CN107167465A - A kind of dual-wavelength laser Raman spectrometer - Google Patents
A kind of dual-wavelength laser Raman spectrometer Download PDFInfo
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- CN107167465A CN107167465A CN201710544662.9A CN201710544662A CN107167465A CN 107167465 A CN107167465 A CN 107167465A CN 201710544662 A CN201710544662 A CN 201710544662A CN 107167465 A CN107167465 A CN 107167465A
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- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 71
- 238000001228 spectrum Methods 0.000 claims abstract description 33
- 238000001514 detection method Methods 0.000 claims abstract description 27
- 230000009977 dual effect Effects 0.000 claims abstract description 27
- 230000000295 complement effect Effects 0.000 claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 239000013307 optical fiber Substances 0.000 claims abstract description 13
- 239000000523 sample Substances 0.000 claims abstract description 11
- 230000003287 optical effect Effects 0.000 claims description 23
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000001237 Raman spectrum Methods 0.000 description 16
- 238000010606 normalization Methods 0.000 description 10
- 238000004611 spectroscopical analysis Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 4
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- 230000005693 optoelectronics Effects 0.000 description 4
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- 239000000463 material Substances 0.000 description 1
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- 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
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
- G01J3/0227—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using notch filters
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
- G01J3/0237—Adjustable, e.g. focussing
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- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/0262—Constructional arrangements for removing stray light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
- G01J3/4412—Scattering spectrometry
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- 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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- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
- G01J2003/4424—Fluorescence correction for Raman spectrometry
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- G01N2201/067—Electro-optic, magneto-optic, acousto-optic elements
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Abstract
The invention discloses a kind of dual-wavelength laser Raman spectrometer, the instrument mainly includes master controller, Raman spectrometer, super continuous spectrums laser and dual wavelength Raman probe.Wherein, dual wavelength Raman probe is made up of launching fiber, reception optical fiber, transmitting beam expanding lens, rf control unit, the complementary narrow pass filters of AOTF, Multicolour mirror, convergent mirror, total reflective mirror, the complementary arrowband resistance-trap filters of AOTF and fibre-coupled mirrors.The beneficial effects of the invention are as follows, complementary acousto-optic tunable filter is applied into dual wavelength Raman probe, and use super continuous spectrums laser and same spectrometer, realize the multiplexing of source and rear end, dual wavelength and the detection of continuous wavelength Raman can be effectively realized, to solve the interference of Raman fluorescence, improve Raman detection effect and provide solution.
Description
Technical field
The present invention relates to a kind of laser spectrum detection system, more particularly to a kind of instrument of use dual-wavelength laser Raman detection
Device, it is adaptable to the molecular chaperones detection of material, belongs to photodetection field.
Background technology
In LR laser raman detection, in addition to the excitation laser Raman scattering spectral line discrete except being inspired in target, also
There are the part of continuous radiation, i.e. fluorescent scattering to disturb, in some cases, hyperfluorescence background can have a strong impact on Raman signal,
Raman signal even is hidden, causes the degradation of LR laser raman Detection results.
Raman emission is distinguished using the laser of two close wavelength of wavelength, fluorescence is then eliminated by calculus of differences
Continuous radiation is a method for preferably suppressing to eliminate fluorescence.Independent dual wavelength system complexity when building increases
Plus twice, inefficiency.How efficiently and rapidly to realize dual-wavelength laser Raman detection is a urgent need to solve the problem.
The present invention is directed to the problem, proposes a kind of instrument for efficiently and rapidly realizing dual-wavelength laser Raman detection and side
Method, applies to dual wavelength Raman probe, and use super continuous spectrums laser and same spectrum by complementary acousto-optic tunable filter
Instrument, realizes the multiplexing of source and rear end, and the instrument and method can effectively realize dual wavelength Raman detection, and can be easily real
Now continuous wavelength Raman detection, to solve the interference of Raman fluorescence, improves Raman detection effect and provides solution.
The content of the invention
It is an object of the invention to provide a kind of instrument and method for efficiently and rapidly realizing dual-wavelength laser Raman detection,
By being multiplexed the portability and ease for use of increase instrument, to solve traditional Single wavelength LR laser raman fluorescence interference problem.
The present invention is achieved like this:
Dual wavelength Raman spectrometer mainly includes master controller, Raman spectrometer, super continuous spectrums laser and dual wavelength and drawn
Graceful probe.
Wherein, dual wavelength Raman probe is complementary by launching fiber, reception optical fiber, transmitting beam expanding lens, rf control unit, AOTF
The complementary arrowband resistance-trap filter of narrow pass filter, Multicolour mirror, convergent mirror, total reflective mirror, AOTF and fibre-coupled mirrors composition;
There is main control software in master controller, for being controlled to super continuous spectrums laser, rf control unit, and pass through
USB interface is powered and received to Raman spectrometer and analyzes its output spectrum signal;
Super continuous spectrums laser is connected by SMA interfaces with launching fiber;Raman spectrometer is connect with receiving optical fiber by SMA
Mouth connection;
Launch optical axis parallel with receiving optical axis, target detection point is located on transmitting optical axis;
Dual wavelength Raman spectrometer works according to the following steps:
(1) dual wavelength Raman signal is obtained
Master controller 3 sends control instruction and starts rf control unit, the passband ripple of the complementary narrow pass filters of setting AOTF
A length of λ1, the sunken bandgap wavelength of AOTF complementations arrowband resistance-trap filter is also λ1;
Master controller sends control instruction and starts super continuous spectrums laser, and the super continuous spectrums that super continuous spectrums laser is sent swash
Light is transmitted by launching fiber, is advanced after transmitting beam expanding lens is expanded along transmitting optical axis, by the complementary narrow passbands of AOTF
Wavelength is changed into λ after wave filter narrow-band filtering1, through Multicolour mirror, concentrated mirror focuses to target detection point;
The Raman echo signal of target detection point is returned along transmitting optical axis, through convergent mirror, after being reflected through Multicolour mirror, towards complete
Anti- mirror is advanced, then receives optical axis through total reflective mirror reflection rear steering, is filtered through the complementary arrowband resistance-trap filter Rayleighs of AOTF, is removed wavelength
For λ1Transmitting echo composition after, remaining Raman signal converges to reception fiber end face through fibre-coupled mirrors, subsequently into connecing
Inside of optical fibre transmission is received, Raman spectrometer is entered back into, by grating beam splitting, the excitation wavelength after opto-electronic conversion is λ1Raman light
Modal data feeding master controller carries out storage analysis;
Master controller sends control instruction and starts rf control unit, the passband wavelength of the complementary narrow pass filters of setting AOTF
For λ2, the sunken bandgap wavelength of AOTF complementations arrowband resistance-trap filter is also λ2;
Now, the super continuous spectrums laser that super continuous spectrums laser is sent is transmitted by launching fiber, by launching beam expanding lens
Advanced after being expanded along transmitting optical axis, wavelength is changed into λ after the complementary narrow pass filter narrow-band filterings of AOTF2, through many
Look mirror, concentrated mirror focuses to target detection point;
The Raman echo signal of target detection point is returned along transmitting optical axis, through convergent mirror, after being reflected through Multicolour mirror, towards complete
Anti- mirror is advanced, then receives optical axis through total reflective mirror reflection rear steering, is filtered through the complementary arrowband resistance-trap filter Rayleighs of AOTF, is removed wavelength
For λ2Transmitting echo composition after, remaining Raman signal converges to reception fiber end face through fibre-coupled mirrors, subsequently into connecing
Inside of optical fibre transmission is received, Raman spectrometer is entered back into, by grating beam splitting, the excitation wavelength after opto-electronic conversion is λ2Raman light
Modal data feeding master controller carries out storage analysis;
(2) dual wavelength Raman signal is handled
The analysis software program of master controller is analyzed the dual wavelength Raman spectrum data of collection according to the following steps:
A. area normalization
By λ1Raman spectrum data and λ2The area that is surrounded below by the curve of spectrum of Raman spectrum data be normalized
Computing, obtains λ1Normalization Raman spectrum data and λ2Normalization Raman spectrum data;
B. calculus of differences
By λ1Normalization Raman spectrum data subtract λ2Normalization Raman spectrum data;Eliminate interference and the shadow of fluorescence
Ring, that is, eliminate curve continuous fluorescence base part;
C. computing is blocked
By the later spectroscopic data of difference along λ2Position is blocked;
D. inverting op
Later spectroscopic data will be blocked and negated (reversion) computing;
E. positive computing is taken
Spectroscopic data after inverting op is carried out to take positive computing, negative spectrum intensity data is eliminated;
F. Raman frequency shift is changed
The abscissa of the spectroscopic data after positive computing will be taken to be converted to wave number cm by wavelength X-1, and and λ2Corresponding wavelength phase
Subtract, obtain Raman frequency shift.
The beneficial effects of the invention are as follows apply to dual wavelength Raman probe, and use by complementary acousto-optic tunable filter
Super continuous spectrums laser and same spectrometer, realize the multiplexing of source and rear end, can effectively realize dual wavelength and continuous many ripples
Long Raman detection, to solve the interference of Raman fluorescence, improves Raman detection effect and provides solution.
Brief description of the drawings
The dual wavelength Raman spectrometer structural representation that Fig. 1 designs for the present invention, Fig. 2 illustrates for the signal transacting of the present invention
In figure, figure:1 --- Raman spectrometer;2 --- super continuous spectrums laser;3 --- master controller;4 --- launching fiber;5——
Receive optical fiber;6 --- transmitting beam expanding lens;7 --- rf control unit;8 --- the complementary narrow pass filters of AOTF;9 --- polychrome
Mirror;10 --- convergent mirror;11 --- target detection point;12-transmitting optical axis;13 --- receive optical axis;14 --- dual wavelength Raman
Probe;15 --- total reflective mirror;16 --- AOTF complementations arrowband resistance-trap filter;17 --- fibre-coupled mirrors.
Note:AOTF, acousto-optic tunable filter, i.e. acousto-optic tunable filter.
Embodiment
The specific embodiment of the invention is as depicted in figs. 1 and 2.
As shown in figure 1, the dual wavelength Raman spectrometer that designs of the present invention mainly include master controller 3, Raman spectrometer 1,
Super continuous spectrums laser 2 and dual wavelength Raman probe 14.
Wherein, dual wavelength Raman probe 14 by launching fiber 4, receive optical fiber 5, transmitting beam expanding lens 6, rf control unit 7,
The complementary narrow pass filters 8 of AOTF, Multicolour mirror 9, convergent mirror 10, total reflective mirror 15, the complementary arrowband resistance-trap filters 16 of AOTF and optical fiber
Coupling mirror 17 is constituted;
Have main control software in master controller 3, for super continuous spectrums laser 2, rf control unit 7, pass through USB interface pair
Raman spectrometer 1 is powered and received and analyzes its output spectrum signal;
Super continuous spectrums laser 2 is connected by SMA interfaces with launching fiber 4;Raman spectrometer 1 passes through with receiving optical fiber 5
SMA interfaces are connected;
Launch optical axis 12 parallel with receiving optical axis 13, target detection point 11 is located on transmitting optical axis 12;
Dual wavelength Raman spectrometer works according to the following steps:
(1) dual wavelength Raman signal is obtained
Master controller 3 sends control instruction and starts rf control unit 7, the passband of the complementary narrow pass filters 8 of setting AOTF
Wavelength is λ1, the sunken bandgap wavelength of AOTF complementations arrowband resistance-trap filter 16 is also λ1;(the present embodiment λ1Take 785nm)
It is (near for 750nm-1250nm in the present embodiment that master controller 3 sends control instruction startup super continuous spectrums laser 2
The fiber optic supercontinuum laser of infrared repetition 2MHz pulsewidth picosecond magnitudes), the super continuous spectrums that super continuous spectrums laser 2 is sent swash
Light is transmitted by launching fiber 4, is advanced after transmitting beam expanding lens 6 is expanded along transmitting optical axis 12, narrow by AOTF complementations
Wavelength is changed into λ after the narrow-band filtering of pass filter 81, through Multicolour mirror 9, concentrated mirror 10 focuses to target detection point 11;
The Raman echo signal of target detection point 11 is returned along transmitting optical axis 12, through convergent mirror 10, is reflected through Multicolour mirror 9
Afterwards, advanced towards total reflective mirror 15, then optical axis 13 is received through the reflection rear steering of total reflective mirror 15, it is auspicious through the complementary arrowband resistance-trap filters 16 of AOTF
Profit filtering, removal wavelength is λ1Transmitting echo composition after, remaining Raman signal converges to reception light through fibre-coupled mirrors 17
Fine 5 end faces, subsequently into the internal transmission of optical fiber 5 is received, enter back into Raman spectrometer 1, by grating beam splitting, after opto-electronic conversion
Excitation wavelength is λ1Raman spectrum data feeding master controller 3 carry out storage analysis;
Master controller 3 sends control instruction and starts rf control unit 7, the passband of the complementary narrow pass filters 8 of setting AOTF
Wavelength is λ2, the sunken bandgap wavelength of AOTF complementations arrowband resistance-trap filter 16 is also λ2;(the present embodiment λ2Take 830nm)
Now, the super continuous spectrums laser that super continuous spectrums laser 2 is sent is transmitted by launching fiber 4, is expanded by transmitting
Mirror 6 is advanced after being expanded along transmitting optical axis 12, and wavelength is changed into λ after the complementary narrow narrow-band filterings of pass filter 8 of AOTF2,
Through Multicolour mirror 9, concentrated mirror 10 focuses to target detection point 11;
The Raman echo signal of target detection point 11 is returned along transmitting optical axis 12, through convergent mirror 10, is reflected through Multicolour mirror 9
Afterwards, advanced towards total reflective mirror 15, then optical axis 13 is received through the reflection rear steering of total reflective mirror 15, it is auspicious through the complementary arrowband resistance-trap filters 16 of AOTF
Profit filtering, removal wavelength is λ2Transmitting echo composition after, remaining Raman signal converges to reception light through fibre-coupled mirrors 17
Fine 5 end faces, subsequently into the internal transmission of optical fiber 5 is received, enter back into Raman spectrometer 1, by grating beam splitting, after opto-electronic conversion
Excitation wavelength is λ2Raman spectrum data feeding master controller 3 carry out storage analysis;
(2) dual wavelength Raman signal is handled
The analysis software program of master controller 3 is analyzed the dual wavelength Raman spectrum data of collection according to the following steps,
As shown in Figure 2:
A. area normalization
By λ1Raman spectrum data and λ2The area that is surrounded below by the curve of spectrum of Raman spectrum data be normalized
Computing, obtains λ1Normalization Raman spectrum data and λ2Normalization Raman spectrum data;
B. calculus of differences
By λ1Normalization Raman spectrum data subtract λ2Normalization Raman spectrum data;Eliminate interference and the shadow of fluorescence
Ring, that is, eliminate curve continuous fluorescence base part;
C. computing is blocked
By the later spectroscopic data of difference along λ2Position is blocked;
D. inverting op
Later spectroscopic data will be blocked and negated (reversion) computing;
E. positive computing is taken
Spectroscopic data after inverting op is carried out to take positive computing, negative spectrum intensity data is eliminated;
F. Raman frequency shift is changed
The abscissa of the spectroscopic data after positive computing will be taken to be converted to wave number cm by wavelength X-1, and and λ2Corresponding wavelength phase
Subtract, obtain Raman frequency shift.
Claims (1)
1. a kind of dual-wavelength laser Raman spectrometer, including master controller (3), Raman spectrometer (1), super continuous spectrums laser
And dual wavelength Raman probe (14) (2), it is characterised in that:
Dual wavelength Raman probe (14) by launching fiber (4), receive optical fiber (5), transmitting beam expanding lens (6), rf control unit (7),
The complementary narrow pass filters (8) of AOTF, Multicolour mirror (9), convergent mirror (10), total reflective mirror (15), the complementary arrowband resistance-trap filters of AOTF
(16) constituted with fibre-coupled mirrors (17);
There is main control software in master controller (3), for being controlled to super continuous spectrums laser (2), rf control unit (7), and
Raman spectrometer (1) is powered and received by USB interface and its output spectrum signal is analyzed;
Super continuous spectrums laser (2) is connected by SMA interfaces with launching fiber (4);Raman spectrometer (1) is with receiving optical fiber (5)
Connected by SMA interfaces;
Launch optical axis (12) parallel with receiving optical axis (13), target detection point (11) is located on transmitting optical axis (12).
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Cited By (2)
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CN110672830A (en) * | 2019-09-10 | 2020-01-10 | 中国科学院上海技术物理研究所 | Confocal Raman time domain resolution fluorescence rare animal blood detector |
CN110672831A (en) * | 2019-09-10 | 2020-01-10 | 中国科学院上海技术物理研究所 | Animal blood detection method based on confocal Raman immune time domain resolved fluorescence |
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CN113252637B (en) * | 2021-05-06 | 2022-06-10 | 河北大学 | Fluorescence background suppression system and suppression method in Raman spectrum detection |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110672830A (en) * | 2019-09-10 | 2020-01-10 | 中国科学院上海技术物理研究所 | Confocal Raman time domain resolution fluorescence rare animal blood detector |
CN110672831A (en) * | 2019-09-10 | 2020-01-10 | 中国科学院上海技术物理研究所 | Animal blood detection method based on confocal Raman immune time domain resolved fluorescence |
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Application publication date: 20170915 |