CN107389652A - A kind of dual-wavelength laser Raman spectra detection process - Google Patents
A kind of dual-wavelength laser Raman spectra detection process Download PDFInfo
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- CN107389652A CN107389652A CN201710544661.4A CN201710544661A CN107389652A CN 107389652 A CN107389652 A CN 107389652A CN 201710544661 A CN201710544661 A CN 201710544661A CN 107389652 A CN107389652 A CN 107389652A
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/061—Sources
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/067—Electro-optic, magneto-optic, acousto-optic elements
Abstract
The invention discloses a kind of dual-wavelength laser Raman spectra detection process, this method is realized on dual-wavelength laser Raman spectrometer, and the instrument mainly includes master controller, Raman spectrometer, super continuous spectrums laser and dual wavelength Raman probe.This method includes dual wavelength Raman signal and obtained and dual wavelength Raman signal two steps of processing.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 method, more particularly to a kind of side using dual-wavelength laser Raman detection
Method, detected suitable for the molecular chaperones of material, belong to photodetection field.
Background technology
In LR laser raman detection, excitation laser in target in addition to inspiring discrete Raman scattering spectral line, also
The part of continuous radiation being present, i.e. fluorescent scattering is disturbed, and 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 structure increases
Add twice, efficiency is low.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, complementary acousto-optic tunable filter is applied into dual wavelength Raman probe, and use super continuous spectrums laser and same spectrum
Instrument, the multiplexing of source and rear end is realized, 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, improve Raman detection effect and provide 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
Narrow pass filter, Multicolour mirror, convergent mirror, total reflective mirror, AOTF complementations arrowband resistance-trap filter 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 reception optical fiber by SMA
Mouth connection；
It is parallel with receiving optical axis to launch optical axis, target detection point is on transmitting optical axis；
Dual wavelength Raman spectrometer works according to the following steps：
(1) dual wavelength Raman signal obtains
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 returns along transmitting optical axis, through convergent mirror, after Multicolour mirror reflects, towards complete
Anti- mirror is advanced, then receives optical axis through total reflective mirror reflection rear steering, is filtered through AOTF complementations arrowband resistance-trap filter Rayleigh, is removed wavelength
For λ1Transmitting echo composition after, remaining Raman signal converges to reception optical fiber end face through fibre-coupled mirrors, subsequently into connecing
Inside of optical fibre transmission is received, enters back into Raman spectrometer, by grating beam splitting, the excitation wavelength after opto-electronic conversion is λ1Raman light
Modal data is sent into master controller and 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 more
Look mirror, concentrated mirror focus to target detection point；
The Raman echo signal of target detection point returns along transmitting optical axis, through convergent mirror, after Multicolour mirror reflects, towards complete
Anti- mirror is advanced, then receives optical axis through total reflective mirror reflection rear steering, is filtered through AOTF complementations arrowband resistance-trap filter Rayleigh, is removed wavelength
For λ2Transmitting echo composition after, remaining Raman signal converges to reception optical fiber end face through fibre-coupled mirrors, subsequently into connecing
Inside of optical fibre transmission is received, enters back into Raman spectrometer, by grating beam splitting, the excitation wavelength after opto-electronic conversion is λ2Raman light
Modal data is sent into master controller and 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, obtain 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, eliminates negative spectrum intensity data；
F. Raman frequency shift is changed
The abscissa for taking the spectroscopic data after positive computing is converted into wave number cm by wavelength X-1, and and λ2Corresponding wavelength phase
Subtract, obtain Raman frequency shift.
The invention has the advantages that 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, can effectively realize dual wavelength and continuous more ripples
Long Raman detection, to solve the interference of Raman fluorescence, improve Raman detection effect and provide solution.
Brief description of the drawings
Fig. 1 is the dual wavelength Raman spectrometer structural representation that the present invention designs, and Fig. 2 is the signal transacting signal of the present invention
Scheme, in figure：1 --- Raman spectrometer；2 --- super continuous spectrums laser；3 --- master controller；4 --- launching fiber；5——
Reception 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, reception optical fiber 5, transmitting beam expanding lens 6, rf control unit 7,
AOTF complementary narrow pass filter 8, Multicolour mirror 9, convergent mirror 10, total reflective mirror 15, AOTF complementations arrowband resistance-trap filter 16 and optical fiber
Coupling mirror 17 forms；
There is main control software in master controller 3, for super continuous spectrums laser 2, rf control unit 7 to be controlled, and led to
USB interface is crossed 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 reception optical fiber 5
SMA interfaces connect；
It is parallel with receiving optical axis 13 to launch optical axis 12, target detection point 11 is on transmitting optical axis 12；
Dual wavelength Raman spectrometer works according to the following steps：
(1) dual wavelength Raman signal obtains
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 returns along transmitting optical axis 12, through convergent mirror 10, is reflected through Multicolour mirror 9
Afterwards, advanced towards total reflective mirror 15, then reflect rear steering through total reflective mirror 15 and receive optical axis 13, it is auspicious through AOTF complementations arrowband resistance-trap filter 16
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 reception optical fiber 5, enter back into Raman spectrometer 1, by grating beam splitting, after opto-electronic conversion
Excitation wavelength is λ1Raman spectrum data be sent into 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 returns along transmitting optical axis 12, through convergent mirror 10, is reflected through Multicolour mirror 9
Afterwards, advanced towards total reflective mirror 15, then reflect rear steering through total reflective mirror 15 and receive optical axis 13, it is auspicious through AOTF complementations arrowband resistance-trap filter 16
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 reception optical fiber 5, enter back into Raman spectrometer 1, by grating beam splitting, after opto-electronic conversion
Excitation wavelength is λ2Raman spectrum data be sent into 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, obtain 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, eliminates negative spectrum intensity data；
F. Raman frequency shift is changed
The abscissa for taking the spectroscopic data after positive computing is converted into 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 spectra detection process, this method are realized on dual-wavelength laser Raman spectrometer,
Described spectrometer mainly includes master controller (3), Raman spectrometer (1), super continuous spectrums laser (2) and dual wavelength Raman and visited
Head (14)；It is characterized in that dual-wavelength laser Raman detection method comprises the following steps：
1) dual wavelength Raman signal obtains
Master controller 3 sends control instruction and starts rf control unit, set the passband wavelength of the narrow pass filter of AOTF complementations as
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 laser that super continuous spectrums laser is sent leads to
Launching fiber transmission is crossed, is advanced after transmitting beam expanding lens is expanded along transmitting optical axis, is filtered by the complementary narrow passbands of AOTF
Wavelength is changed into λ after device narrow-band filtering1, through Multicolour mirror, concentrated mirror focuses to target detection point；
The Raman echo signal of target detection point returns along transmitting optical axis, through convergent mirror, after Multicolour mirror reflects, towards total reflective mirror
Advance, then optical axis is received through total reflective mirror reflection rear steering, filtered through AOTF complementations arrowband resistance-trap filter Rayleigh, removal wavelength is λ1
Transmitting echo composition after, remaining Raman signal converges to reception optical fiber end face through fibre-coupled mirrors, subsequently into receive light
Fine internal transmission, enters back into Raman spectrometer, and by grating beam splitting, the excitation wavelength after opto-electronic conversion is λ1Raman spectrum number
Storage analysis is carried out according to master controller is sent into；
Master controller sends control instruction and starts rf control unit, sets the passband wavelength of the complementary narrow pass filters of AOTF as 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, is carried out by launching beam expanding lens
Advanced after expanding along transmitting optical axis, wavelength is changed into λ after the complementary narrow pass filter narrow-band filterings of AOTF2, through Multicolour mirror,
Concentrated mirror focuses to target detection point；
The Raman echo signal of target detection point returns along transmitting optical axis, through convergent mirror, after Multicolour mirror reflects, towards total reflective mirror
Advance, then optical axis is received through total reflective mirror reflection rear steering, filtered through AOTF complementations arrowband resistance-trap filter Rayleigh, removal wavelength is λ2
Transmitting echo composition after, remaining Raman signal converges to reception optical fiber end face through fibre-coupled mirrors, subsequently into receive light
Fine internal transmission, enters back into Raman spectrometer, and by grating beam splitting, the excitation wavelength after opto-electronic conversion is λ2Raman spectrum number
Storage analysis is carried out according to master controller is sent into；
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 fortune is normalized
Calculate, obtain λ1Normalization Raman spectrum data and λ2Normalization Raman spectrum data；
B. calculus of differences
By λ1Normalization Raman spectrum data subtract λ2Normalization Raman spectrum data；The interference and influence of fluorescence are eliminated, i.e.,
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, eliminates negative spectrum intensity data；
F. Raman frequency shift is changed
The abscissa for taking the spectroscopic data after positive computing is converted into wave number cm by wavelength X-1, and and λ2Corresponding wavelength subtraction,
Obtain Raman frequency shift.
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| CN110398486B (en) * | 2018-04-24 | 2024-01-30 | 南京简智仪器设备有限公司 | Differential Raman spectrum detection device with movable light spots and detection method |
| CN109580587A (en) * | 2019-02-01 | 2019-04-05 | 浙江澍源智能技术有限公司 | A kind of difference Raman spectrometer that can deduct fluorescence in real time and its method |
| CN110174393B (en) * | 2019-06-27 | 2023-09-05 | 安徽大学 | Device and method for detecting vomitoxin of wheat by differential single photon Raman |
| CN111562252A (en) * | 2020-06-30 | 2020-08-21 | 普识和康(杭州)科技有限公司 | Raman detection system based on coaxial dual-wavelength fluorescence elimination |
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Application publication date: 20171124 |