comprises: based on the characteristic laser wavelength of the sample, the micro control system (1) sets the other one or two of the three lasers of ultraviolet, visible and near infrared as a fluorescence quenching light source, so that the fluorescence background signal interference of the sample is effectively reduced.
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