CN106680260A - Portable coherent anti-Stokes Raman spectrometer - Google Patents
Portable coherent anti-Stokes Raman spectrometer Download PDFInfo
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- CN106680260A CN106680260A CN201510749716.6A CN201510749716A CN106680260A CN 106680260 A CN106680260 A CN 106680260A CN 201510749716 A CN201510749716 A CN 201510749716A CN 106680260 A CN106680260 A CN 106680260A
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- photonic crystal
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- stokes
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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
- G01N21/62—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
- G01N2021/653—Coherent methods [CARS]
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Abstract
The invention relates to a portable coherent anti-Stokes Raman spectrometer which is related to the detection characterization of a Raman active medium. The portable coherent anti-Stokes Raman spectrometer provided by the invention adopts a coherent anti-Stokes Raman spectrum technology; a fixed-wavelength laser is adopted, a hollow photonic crystal fiber is adopted as a light source, and a tunable laser can be replaced, so that the purpose of effectively reducing the instrument size is achieved. The portable coherent anti-Stokes Raman spectrometer comprises a solid laser, the hollow photonic crystal fiber, a dichroic mirror, a focusing lens, a detector and a data acquisition and processing unit. The solid laser and the hollow photonic crystal fiber are sequentially placed along an optical axis, the hollow photonic crystal fiber is full of the Raman active medium, the lasers emitted by the solid laser are partially converted into Stokes Raman light inside the hollow photonic crystal fiber, residual laser and the Stokes Raman light are focused by the focusing lens on a to-be-measured target after passing through the dichroic mirror, backward anti-Stokes signal light generated by the to-be-measured target under two beams of light is reflected by the dichroic mirror to the detector on one side of a transmitting optical axis after being focused by the focusing lens, and target component information is obtained by acquiring and processing a detection signal.
Description
Technical field
The present invention is a kind of portable coherent antistockes Raman spectroscopy instrument, with Raman active medium
Detection sign is relevant, and the present invention uses coherent antistockes Raman spectroscopy technology, using one
Laser with fixed wavelength and Hollow-Core Photonic Crystal Fibers as light source, realize obtaining testing sample it is anti-this
Lentor Raman spectrum, compared with the Raman spectrum of conventional detection stokes light, can reduce instrument
Volume, and reduce the interference of fluorescence or phosphorescence.
Background technology
Raman spectroscopy as spectral technique an important branch, in scientific research, industrial production,
The field such as environmental monitoring and science and techniques of defence has played great function.Currently employed Raman spectroscopy is more
By the way of detection stokes light, the interference such as generally existing phosphorescence, and due to spontaneous drawing
Graceful scattering it is less efficient, therefore generally require the longer time of integration collecting Stokes optical signal,
This there is very big difficulty when low component species are detected so that low component or Raman active compared with
The situation that the Raman signal of poor species is submerged.To obtain the Raman light in the certain spectral region of sample
Spectrum, current Raman spectrometer typically adopts monochromator and ICCD or mode associated with single point detector,
This also greatly improved cost and equipment complexity.Ask for above-mentioned present in Raman spectroscopy
Topic, the present invention proposes that a solid state laser combines generation pump light with a Hollow-Core Photonic Crystal Fibers
And stokes light, the method for resonant excitation sample anti-stockes line, detect the relevant of sample
Anti-Stokes spectrum, can avoid fluorescence or phosphorescence interference, effectively improve signal to noise ratio, hollow light
The use of photonic crystal fiber, can replace the tunable laser such as dye laser or OPO, with reference to suitable
When Raman active medium produce need stokes light, equipment instrument can be substantially reduced, realize
The miniaturization of detection instrument, is adapted to the Raman detection of various media and characterizes.
The content of the invention
The present invention includes the shortcoming of coherent antistockes Raman spectroscopy instrument for normal Raman spectroscopy instrument,
Using Hollow-Core Photonic Crystal Fibers, it is aided with appropriate Raman active medium and rational structure design,
The stokes light of appropriate spectral region can be produced, tunable laser can be replaced, reached effectively
Reduce the purpose of equipment instrument.
Particular content of the present invention includes：Solid state laser (1), Hollow-Core Photonic Crystal Fibers (2), two
Phase Look mirror (3), condenser lens (4), detector (5) and data acquisition process unit (6)；It is special
Levy and be：Its set-up mode is one of the following two kinds；
First kind of way, the laser that solid state laser sends is from the incidence end with Hollow-Core Photonic Crystal Fibers
Into in Hollow-Core Photonic Crystal Fibers, Hollow-Core Photonic Crystal Fibers filled with Raman active medium, solid swashs
The laser of light device transmitting is converted into Stokes Raman light in Hollow-Core Photonic Crystal Fibers interior part, remaining
Laser exports Jing two-phase Look mirrors by the exit end of Hollow-Core Photonic Crystal Fibers jointly with Stokes Raman light
Afterwards, then by condenser lens focus on measured target, measured target two-beam photograph under produce it is rear to
After Anti-Stokes signal light line focus lens focus, then reflexed on detector by two-phase Look mirror, visited
Again Jing data lines are gathered and processed the signal of survey device output by data acquisition and procession unit；
Or the second way, laser that solid state laser sends with Hollow-Core Photonic Crystal Fibers from entering
Penetrate end to enter in Hollow-Core Photonic Crystal Fibers, Hollow-Core Photonic Crystal Fibers filled with Raman active medium, Gu
The laser of body laser transmitting is converted into Stokes Raman light in Hollow-Core Photonic Crystal Fibers interior part,
The exit end output jointly by Hollow-Core Photonic Crystal Fibers of remaining laser and Stokes Raman light is by focusing on
Lens focus on measured target, believe by the forward direction anti-Stokes that measured target is produced under two-beam photograph
Number light is incided on detector Jing after the filtration of two-phase Look mirror, the signal of detector output Jing data transfers again
Line is gathered and processed by data acquisition and procession unit；The measured target that the second way is surveyed is transparent
Sample.
The solid state laser adopted in the present invention can be optical fiber laser, semiconductor laser or YAG
Laser instrument, or can also be the laser instrument of other any small volumes.
The Hollow-Core Photonic Crystal Fibers for being adopted through appropriate design, and must be filled with inside reasonable selection
Raman active medium so that the Stokes Raman light spectrum that Hollow-Core Photonic Crystal Fibers are produced can cover
The Stokes Raman light spectrum of lid measured target；The Raman active filled in Hollow-Core Photonic Crystal Fibers is situated between
Matter can be CH4, oxygen, nitrobenzene etc.；Or fibre core is done using suitable material, can produce it is same or
The solid photonic crystal fiber of similar Stokes optical wavelength, it is also possible to replace the hollow photon crystal
Optical fiber.
Using dichroscope optical wavelength that solid state laser is launched more than the light that (contains) it is high thoroughly,
It is high for the light below the wavelength anti-.
Using condenser lens using tightly focused mode (such as NA>0.1 or f<20mm), or using aobvious
Micro mirror group, can improve flashlight yield and collection efficiency.
One or more wave filters can also be increased between two-phase Look mirror and detector, play filter it is miscellaneous
The effect of astigmatism, can improve the signal to noise ratio of the present invention.Data acquisition and procession unit be computer or
Single-chip microcomputer.
Description of the drawings
Fig. 1 is the basic block diagram of the present invention, wherein：1- solid state lasers, 2- hollow photon crystals
Optical fiber, 3- two-phase Look mirrors, 4- condenser lenses, 5- detectors, 6- data acquisition process units.
Fig. 2 is another kind of form of the present invention, wherein：1- solid state lasers, 2- hollow photon crystals
Optical fiber, 3- two-phase Look mirrors, 4- condenser lenses, 5- detectors, 6- data acquisition process units.
Specific embodiment
To describe the specific work process and using method of the present invention in detail, with reference to practical situations,
Illustrate the specific embodiment of the present invention.
Embodiment 1, the methane content in test mixing gas.
To detect coherent anti-Stokes Raman (CARS) spectrum of methane, adoptable Solid State Laser
Device includes YAG laser, YLF laser etc., and gain media is adopted in the present embodiment for the optical fiber of YAG
Laser instrument, Output of laser wavelength is about 1.06 microns, and pulsewidth is several nanoseconds, corresponding hollow photon
Crystal optical fibre is designed using band gap type, pure CH of the inside filled with an atmospheric pressure4Gas is used as Raman gain
Medium, 1.06 mum lasers are in the Si Tuo that the conversion of Hollow-Core Photonic Crystal Fibers interior part is for about 1.54 microns
Ke Si light, pulsewidth is suitable with optical-fiber laser, and the light exported from Hollow-Core Photonic Crystal Fibers just includes 1.06
The laser of micron and 1.54 microns of two wavelength, the two-phase Look mirror 3 adopted in the present embodiment is logical for long wave
(longpass) two-phase Look mirror, cutoff wavelength is 1 micron, 1.05 microns to 1.6 microns intervals
Typical transmitance is more than 99%, in 700 nanometers of reflectivity to 1 micron waveband more than 99%, focuses on
Lens 4 adopt the microlens of numerical aperture NA=1.1, and detector 5 is using Thorlabs companies
APD210 snowslide silicon photoelectric diodes, data acquisition process unit 6 is homemade Signal acquiring and processing
Component is integrated.Jing after Hollow-Core Photonic Crystal Fibers, a part exists the laser of optical fiber laser transmitting
The interior part of Hollow-Core Photonic Crystal Fibers 2 is converted into Stokes Raman light, remaining laser and Stokes
Raman light is common Jing after two-phase Look mirror 3, then is focused in tested mixed gas pond by condenser lens 4,
Methane produce under the collective effect of two beam exciting lights after to coherent optical signal, it is backward anti-
Stokes light is converged again by condenser lens 4, measured target produce under two-beam photograph it is rear to it is anti-this
After lentor flashlight line focus lens 4 are focused on, then reflexed on detector 5 by two-phase Look mirror 3,
Band pass filter or short-pass filter plate can be increased in light path between detector 5 and two-phase Look mirror
Or dispersion element etc., to filter the interference of stokes light and pump light, it is also possible to filter the dry of fluorescence
Disturb, wherein relative more preferably effect can more be played with the combination of dispersion element using notch filter,
The electric signal Jing data lines of detector output are carried out electric signal by data acquisition and procession unit
Process and show, you can obtain the concentration information of methane.Because gain media is the optical-fiber laser of YAG
Device can accomplish higher repetition rate (MHz), therefore portable excited Raman involved in the present invention
Spectrometer can realize the quick detection to object gas.
Embodiment 2, the content of the ethene in test mixing gas.
To detect coherent anti-Stokes Raman (CARS) spectrum of ethene, using increasing in the present embodiment
Beneficial medium is the compact solid state laser of YAG, and with frequency multiplication part, Output of laser wavelength is about
532 nanometers, pulsewidth is several nanoseconds, and repetition rate is 1KHz, corresponding Hollow-Core Photonic Crystal Fibers
Designed using band gap type, pure C of the inside filled with an atmospheric pressure2H6Gas as raman gain medium,
532nm rice laser converts for about 630 nanometers of stokes light in Hollow-Core Photonic Crystal Fibers interior part,
Pulsewidth is suitable with Solid State Laser, and the light exported from Hollow-Core Photonic Crystal Fibers just includes about 532 nanometers
The laser of about 630 microns of two wavelength, the two-phase Look mirror 3 adopted in the present embodiment is logical for long wave
(longpass) two-phase Look mirror, cutoff wavelength is 530 nanometers, 530 nanometers to 650 nanometers intervals
Typical transmitance is more than 99%, in 400 nanometers of reflectivity to 500 nano wavebands more than 99%, gathers
Focus lens 4 adopt the microlens of numerical aperture NA=1.1, detector 5 to adopt Thorlabs companies
APD210 snowslide silicon photoelectric diodes, data acquisition process unit 6 be homemade signals collecting with place
Reason component is integrated.The laser of solid state laser transmitting is a part of Jing after Hollow-Core Photonic Crystal Fibers
Stokes Raman light, remaining laser and stoke are converted into the interior part of Hollow-Core Photonic Crystal Fibers 2
This Raman light is common Jing after two-phase Look mirror 3, then is focused in tested mixed gas pond by condenser lens 4,
Ethene produce under the collective effect of two beam exciting lights after to coherent optical signal, it is backward anti-
Stokes light is converged again by condenser lens 4, measured target produce under two-beam photograph it is rear to it is anti-this
After lentor flashlight line focus lens 4 are focused on, then reflexed on detector 5 by two-phase Look mirror 3,
Band pass filter or short-pass filter plate can be increased in light path between detector 5 and two-phase Look mirror
Or dispersion element etc., to filter the interference of stokes light and pump light, it is also possible to filter the dry of fluorescence
Disturb, wherein relative more preferably effect can more be played with the combination of dispersion element using notch filter,
The electric signal Jing data lines of detector output are carried out electric signal by data acquisition and procession unit
Process and show, you can obtain the concentration information of ethene.
Claims (9)
1. a kind of portable coherent antistockes Raman spectroscopy instrument, including：Solid state laser (1),
Hollow-Core Photonic Crystal Fibers (2), two-phase Look mirror (3), condenser lens (4), detector (5) sum
According to acquisition process unit (6)；It is characterized in that：Its set-up mode is one of the following two kinds；
First kind of way, the laser that solid state laser sends is from the incidence end with Hollow-Core Photonic Crystal Fibers
Into in Hollow-Core Photonic Crystal Fibers, Hollow-Core Photonic Crystal Fibers filled with Raman active medium, solid swashs
The laser of light device transmitting is converted into Stokes Raman light in Hollow-Core Photonic Crystal Fibers interior part, remaining
Laser exports Jing two-phase Look mirrors by the exit end of Hollow-Core Photonic Crystal Fibers jointly with Stokes Raman light
Afterwards, then by condenser lens focus on measured target, measured target two-beam photograph under produce it is rear to
After Anti-Stokes signal light line focus lens focus, then reflexed on detector by two-phase Look mirror, visited
Again Jing data lines are gathered and processed the signal of survey device output by data acquisition and procession unit；
Or the second way, laser that solid state laser sends with Hollow-Core Photonic Crystal Fibers from entering
Penetrate end to enter in Hollow-Core Photonic Crystal Fibers, Hollow-Core Photonic Crystal Fibers filled with Raman active medium, Gu
The laser of body laser transmitting is converted into Stokes Raman light in Hollow-Core Photonic Crystal Fibers interior part,
The exit end output jointly by Hollow-Core Photonic Crystal Fibers of remaining laser and Stokes Raman light is by focusing on
Lens focus on measured target, believe by the forward direction anti-Stokes that measured target is produced under two-beam photograph
Number light is incided on detector Jing after the filtration of two-phase Look mirror, the signal of detector output Jing data transfers again
Line is gathered and processed by data acquisition and procession unit.
2. according to the portable coherent antistockes Raman spectroscopy instrument described in claim 1, its feature
It is：Using solid state laser can be optical fiber laser, semiconductor laser or YAG laser,
Or can also be the laser instrument of other any small volumes.
3. according to the portable coherent antistockes Raman spectroscopy instrument described in claim 1, its feature
It is：Using Hollow-Core Photonic Crystal Fibers must be through appropriate design, and the drawing being filled with inside reasonable selection
Graceful active medium so that the Stokes Raman light spectrum that Hollow-Core Photonic Crystal Fibers are produced can be covered
The Stokes Raman light spectrum of measured target；Or fibre core is done using suitable material, can produce same
Or the solid photonic crystal fiber of similar Stokes optical wavelength, it is also possible to replace the hollow photon brilliant
Body optical fiber.
4. according to the portable coherent antistockes Raman spectroscopy instrument described in claim 1, its feature
It is：Using dichroscope optical wavelength that solid state laser is launched more than the light that (contains) it is high thoroughly,
It is high for the light below the wavelength anti-.
5. according to the portable coherent antistockes Raman spectroscopy instrument described in claim 1, its feature
It is：Using condenser lens using tightly focused mode (such as NA>0.1 or f<20mm), or using aobvious
Micro mirror group, can improve flashlight yield and collection efficiency.
6. according to the portable coherent antistockes Raman spectroscopy instrument described in claim 1, its feature
It is：One or more wave filters can also be increased between two-phase Look mirror and detector, play filter it is miscellaneous
The effect of astigmatism, can improve the signal to noise ratio of the present invention.
7. according to the portable coherent antistockes Raman spectroscopy instrument described in claim 1, its feature
It is：The measured target that the second way is surveyed is transparent sample.
8. according to the portable coherent antistockes Raman spectroscopy instrument described in claim 1, its feature
It is：Data acquisition and procession unit is computer or single-chip microcomputer.
9. according to the portable coherent antistockes Raman spectroscopy instrument described in claim 1 or 3, its
It is characterized in that：The Raman active medium filled in Hollow-Core Photonic Crystal Fibers can be CH4, oxygen, nitrobenzene
In one or two or more kinds.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110018149A (en) * | 2019-02-21 | 2019-07-16 | 中智科仪（北京）科技有限公司 | A kind of long-range Raman analyser based on the low recurrent frequency pulse laser device of 532nm |
| CN112097953A (en) * | 2020-09-21 | 2020-12-18 | 上海交通大学 | High-frequency two-color coherent anti-Stokes Raman spectrum temperature measuring device and method |
| CN112748100A (en) * | 2020-12-23 | 2021-05-04 | 华中科技大学 | System and method for analyzing spectral components of methane in MOCVD (metal organic chemical vapor deposition) based on femtosecond CARS (coherent anti-coherent emitter-emitter) |
| CN114088688A (en) * | 2022-01-17 | 2022-02-25 | 武汉光谷航天三江激光产业技术研究院有限公司 | Automatic collimation backward CARS detection system and method of all-fiber structure |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110018149A (en) * | 2019-02-21 | 2019-07-16 | 中智科仪（北京）科技有限公司 | A kind of long-range Raman analyser based on the low recurrent frequency pulse laser device of 532nm |
| CN112097953A (en) * | 2020-09-21 | 2020-12-18 | 上海交通大学 | High-frequency two-color coherent anti-Stokes Raman spectrum temperature measuring device and method |
| CN112097953B (en) * | 2020-09-21 | 2022-03-01 | 上海交通大学 | High-frequency two-color coherent anti-Stokes Raman spectrum temperature measuring device and method |
| CN112748100A (en) * | 2020-12-23 | 2021-05-04 | 华中科技大学 | System and method for analyzing spectral components of methane in MOCVD (metal organic chemical vapor deposition) based on femtosecond CARS (coherent anti-coherent emitter-emitter) |
| CN112748100B (en) * | 2020-12-23 | 2022-03-01 | 华中科技大学 | System and method for analyzing spectral components of methane in MOCVD (metal organic chemical vapor deposition) based on femtosecond CARS (coherent anti-coherent emitter-emitter) |
| CN114088688A (en) * | 2022-01-17 | 2022-02-25 | 武汉光谷航天三江激光产业技术研究院有限公司 | Automatic collimation backward CARS detection system and method of all-fiber structure |
| CN114088688B (en) * | 2022-01-17 | 2022-06-17 | 武汉光谷航天三江激光产业技术研究院有限公司 | Automatic collimation backward CARS detection system and method of all-fiber structure |
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