CN104568897B - Raman spectrum intensifier, system and method based on chamber exterior resonant cavity technology - Google Patents
Raman spectrum intensifier, system and method based on chamber exterior resonant cavity technology Download PDFInfo
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Abstract
Present invention is disclosed a kind of Raman spectrum intensifier, system and method based on chamber exterior resonant cavity technology, described device includes laser, laser transmission fiber, excites crystal, transflection mirror, frequency-doubling crystal and resonator；The laser provides LASER Light Source for Raman detection, and laser excites crystal by laser transmission fiber connection, excites crystal to produce the laser of specific wavelength；The transflection mirror passes through coating film treatment, only allows specific frequency light by being totally reflected the light of other wavelength；Frequency-doubling crystal is used for the frequency for changing laser；The resonator is used to ensure that the laser after change frequency can realize total reflection.Instant invention overcomes online Raman spectrum when detecting relatively low component materials, the incomplete inaccurate influence of spectrogram caused by Ramam effect is weak, it ensure that Raman spectrometer obtains effectively analysis detection to online complicated multi-component material.
Description
Technical field
The invention belongs to field of photoelectric technology, is related to a kind of Raman spectrum intensifier, more particularly to a kind of based on outside chamber
The Raman spectrum intensifier of resonator technology；Meanwhile the invention further relates to a kind of Raman light based on chamber exterior resonant cavity technology
Compose strengthening system and Enhancement Method.The present invention is used for Raman spectrometer real time on-line monitoring gas, liquid or gas-liquid mixed material
The enhancing of Raman spectrum effect during component, so as to realize that online Raman spectrum when detecting relatively low component materials, accurately enters
Row qualitative and quantitative analysis.
Background technology
Raman scattering refers to light by causing the frequency of light to become due to incident light and molecular motion interaction during medium
Change, nineteen twenty-eight is found by India physicist Chandrasekhar La Laman.Raman spectrum analysis technology is that one kind is dissipated with Raman
The contactless spectral analysis technique penetrated based on effect, it can carry out qualitative and quantitative analysis to the composition and structure of material.Draw
Graceful spectral measurement speed is fast, can accomplish measurement in real time in situ using Raman spectrum analysis, be advantageous to process control it is real-time
Line monitors.From nineteen twenty-eight to 1940, Raman spectrum is always the focus in studying, but because Ramam effect is too weak, Ren Menwu
Weaker Raman scattering signal is studied in method detection, survey timing demands sample volume it is sufficiently large, it is colourless, without dust, unstressed configuration etc..
These shortcomings largely constrain further research and the practical application of Raman spectrum, therefore with the infrared spectrum forties
The progress and commercialization of technology, the status of Raman spectrum receive great weakening.Because Raman diffused light is too faint, scientist
In decades it is difficult to which Raman scattering is committed to put into practice.After there is laser from nineteen sixty, because laser has, monochromaticjty is good, energy
Concentrate, output power the features such as, especially spectral radiance density height, lasing light emitter small volume, in light weight, easy automation mechanized operation etc.
Advantage, so laser is used for the excitation source of Raman spectrometer quickly, so that Raman spectrum obtains new starting point.Using
Laser is energized into a certain virtual stake as monochromatic source, by sample molecule, subsequent excited molecule transit to one it is different from ground state
Vibration level, now, the frequency for scattering radiation will be different from incident frequencies.This frequency change and ground state and the vibrational energy of final state
It is differential suitable.This " inelastic scattering " light is just referred to as Raman scattering.The advantages of Raman spectrum, is the quick of it, accurately,
Sample (solid, semisolid, liquid or gas) is not destroyed during measurement generally, sample preparation is simply even not required to sample preparation.
Present Raman spectrum detection can carry out carrying out direct feedback control directly against the specific targets of product completely.
At the scene in actual Raman spectra qualitative quantitative analysis, the accurate acquisition of Raman Spectral Signal is whole Raman spectrum analysis flow
In key, only signal accurately and reliably, can just talk about its qualitative, quantitative precision.Field monitoring material low concentration,
When micro, its Ramam effect is not strong, fainter with respect to Raman signal, accurate when carrying out online raman monitoring so as to cause
Property reduce, and exactly these micro material composition contents are that the material of detection is needed most in on-line checking.
In view of this, how to solve this Raman spectrum monitoring of low concentration, minimal feeding to apply in process industry
Bottleneck problem, be the thorny problem of online Raman spectrometer application at present, and must solve the problems, such as.Apparatus of the present invention are just
It is to be based on resonator total reflection principle, the outer frequency doubling technology of binding cavity, strengthens Ramam effect, there is provided the Raman signal of high quality, make
It is more accurate that Raman detects for low concentration material, will produce far-reaching influence to the following of process industry.
The content of the invention
The technical problems to be solved by the invention are：A kind of Raman spectrum enhancing dress based on chamber exterior resonant cavity technology is provided
Put, it is possible to provide the Raman signal of high quality, Raman spectrum is detected for low concentration material more accurate, by process industry
Future produces far-reaching influence.
Meanwhile the present invention provides a kind of Raman spectrum strengthening system based on chamber exterior resonant cavity technology, it is possible to provide high quality
Raman signal, make Raman spectrum for low concentration material detect it is more accurate, will to the future of process industry produce it is far-reaching
Influence.
In addition, the present invention also provides a kind of Raman spectrum Enhancement Method based on chamber exterior resonant cavity technology, it is possible to provide high-quality
The Raman signal of amount, Raman spectrum is set to be detected for low concentration material more accurate, it is far-reaching by being produced to the future of process industry
Influence.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of Raman spectrum intensifier based on chamber exterior resonant cavity technology, for liquid, gas and gas-liquid mixed material
The enhancing of Raman signal when carrying out online Raman spectrum detection；
Described device includes laser, laser transmission fiber, excites crystal, transflection mirror, frequency-doubling crystal and resonator；
The laser provides LASER Light Source for Raman detection, and laser excites crystal by laser transmission fiber connection,
Crystal is excited to produce the laser of specific wavelength；
The transflection mirror passes through coating film treatment, only allows specific frequency light by being totally reflected the light of other wavelength；Frequency multiplication is brilliant
Body is used for the frequency for changing laser；The resonator is used to ensure that the laser after change frequency can realize total reflection.
As a preferred embodiment of the present invention, the resonator includes two sides speculum parallel to each other, two reflections
Operation material is placed between mirror, two total reflective mirrors for forming this resonator are transflection mirror；When specific wavelength laser enter it is humorous
Shake after chamber, carry out the reflection of unlimited number in intracavitary, carry out being totally reflected the two of enhancing in the laser resonant cavity of laser transmitting
The frequency of individual light is different.
As a preferred embodiment of the present invention, the completely reflecting mirror collection in the transflection mirror, frequency-doubling crystal and resonator
On Cheng Yi plated film crystal, the plated film crystal can be changed and ad hoc swashed transmitted through the laser of specific frequency by frequency doubling technology
Light frequency, and it is totally reflected the laser of the specific frequency after frequency multiplication.
As a preferred embodiment of the present invention, described device uses cavity external frequency multiplication technology；Certain wavelength of laser transmitting
Laser, irradiation excite crystal accordingly, by only allow pass through specific wavelength laser transflection mirror, enter frequency-doubling crystal；
The frequency-doubling crystal makes the light through its certain frequency pass through frequency increase after it by coating technique；Use two
Times frequency-doubling crystal, even if original laser frequency increase is original twice, shortened wavelengths are original half.
As a preferred embodiment of the present invention, the laser after wavelength shift is strengthened in resonator, in transit chamber
Completely reflecting mirror can make optical maser wavelength reach almost free of losses total reflection reinforcement.
A kind of Raman spectrum strengthening system based on chamber exterior resonant cavity technology, it is characterised in that the system includes：It is described
Raman spectrum intensifier, Raman detector, the second optical fiber, Raman spectrometer；
The Raman detector is set in the resonator of the Raman spectrum intensifier, and Raman signal passes through the second optical fiber
Conduction to Raman spectrometer carries out spectrum analysis.
As a preferred embodiment of the present invention, it is primary penetrate laser frequency change after, resonator through total reflection, Yu Xie
Shake in the cavity of chamber by repeatedly vibration enhancing repeatedly, while the contact area with sample is increased, so as to enhance sample
Raman scattering signal, by being transferred to after collecting enhancing signal positioned at the Raman detector of resonator side by the second optical fiber
Raman spectrometer, obtain the Raman spectroscopy of enhancing.
A kind of Enhancement Method of above-mentioned Raman spectrum intensifier, methods described include：
The laser irradiation of laser transmitting is excited into crystal, produces the laser of specific wavelength, reaching only allows specific frequency
The transflection mirror that light passes through, filter out the veiling glare being likely to occur during laser produces；The transflection mirror of selection is with exciting crystal
The wavelength excited is identical, and so, into after frequency-doubling crystal, the change into multiple occurs for laser frequency；
Change the laser after frequency in resonator, carry out total reflection enhancing laser effect；Due to entering resonance in laser
Frequency-doubling crystal is provided with during chamber, the laser being totally reflected in resonator will not lose through transflection mirror above again；
It is different be totally reflected the frequency of the light of enhancing in the laser resonant cavity of laser transmitting, is carried out in intracavitary multiple
The multiple direct irradiation of laser of enhancing is totally reflected on material to be measured to be detected, Raman signal collection is now carried out, is increased
Material Raman detection spectrogram after strong.
The beneficial effects of the present invention are：Raman spectrum enhancing dress proposed by the present invention based on chamber exterior resonant cavity technology
Put, system and method, raman spectral signal when realizing real time on-line monitoring gas, liquid or gas-liquid mixed material component
Enhancing, makes laser by the wavelength shift for the specific wavelength laser launched laser, and using Fabry-Perot resonators
Carry out multiple total reflection, reach laser enhancing and increase contact area purpose, overcome online Raman spectrum detection compared with
During low component materials, the incomplete inaccurate influence of spectrogram caused by Ramam effect is weak, it ensure that Raman spectrometer to online complicated
Multi-component material obtains effectively analysis detection.
Brief description of the drawings
Fig. 1 is the principle schematic of Raman spectrum strengthening system of the present invention.
Fig. 2 is the intra resonant cavity structural representation of apparatus of the present invention.
Embodiment
The preferred embodiment that the invention will now be described in detail with reference to the accompanying drawings.
Embodiment one
Present invention is disclosed a kind of Raman spectrum intensifier and system based on chamber exterior resonant cavity technology, apparatus of the present invention
The increasing of raman spectral signal when can be applied to Raman spectrometer real time on-line monitoring gas, liquid or gas-liquid mixed material component
By force, so as to realizing that online Raman spectrum when detecting relatively low component materials, can carry out accurate qualitative and quantitative analysis.Due to light
Spectrum on-line checking scene is more complicated, severe, and the scope that online Raman spectrum detection passes through fiber optic conduction is preferable in 150m
State, so the means for correcting of the present invention is placed in analyzer house with online Raman detector agent set, simultaneously
The structural volume of apparatus of the present invention is smaller, using more convenient.
Below in conjunction with preferred embodiment, to according to embodiment provided by the invention, feature and its effect, specifically
After bright, for simple clearly purpose, hereafter the appropriate description for eliminating known technology is in order to avoid those unnecessary details shadows
Ring the description to the technical program.
Referring to Fig. 1, in the present embodiment, the laser that selection wavelength is 808nm is examined as laser 1 for follow-up Raman
Survey and excitation source is provided, laser frequency and strengthening part include：Laser conduction optical fiber 2, excite and produce 1064nm wavelength lasers
Excite crystal 3, it is allowed to the transflection mirror 6,7 that specific frequency laser passes through, change the frequency-doubling crystal 4 of laser frequency, and ensure to change
Laser after Frequency can realize the Fabry-Perot resonators 5 of total reflection；The intracavitary of Fabry-Perot resonators 5 is filled with
Material to be detected, cavity is interior to be provided with Raman detector 8, and Raman signal is conducted to Raman spectrometer 10 by optical fiber 9 carries out spectrum
Analysis.
As Fig. 2, Fig. 2 disclose the internal structure schematic diagram of above-mentioned resonator, the permission specific frequency selected in the present invention
The transflection mirror 6,7 that laser passes through, change the frequency-doubling crystal 4 of laser frequency, and ensure that the laser after change frequency can be realized
The Fabry-Perot resonators 5 of total reflection, in actual applications, it can be integrated on a plated film crystal 11, plated film crystal 11
It is characterised by that ad hoc laser frequency can be changed by frequency doubling technology, and be totally reflected transmitted through the laser of specific frequency
The laser of specific frequency after frequency multiplication.
Change for specific laser frequency, the laser for the 808nm that laser 1 is launched, conducted by optical fiber 2,
The laser for exciting crystal 3 to produce 1064nm is reached, then by the transflection mirror 6 for only allowing specific wavelength 1064nm to pass through, so
It is 1064nm into the optical maser wavelength before frequency-doubling crystal 4.The laser that specific wavelength is 1064nm after frequency-doubling crystal 4 by that will change
The wavelength of its original, wavelength are modified in that the selected of frequency-doubling crystal, and from twice of frequency-doubling crystal, 1064nm laser is converted into
Originally the half of wavelength is 532nm.
For specific laser enhancing, change the laser after frequency in Fabry-Perot resonators 5, be totally reflected, instead
Multiple concussion enhancing,.Because we are provided with frequency-doubling crystal 4 when laser enters Fabry-Perot resonators, carried out in intracavitary complete
The transflection mirror that the laser of reflection will not pass through above loses.The laser that multiple total reflection enhancing is carried out in intracavitary repeatedly directly shines
Penetrate on material to be measured to be detected, produce Raman light, and the Ramam effect detector 8 by being placed on intracavitary carries out Raman signal
Collection, obtains enhanced material Raman detection signal, reaches Raman spectrum imaging system by optical fiber 9, finally strengthened
Detection material Raman spectrum figure afterwards.
Raman spectrum intensifier and system of the invention based on chamber exterior resonant cavity technology are described above, the present invention is taking off
While showing said apparatus and system, a kind of Enhancement Method of above-mentioned Raman spectrum intensifier is also disclosed, methods described includes：
The laser irradiation of laser transmitting is excited into crystal, produces the laser of specific wavelength, reaching only allows what specific frequency light passed through
Transflection mirror, filter out the veiling glare being likely to occur during all laser produce；The transflection mirror of selection is with exciting what crystal excited
Wavelength is identical, and so, into after frequency-doubling crystal, the change into multiple occurs for laser frequency.Change the laser after frequency in resonance
Intracavitary, carry out total reflection enhancing laser effect；Due to being provided with frequency-doubling crystal when laser enters resonator, enter in resonator
The laser of row total reflection will not lose through transflection mirror above again.It is all-trans in the laser resonant cavity of laser transmitting
Penetrate that the frequency of the light of enhancing is different, the multiple direct irradiation of laser of multiple total reflection enhancing is carried out to be detected to be measured in intracavitary
On material, Raman signal collection is now carried out, obtains enhanced material Raman detection spectrogram.
In summary, Raman spectrum intensifier, system and method proposed by the present invention based on chamber exterior resonant cavity technology,
The enhancing of raman spectral signal when realizing real time on-line monitoring gas, liquid or gas-liquid mixed material component, by swashing
The wavelength shift of the specific wavelength laser of light device transmitting, and laser is repeatedly all-trans using Fabry-Perot resonators
Penetrate, reach the enhancing of laser and increase the purpose of contact area, overcome online Raman spectrum when detecting relatively low component materials,
The incomplete inaccurate influence of spectrogram caused by Ramam effect is weak, ensure that Raman spectrometer obtains to online complicated multi-component material
Effectively analysis detection.
Here description of the invention and application are illustrative, are not wishing to limit the scope of the invention to above-described embodiment
In.The deformation and change of embodiments disclosed herein are possible, real for those skilled in the art
The replacement and equivalent various parts for applying example are known.It should be appreciated by the person skilled in the art that the present invention is not being departed from
Spirit or essential characteristics in the case of, the present invention can in other forms, structure, arrangement, ratio, and with other components,
Material and part are realized.In the case where not departing from scope and spirit of the present invention, embodiments disclosed herein can be entered
The other deformations of row and change.
Claims (5)
1. a kind of Raman spectrum intensifier based on chamber exterior resonant cavity technology, exists for liquid, gas and gas-liquid mixed material
Carry out the enhancing of Raman signal during online Raman spectrum detection；It is characterized in that：
Described device includes laser, laser transmission fiber, excites crystal, transflection mirror, frequency-doubling crystal and resonator；
The laser provides LASER Light Source for Raman detection, and laser excites crystal by laser transmission fiber connection, excited
Crystal produces the laser of specific wavelength；
The transflection mirror passes through coating film treatment, only allows specific frequency light by being totally reflected the light of other wavelength；Frequency-doubling crystal is used
In the frequency for changing laser；The resonator is used to ensure that the laser after change frequency can realize total reflection；
The resonator includes two sides speculum parallel to each other, places operation material between two speculums, forms this humorous
Two speculums of chamber of shaking are transflection mirror；After the laser of specific wavelength enters resonator, the anti-of unlimited number is carried out in intracavitary
Penetrate, the frequency for be totally reflected two light of enhancing in the laser resonant cavity of laser transmitting is different；
Completely reflecting mirror in the transflection mirror, frequency-doubling crystal and resonator is integrated on a plated film crystal, the plated film crystal
Ad hoc laser frequency can be changed by frequency doubling technology transmitted through the laser of specific frequency, and be totally reflected specific after frequency multiplication
The laser of frequency.
2. the Raman spectrum intensifier according to claim 1 based on chamber exterior resonant cavity technology, it is characterised in that：
Described device uses cavity external frequency multiplication technology；The laser of certain wavelength of laser transmitting, irradiation excite crystal accordingly, passed through
Only allow the transflection mirror through specific wavelength laser, enter frequency-doubling crystal；The frequency-doubling crystal makes transmission by coating technique
The light of its certain frequency passes through frequency increase after it；2 octave frequency crystal is used, even if original laser frequency increases
Original twice is added as, shortened wavelengths are original half.
3. the Raman spectrum intensifier according to claim 1 based on chamber exterior resonant cavity technology, it is characterised in that：
Laser after wavelength shift is is strengthened in resonator, and transit chamber inner total reflection mirror can be such that optical maser wavelength reaches almost
Free of losses total reflection is strengthened.
4. a kind of Raman spectrum strengthening system based on chamber exterior resonant cavity technology, it is characterised in that the system includes：Right will
Seek Raman spectrum intensifier, Raman detector, the second optical fiber, the Raman spectrometer described in 1；
The Raman detector is set in the resonator of the Raman spectrum intensifier, and Raman signal passes through the second fiber optic conduction
Spectrum analysis is carried out to Raman spectrometer；
It is primary to penetrate after laser frequency changes, in resonator by being totally reflected, in the cavity of resonator by repeatedly vibrating repeatedly
Enhancing, while the contact area with sample is increased, so as to enhance the Raman scattering signal of sample, by positioned at resonator side
The Raman detector collect enhancing signal after Raman spectrometer is transferred to by the second optical fiber, obtain the Raman spectrum of enhancing
Spectrogram.
5. the Enhancement Method of Raman spectrum intensifier described in a kind of claim 1, it is characterised in that methods described includes：
The laser irradiation of laser transmitting is excited into crystal, produces the laser of specific wavelength, reaching only allows specific frequency light to lead to
The transflection mirror crossed, filter out the veiling glare being likely to occur during all laser produce；The transflection mirror of selection is with exciting crystal to swash
The wavelength of hair is identical, and so, into after frequency-doubling crystal, the change into multiple occurs for laser frequency；
Change the laser after frequency in resonator, carry out total reflection enhancing laser effect；Due to when laser enters resonator
There is provided frequency-doubling crystal, the laser being totally reflected in resonator will not lose through transflection mirror above again；
It is different be totally reflected the frequency of the light of enhancing in the laser resonant cavity of laser transmitting, is repeatedly all-trans in intracavitary
The multiple direct irradiation of laser of enhancing is penetrated on material to be measured to be detected, Raman signal collection is now carried out, after being strengthened
Material Raman detection spectrogram.
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