CN107064100A - Fiber Raman spectrometer based on dispersion time-varying - Google Patents

Fiber Raman spectrometer based on dispersion time-varying Download PDF

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Publication number
CN107064100A
CN107064100A CN201611042228.2A CN201611042228A CN107064100A CN 107064100 A CN107064100 A CN 107064100A CN 201611042228 A CN201611042228 A CN 201611042228A CN 107064100 A CN107064100 A CN 107064100A
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light
optical fiber
fiber
raman
raman spectrometer
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CN107064100B (en
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祝连庆
姚齐峰
张雯
董明利
娄小平
何巍
刘锋
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Beijing Information Science and Technology University
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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
    • G01J3/28Investigating the spectrum
    • G01J3/44Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Spectrometry And Color Measurement (AREA)

Abstract

The invention discloses a kind of fiber Raman spectrometer based on dispersion time-varying, including laser detection system and Raman spectroscopic detection system, it is a kind of using the different phenomenon of speed that different frequency is propagated in dispersive optical fiber, so as to tell the spectrometer of the spectral signature of Raman signal in time domain.Spectrometer does not need traditional light-splitting device, while avoiding complex optical path design, can improve mechanical stability, and device size and weight can be reduced again, saves cost again portable.

Description

Fiber Raman spectrometer based on dispersion time-varying
Technical field
The present invention relates to Raman spectrometer field, and in particular to a kind of fiber Raman spectrometer based on dispersion time-varying.
Background technology
Raman line is to be found first when Study of Liquid benzene is scattered India physicist Raman nineteen twenty-eight, and it is a kind of Scattering spectrum.When illumination is mapped on object, there is part light to occur in inelastic scattering, scattered light except identical with incident light Elastic component it is outer (Rayleigh scattering), also have the composition for increasing than incident light frequency and reducing, the composition that wherein frequency reduces claims For stockes line, the composition of frequency increase is referred to as anti-stockes line, and twenty percent crossover rate, which is symmetrically distributed in, excites light frequency Both sides.
This result for mainly being interacted by the optical phonon in molecular vibration, lattice and excitation source of Ramam effect. When a photon and a molecule interact, a unstable virtual energy state is entered after one photon of molecule absorption, Then a photon can be radiated quickly, if the at this moment vibration of molecule or rotational energy level are higher than initial energy level, then transmitting The frequency of photon will be lower than primary photon, referred to as stokes light, otherwise the vibration of molecule or rotational energy level are than initial low, light The energy of son can increase, and frequency can be improved, and be referred to as anti-Stokes light, record what photon frequency occurred by Raman spectrometer The change of rule is referred to as Raman spectrum.
Each material has specific vibration or rotational energy level, to that should have a specific Raman line, and it is general not with Incident wavelength changes and changed, so Raman line is also referred to as fingerprint spectral line, is widely used in the demarcation of object components.
Current Raman spectrum analysis instrument develops into main following several forms:Confocal microscope Raman spectrum, resonance raman Spectrum, SERS and the enhanced Raman scattering of needle surface, these spectrometers are all by space spectroscopic modes To obtain spectral information, it is necessary to which the lens of grating and anaberration, light path design is complicated, calibration is also comparatively laborious, and machinery is steady It is qualitative not high;Simultaneously in the case where CCD sizes are certain, it is impossible to while meeting big spectral measurement ranges and high spectral resolution It is required that.
The content of the invention
The present invention provides the weight that a kind of fiber Raman spectrometer purpose based on dispersion time-varying is to mitigate spectrometer, together When ensure resolution ratio in the case of again can expand spectral measurement ranges.
The technical scheme is that:A kind of fiber Raman spectrometer based on dispersion time-varying include laser detection system and Raman spectroscopic detection system.
Described laser detection system includes pulse laser, first collimator and acousto-optic modulator.
Described Raman spectroscopic detection system includes the second collimater, coupler, the first photodetector and the two the second Detector, oscillograph, ordinary optic fibre and dispersive optical fiber.
The pulse laser is connected with first collimator by optical fiber, and acousto-optic modulator is opposing parallel with first collimator Place.
Second collimater is connected with coupler by optical fiber, and the coupler passes through common with the first photodetector Optical fiber is connected;The coupler is connected with the second photodetector by dispersive optical fiber;First photodetector and second Photodetection is connected by universal serial bus with oscillograph respectively.
It is preferred that, the ordinary optic fibre length specific dispersion fiber lengths are short.
It is preferred that, the coupler is 3dB photo-couplers.
It is preferred that, the laser is optical fiber locked mode soliton laser, and the laser uses nonlinear polarization rotation side Formula locked mode, graphene locked mode, make dye passive locked mode or active mode locking.
It is preferred that, the dispersive optical fiber is distributed linear chirp grating or photonic crystal fiber.
It is preferred that, the spectrometer also includes prism group and lens combination.
It is preferred that, the prism group includes reflecting prism and two to colour splitting prism, and the reflecting prism and two is to color separation rib Mirror is placed in longitudinal direction relative level;The lens group includes front end object lens and rear end object lens, and the lens group is placed in sample And second between collimater.
A kind of fiber Raman spectrometer method of testing based on dispersion time-varying, methods described comprises the following steps:
1) pulse laser sends pulse laser, and spatial light is formed after first collimator or speculum;
2) a portion light is selected using acousto-optic modulator so that go out light frequency for tens to hundreds of hertz;
3) pulse laser reaches and is reflected and scattered behind object under test surface, and a portion light passes through the second collimater quilt Optical fiber is collected;
4) reflection and scattered light collected enter coupler by optical fiber, are divided into two-way light;
5) wherein light is propagated in ordinary optic fibre all the way, it is more advanced enter photodetector in, in oscilloscope display pulse, make For the moment of start time 0;
6) another road light is propagated in dispersive optical fiber, because each frequency content light propagation constant differs in dispersive optical fiber Sample, another part reflected light and Raman diffused light are after dispersive optical fiber, and the light of different frequency composition reaches the time of detector It is different, if the receptance function of the detector is f (t);
7) in the case where parameter is fixed, the delay letter that light of the demarcation with different wave length is propagated in two-way optical fiber Number, i.e. λ=g (t);
8) time response function according to measured by fixed relationship, obtains the spectrum of reflected light and Raman light:Raman(λ) =f (g-1(λ)), its time graph responded is shown on oscillograph.
The beneficial effects of the invention are as follows:A kind of fiber Raman spectrometer based on dispersion time-varying eliminates original space point Light composition and ccd array detector, the substitute is dispersive optical fiber and high speed detector, can mitigate the weight of spectrometer, Again can ensure resolution ratio while more extended measurements spectral region;Spectrometer does not need traditional light-splitting device, avoids simultaneously Complex optical path design, can improve mechanical stability, and device size and weight are reduced again, save cost again portable.This Spectrometer is the spectrometer differentiated in time domain, and its precision is the speed of response decision by detector, but its measurement range not by Limitation, and conventional spectrometers are the light splitting on spatial domain, and its resolution ratio is determined by grating length, meet it is high-precision simultaneously, nothing Method meets the measurement of a wide range of spectrum.
Brief description of the drawings
With reference to the accompanying drawing enclosed, the present invention more purpose, function and advantages will pass through the as follows of embodiment of the present invention Description is illustrated, wherein:
Fig. 1 shows a kind of structural representation of the fiber Raman spectrometer based on dispersion time-varying of the present invention;
Fig. 2 shows a kind of structural representation of the fiber Raman spectrometer embodiment 2 based on dispersion time-varying of the present invention.
Embodiment
By reference to one exemplary embodiment, the purpose of the present invention and function and the side for realizing these purposes and function Method will be illustrated.However, the present invention is not limited to one exemplary embodiment as disclosed below;Can by multi-form come It is realized.The essence of specification is only to aid in the detail of the various equivalent modifications Integrated Understanding present invention.
Hereinafter, embodiments of the invention will be described with reference to the drawings.In the accompanying drawings, identical reference represents identical Or similar part, or same or like step.
Embodiment 1
Fig. 1 is a kind of structural representation of the fiber Raman spectrometer based on dispersion time-varying of the present invention.As shown in figure 1, one Planting the fiber Raman spectrometer based on dispersion time-varying includes laser detection system and Raman spectroscopic detection system.
Laser detection system includes pulse laser 101, first collimator 102 and acousto-optic modulator 103;Pulse laser 101 are connected with first collimator 102 by optical fiber, acousto-optic modulator 103 and the opposing parallel placement of first collimator 102, acousto-optic The pulsed light that modulator 103 is sent reaches testing sample 104 just.
Pulse laser 101 is optical fiber locked mode soliton laser, and pulse laser 101 can use nonlinear polarization rotation Mode locked mode can also be graphene or dye passive locked mode can also be active mode locking, and locked mode mode is determined according to actual conditions It is fixed.
Raman spectroscopic detection system includes the second collimater 110, coupler 105, the first photodetector 108 and the second light Electric explorer 111, oscillograph 109, ordinary optic fibre 106 and dispersive optical fiber 107.
Second collimater 110 is connected with coupler 105 by optical fiber, and coupler 105 passes through with the first photodetector 108 Ordinary optic fibre 106 is connected;Coupler 105 is connected with the second photodetector 111 by dispersive optical fiber 107;First photodetection The photodetection 111 of device 108 and second is connected by universal serial bus with oscillograph 109 respectively.
Length specific dispersion 107 length of optical fiber of ordinary optic fibre 106 are short.The dispersion of ordinary optic fibre 106 is small, and pulse is short, forms sharp arteries and veins Punching;The optical fiber of dispersive optical fiber 107 is long, and abbe number is big so that the light delay of two frequencies of each nanometer intervals wavelength can be arrived 500ps or so;Coupler 105 is 3dB photo-couplers;Dispersive optical fiber 107 can be that distributed linear chirp grating can also be Photonic crystal fiber.
There is more complicated index distribution on the cross section of photonic crystal fiber, usually contain the gas of multi-form arrangement Hole, the yardstick of stomata is with optical wavelength substantially in same magnitude and through the whole length of device, and the glistening light of waves can be limited in low Propagate in the fiber cores area of refractive index.
Distributed linear chirp grating is the grating that a kind of longitudinal direction of screen periods along optical fiber changes.
The pulse laser 101 that the present embodiment is used is optical fiber locked mode soliton laser.
The specific method that a kind of fiber Raman spectrometer based on dispersion time-varying obtains spectrum comprises the following steps:
1) optical fiber locked mode soliton laser 101 sends the pulse laser of about 1 micron wave length, and pulse width arrives several for tens Hundred femtoseconds, spatial light is become after first collimator 102;
2) because the repetition rate of mode-locked laser is very high, a portion light is selected using acousto-optic modulator 103 so that Go out light frequency for tens to hundreds of hertz;
3) pulse laser reaches and is reflected and scattered behind the surface of testing sample 104, and a portion light can be accurate by second Straight device 110 is collected by optical fiber;
4) reflection and scattered light collected enter 3dB photo-couplers 105 by optical fiber, are divided into two-way light;
5) wherein light is propagated in ordinary optic fibre 106 all the way, it is more advanced enter photodetector 108 in, because dispersion is small, arteries and veins Punching is very short, can be a very sharp pulse in oscillograph 109, be used as the moment of start time 0;
6) another road light is propagated in dispersive optical fiber 107, due in each frequency content light propagation constant of dispersive optical fiber 107 Different, another part reflected light and Raman diffused light are after dispersive optical fiber 107, and the light of different frequency composition reaches detector Time it is different, if the receptance function of the detector be f (t), for moment t is 0 at the time of being previously noted;
7) in the case where parameter is fixed, can demarcate that the light with different wave length propagates in this two-way optical fiber prolongs When function, i.e. λ=g (t);
8) according to fixed relationship above and measured time response function, pulse laser is opened up by dispersive optical fiber 107 It is wide after reach at a high speed the second photodetector 111, its respond time graph show on oscillograph 109, obtain reflected light with The spectrum of Raman light:Raman (λ)=f (g-1(λ))。
Utilize the relation of delay and dispersion, it is possible to obtain corresponding Raman spectrum.Arteries and veins needed for close-in measurement mode It is very small to rush energy, therefore laser pulse need not be amplified, nor infringement sample surfaces, is a kind of real Non-Destructive Testing.
Embodiment 2
Fig. 2 is a kind of structural representation of the fiber Raman spectrometer embodiment 2 based on dispersion time-varying of the present invention.This implementation The difference of example and embodiment 1 is:Added in the structure chart of embodiment 1 reflecting prism 211, two to dichronic mirror 212 and thoroughly Mirror system 213, realizes that remote Raman Measurement technology suppresses bias light and avoids the influence of fluorescence.
Reflecting prism 211 and testing sample 204 are placed in two reflection directions to dichronic mirror 212, lens combination 213 along light path It is placed in two transmission directions to dichronic mirror 212.
Wherein, reflecting prism 211 and two is not limited to isosceles right angle to the shape of dichronic mirror 212, can realize laser beam Reflection and transmission.
The pulse laser 210 that the present embodiment is used is solid state laser Nd:YAG laser.
A kind of specific method of the fiber Raman spectrometer telemeasurement technology based on dispersion time-varying comprises the following steps:
1) solid state laser Nd:YAG laser 210 sends the pulse laser of about 1.064 micron wave lengths, and pulse width is 150 femtoseconds;
2) because the repetition rate of laser is very high, it is necessary to select a portion light using acousto-optic modulator 203 so that Go out light frequency for tens to hundreds of hertz;
3) pulsed light reaches testing sample 204 after reflecting prism 211 and two reflects to dichronic mirror 212, and two to color separation Mirror 212 is that shortwave direction is reflected, and long wave direction is transmitted;
4) the reflected impulse light of testing sample 204, is transmitted through two to dichronic mirror 212, and reflected light and scattered light pass through optical lens Mirror system 213, becomes directional light into collimater 202, the front lens bore of optical lens system is 2 inches to 4 inches, is surveyed Distance is tried from 1 to 20m;
5) reflected light and scattered light enter 3dB photo-coupler 205, are divided into two-way light;
6) wherein light is propagated in ordinary optic fibre 206 all the way, it is more advanced enter photodetector 208 in, because dispersion is small, arteries and veins Punching is very short, can be a very sharp pulse in oscillograph 209, be used as the moment of start time 0;
7) light is propagated in dispersive optical fiber 207 all the way in addition, and because optical fiber is long, abbe number is big so that Mei Yina The light delay of two frequencies of rice interval wavelength can arrive 500ps or so, be higher than the minimum response time of photodetector, so right In 200nm spectral region, pulse stretcher to 100ns;
Due to dispersive optical fiber 207, each frequency content light propagation constant is different, another part reflected light and Raman scattering Light is after dispersive optical fiber 207, and the time of the light arrival detector of different frequency composition is different, if the response letter of the detector Number is f (t), for moment t is 0 at the time of being previously noted;
8) in the case where parameter is fixed, can demarcate that the light with different wave length propagates in this two-way optical fiber prolongs When function, i.e. λ=g (t);
9) according to fixed relationship above, and measured time response function, pulse laser is opened up by dispersive optical fiber 207 It is wide after reach at a high speed the second photodetector 214, its respond time graph show on oscillograph 209, obtain reflected light with The spectrum of Raman light:Raman (λ)=f (g-1(λ))。
With reference to the explanation of the invention disclosed here and practice, other embodiment of the invention is for those skilled in the art It all will be readily apparent and understand.Illustrate and embodiment is to be considered only as exemplary, of the invention true scope and purport is equal It is defined in the claims.

Claims (8)

1. a kind of fiber Raman spectrometer based on dispersion time-varying, the fiber Raman spectrometer includes laser detection system and drawing Graceful spectrum investigating system;
Described laser detection system includes pulse laser, first collimator and acousto-optic modulator;
Described Raman spectroscopic detection system includes the second collimater, coupler, the first photodetector, the second detector, shown Ripple device, ordinary optic fibre and dispersive optical fiber;
The pulse laser is connected with first collimator by optical fiber, acousto-optic modulator with first collimator is opposing parallel puts Put;
Second collimater is connected with coupler by optical fiber, and the coupler and the first photodetector pass through ordinary optic fibre Connection;The coupler is connected with the second photodetector by dispersive optical fiber;First photodetector and the second photoelectricity Detection is connected by universal serial bus with oscillograph respectively.
2. a kind of fiber Raman spectrometer based on dispersion time-varying according to claim 1, it is characterised in that described common Fiber lengths specific dispersion fiber lengths are short.
3. a kind of fiber Raman spectrometer based on dispersion time-varying according to claim 1, it is characterised in that the coupling Device is 3dB photo-couplers.
4. a kind of fiber Raman spectrometer based on dispersion time-varying according to claim 1, it is characterised in that the laser Device is optical fiber locked mode soliton laser, and the laser uses nonlinear polarization rotation mode locked mode, graphene locked mode, dyestuff quilt Dynamic locked mode or active mode locking.
5. a kind of fiber Raman spectrometer based on dispersion time-varying according to claim 1, it is characterised in that the dispersion Optical fiber is distributed linear chirp grating or photonic crystal fiber.
6. a kind of fiber Raman spectrometer based on dispersion time-varying according to claim 1, it is characterised in that spectrometer is also Including prism group and lens combination.
7. a kind of fiber Raman spectrometer based on dispersion time-varying according to claim 6, it is characterised in that the prism Group includes reflecting prism and two to colour splitting prism, and the reflecting prism is placed in two reflection directions to colour splitting prism;The lens System includes front end object lens and rear end object lens, and lens group is placed in two transmission directions to colour splitting prism.
8. a kind of method of testing of the fiber Raman spectrometer based on dispersion time-varying described in utilization claim 1, methods described Comprise the following steps:
1) pulse laser sends pulse laser, and spatial light is formed after first collimator or speculum group;
2) acousto-optic modulator selects a portion light so that go out light frequency for tens hertz to hundreds of hertz;
3) pulse laser reaches and is reflected and scattered behind object under test surface, and a portion light is directly over the second collimater quilt Optical fiber is collected or two become directional light and collected by the second collimater by optical fiber to dichronic mirror transmission and lens combination collection;
4) reflection and scattered light collected enter coupler by optical fiber, are divided into two-way light;
5) wherein light is propagated in ordinary optic fibre all the way, it is more advanced enter photodetector in, in oscilloscope display pulse, as when Between the moment of starting point 0;
6) another road light is propagated in dispersive optical fiber, because each frequency content light propagation constant is different in dispersive optical fiber, Another part reflected light and Raman diffused light are after dispersive optical fiber, and the time of the light arrival detector of different frequency composition differs Sample, if the receptance function of the detector is f (t);
7) in the case where parameter is fixed, the delay function that light of the demarcation with different wave length is propagated in two-way optical fiber, i.e. λ =g (t);
8) time response function according to measured by fixed relationship, obtains the spectrum of reflected light and Raman light:Raman (λ)=f (g-1(λ)), its respond time graph oscillograph on show.
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CN108398244A (en) * 2018-05-02 2018-08-14 中国人民解放军国防科技大学 Optical fiber laser parameter real-time measuring device based on inclined fiber bragg grating
CN109884025A (en) * 2019-01-21 2019-06-14 东莞理工学院 A kind of long-range SERS spectra detection system and method
CN110454142A (en) * 2019-05-23 2019-11-15 王恒 A kind of cable transmission underground LR laser raman testing tool
CN110864806A (en) * 2019-11-15 2020-03-06 天津大学 Real-time spectral measurement system based on grating-centered time domain spread dispersion Fourier transform
CN111766228A (en) * 2020-07-14 2020-10-13 中国科学院西安光学精密机械研究所 Non-invasive Raman fiber probe
CN113109316A (en) * 2021-03-25 2021-07-13 东莞市中科原子精密制造科技有限公司 Miniaturized spectrum detection module and spectrometer

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CN105866100A (en) * 2016-05-16 2016-08-17 浙江医药高等专科学校 Raman spectrum detection optical path device and detection method thereof

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