CN107167465A - A kind of dual-wavelength laser Raman spectrometer - Google Patents

A kind of dual-wavelength laser Raman spectrometer Download PDF

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Publication number
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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raman
wavelength
dual
mirror
aotf
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万雄
万嘉杰
王建宇
殷海玮
王泓鹏
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Shanghai Institute of Technical Physics of CAS
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0227Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using notch filters
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0237Adjustable, e.g. focussing
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0262Constructional arrangements for removing stray light
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/44Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/44Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • G01J3/4412Scattering spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/44Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • G01J2003/4424Fluorescence correction for Raman spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • G01N2021/0106General arrangement of respective parts
    • G01N2021/0112Apparatus in one mechanical, optical or electronic block
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/06Illumination; Optics
    • G01N2201/061Sources
    • G01N2201/06113Coherent sources; lasers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/06Illumination; Optics
    • G01N2201/067Electro-optic, magneto-optic, acousto-optic elements
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00Features of devices classified in G01N21/00
    • G01N2201/08Optical fibres; light guides

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

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

A kind of dual-wavelength laser Raman spectrometer
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).
CN201710544662.9A 2017-01-06 2017-07-06 A kind of dual-wavelength laser Raman spectrometer Pending CN107167465A (en)

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Cited By (2)

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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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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