CN105181672B - A kind of Raman spectrum wave number and intensity real-time correction method - Google Patents
A kind of Raman spectrum wave number and intensity real-time correction method Download PDFInfo
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- CN105181672B CN105181672B CN201510621878.1A CN201510621878A CN105181672B CN 105181672 B CN105181672 B CN 105181672B CN 201510621878 A CN201510621878 A CN 201510621878A CN 105181672 B CN105181672 B CN 105181672B
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Abstract
The present invention relates to a kind of Raman spectrum wave number and intensity correction method, belongs to raman spectroscopy measurement technical field, including：External reference optical fiber is set to be placed on same position with measurement optical fiber, External reference optical fiber is set to be in measurement optical fiber under identical environment, detect the raman spectral signal of reference material, after the raman spectral signal for measuring optical fiber measurement material to be detected, the fine signal returned of two-beam is logical to be transported to FT Raman spectrometers；The crest location and peak intensity that the raman spectral signal that External reference optical fiber is transmitted obtains are as reference, and the raman spectral signal obtained to measurement optical fiber carries out wave number and strength signal is corrected；Test substance raman spectral signal after correction is pre-processed, realizes Qualitative and quantitative analysis.Wave number and intensity drift caused by the present invention can eliminate extraneous factor (such as external environment converts, and flashing is fixed), obtain more stable raman spectral signal.
Description
Technical field
The present invention relates to a kind of Raman spectrum wave number and intensity correction method, by by External reference thing and fiber multiplex
Raman spectrum wave number and the method for intensity stabilization are realized, belongs to raman spectroscopy measurement technical field.
Background technology
When illumination is mapped on Cucumber, scatter light in except with addition to incident light frequency identical spectral line, also one is small
The spectral line that partial intensities are extremely weak, frequency changes (i.e. frequency increases or decreases), this phenomenon are referred to as Ramam effect, also referred to as
Raman spectrum.Raman spectrum is the inelastic scattering of reaction molecular vibration and rotation information, so Raman spectrum falls within molecule
Spectrum.Because Raman spectrum has the characteristics of frequency and intensity, polarization etc. indicate scatterer so that Raman spectrum, which turns into, to be ground
Study carefully the Main Means of structure of matter analysis test.But because weaker (about the 10 of incident intensity of Raman light intensity-6), and require nothing
Color, without dust, unstressed configuration, and the progress and commercialization of the infrared spectrum technology thirties in last century cause the application of Raman spectrum
It is plummeted.Until the sixties in last century, the development of laser technology enables Raman technology to revive, due to the high brightness of laser beam,
The advantages that directionality and polarizability, turn into the perfect light source of Raman spectrum.
The Raman spectrum of high quality is most important for follow-up qualitative and quantitative analysis.Raman spectrum is being utilized to sample
When being analyzed, although without being pre-processed to sample, Raman spectrum is vulnerable to the interference in the external world, such as：Laser machine is drawn
The graceful scattering shot noise of light, the shot noise of ccd detector, dark current noise, sample or the fluorescence of container and phosphorescence Beijing,
Spike etc. caused by being accused of in the black body radiation of surrounding environment, environment.These will result directly in the spectral peak or strong of Raman spectrum
Degree converts so that the inaccuracy and unstability of follow-up analysis result.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of Raman spectrum wave number and intensity real-time correction method, are somebody's turn to do
Method is based on External reference thing and fiber multiplex, realizes Raman spectrum wave number and intensity real-time stabilization, solve Raman spectrum by
To the interference in the external world, the problem of so as to cause the inaccuracy of follow-up analysis result and unstability.
The present invention is achieved in that a kind of Raman spectrum wave number and intensity real-time correction method, including the step of it is as follows：
1) set External reference optical fiber to be placed on same position with measurement optical fiber, External reference optical fiber is in phase with measurement optical fiber
Under same environment, the raman spectral signal of reference material is detected, after the raman spectral signal for measuring optical fiber measurement material to be detected,
The fine signal returned of two-beam is transported to FT Raman spectrometers；
2) crest location and peak intensity that the raman spectral signal for transmitting External reference optical fiber obtains are as reference, to surveying
The raman spectral signal that amount optical fiber obtains carries out wave number and strength signal is corrected；
3) the test substance raman spectral signal after correction is pre-processed, realizes Qualitative and quantitative analysis.
2nd, according to the Raman spectrum wave number and intensity real-time correction method described in claim 1, it is characterised in that the survey
Measure optical fiber and External reference optical fiber is placed side by side.
Further, the calculating process of wave number correction is in step 2)：By reference to the raman spectral signal of fibre-optical probe
Compared with standard spectrum, wave number calibration curve equation is obtained：V=v0+ Dvr, wherein v are that reference optical fiber probe is drawn
Graceful spectrum wave number, v0For the Raman spectrum of standard spectrum, Dv is wave number rate of change, and r is external disturbance factor, passes through correction equation
Wave number correction is carried out to the Raman spectrum for measuring fibre-optical probe.
Further, it is for intensity correction process：The spectral intensity of the specific wave number obtained by reference to fibre-optical probe,
Then compared with standard spectrum intensity, intensity correction curve I (v)=I is obtained0(v) (1+DI), wherein I (v) are reference light
The spectral intensity of fibre probe, I0(v) it is standard spectrum intensity, DI is light intensity rate of change, then will measure the Raman of optical fiber acquisition
Spectrum carries out division arithmetic with intensity correction curve, carries out intensity correction.
Further, in step 1), using fiber multiplex, two-way is alternately being obtained with a branch of optical fiber using photoswitch
Raman spectral signal.
Further, in step 1), two-way raman spectral signal is obtained simultaneously using double fiber-optic probe systems.
Compared with prior art, beneficial effect is the present invention：Compared with existing Raman spectrum wave number stabilization technique, this hair
The bright method for realizing Raman spectrum wave number and intensity real-time stabilization based on External reference thing and optical fiber multiplexing method, can pass through ripple
Multiplexing technology or double measuring probe structures is divided to realize the transmission of two-way raman spectral signal：It is measurement signal all the way, is all the way ginseng
Signal is examined, the real-time stabilization of measurement Raman signal wave number and intensity is realized by reference to signal.
Method of the invention based on the real-time Raman spectrum wave number of External reference thing method and intensity correction, can eliminate extraneous factor
Wave number and intensity drift caused by (such as external environment converts, and flashing is fixed), obtain more stable raman spectral signal.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
A kind of Raman spectrum wave number and intensity real-time correction method, including：
(1) system building：
Set External reference optical fiber to be placed on same position with measurement optical fiber, External reference optical fiber is in identical with measurement optical fiber
In the environment of, the raman spectral signal of reference material is detected, after the raman spectral signal for measuring optical fiber measurement material to be detected, two
The signal that beam optical fiber returns is transported to FT Raman spectrometers；The external environment of two-way spectral signal is realized by fiber multiplex
(such as temperature, light intensity) is identical, so as to obtain the Raman spectrum under identical environment.Because the External reference thing of selection is with very strong
Stability, therefore Raman spectrum crest location and the peak intensity fluctuation obtained under various circumstances has certain rule, according to
This characteristic is corrected to the peak intensity and crest location of test substance Raman spectrum.Or double fiber-optic probes can also be utilized
System obtains two-way raman spectral signal simultaneously.
The structure of External reference thing fibre-optical probe is：Fibre-optical probe directly contacts (transparent to refer to using light with clear glass
The light thing in source absorbs) the External reference thing sample cell of encapsulation, then carry out water proof anti-soil encapsulation with quartz glass.Test substance optical fiber
Sonde configuration is：Fibre-optical probe is encapsulated with clear glass, so as to reduce pollution of the extraneous test substance to fibre-optical probe and viscous
Even.
(2) spectral measurement
(1) Raman of determinand and External reference material alternately or is continuously obtained by measuring optical fiber and External reference optical fiber
Spectrum is measured to gather two groups of raman spectral signals；Measure optical fiber and External reference optical fiber is placed side by side, so as to ensure Raman
Spectra collection environment is identical.
(2) fiber multiplex is used, two-way raman spectral signal is alternately being obtained with a branch of optical fiber using photoswitch；Or
Person obtains two-way raman spectral signal simultaneously using double fiber-optic probe systems；
(3) the two groups of raman spectral signals obtained are transferred to FT Raman spectrometers, and Raman is obtained by data acquisition software
Spectroscopic data；
(4) crest location and peak intensity that the raman spectral signal transmitted External reference optical fiber obtains are right as reference
The raman spectral signal that measurement optical fiber obtains carries out wave number and strength signal is corrected；
Wave number correction calculating process be：Compared by reference to the raman spectral signal and standard spectrum of fibre-optical probe
Compared with acquisition wave number calibration curve equation：V=v0+ Dvr, wherein v are that reference optical fiber probe obtains Raman spectrum wave number, v0For mark
The Raman spectrum of quasi-optical spectrum, Dv are wave number rate of change, and r is external disturbance factor, by correction equation to measurement fibre-optical probe
Raman spectrum carries out wave number correction.
It is for intensity correction process：By reference to fibre-optical probe obtain specific wave number spectral intensity, then with mark
Quasi-optical spectral intensity is compared, and obtains intensity correction curve I (v)=I0(v) (1+DI), wherein I (v) are reference optical fiber probe
Spectral intensity, I0(v) it is standard spectrum intensity, DI is light intensity rate of change, then by the Raman spectrum of measurement optical fiber acquisition and by force
Spend calibration curve and carry out division arithmetic, carry out intensity correction.
(5) the test substance raman spectral signal after correction is pre-processed, realizes Qualitative and quantitative analysis.
Spectral signal pre-processes：Wavelet transformation or curve matching can be utilized to realize the removal of fluorescence background；Smoothly, filter
Ripple, Fourier transformation method realize CCD detection noises；Standard normal conversion, multiplicative scatter correction, Orthogonal Signal Correction Analyze, or
Intensity or area by the use of specific spectral peak are normalized as reference, realize the removal of sample spectra otherness；
Qualitative spectrometric or quantitative analysis.It is qualitative refer to realize with the method that standard spectrum compares by measure spectrum it is to be measured
The analysis of material composition, quantitative analysis refer to the spectroscopic data for having light with sample to be tested component by Raman spectrometer acquisition, so
Afterwards by the spectroscopic data of known sample collection and the relation of sample to be tested component, the calibration model (modeling) of property value is established；
The sample of unknown component property is predicted finally by the model established.Due to sample Raman spectrum spectral strength and sample
Linear relationship be present between this concentration of component, so quantitative analysis can be realized by modeling.Method can use：Polynary line
Property recurrence, ridge regression, principal component regression, offset minimum binary, artificial neural network, SVMs, genetic algorithm etc..
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (3)
1. a kind of Raman spectrum wave number and intensity real-time correction method, it is characterised in that including the step of it is as follows：
1) set External reference optical fiber to be placed on same position with measurement optical fiber, External reference optical fiber is in identical with measurement optical fiber
Under environment, the raman spectral signal of reference material is detected, after the raman spectral signal for measuring optical fiber measurement material to be detected, two beams
The signal that optical fiber returns is transported to FT Raman spectrometers；
2) crest location and peak intensity that the raman spectral signal for transmitting External reference optical fiber obtains are as reference, to measuring light
The raman spectral signal that fibre obtains carries out wave number and strength signal is corrected；
3) the test substance raman spectral signal after correction is pre-processed, realizes Qualitative and quantitative analysis；
The measurement optical fiber and External reference optical fiber are placed side by side；
The calculating process of wave number correction is in step 2)：Carried out by reference to the raman spectral signal and standard spectrum of fibre-optical probe
Compare, obtain wave number calibration curve equation：V=v0+ Δ vr, wherein v are that reference optical fiber probe obtains Raman spectrum wave number, v0
For the Raman spectrum of standard spectrum, Δ v is wave number rate of change, and r is external disturbance factor, and measurement optical fiber is visited by correction equation
The Raman spectrum of head carries out wave number correction；
It is for intensity correction process：By reference to fibre-optical probe obtain specific wave number spectral intensity, then with standard light
Spectral intensity is compared, and obtains intensity correction curve I (v)=I0(v) (1+ Δ I), wherein I (v) are the light of reference optical fiber probe
Spectral intensity, I0(v) it is standard spectrum intensity, Δ I is light intensity rate of change, then will measure Raman spectrum and the intensity that optical fiber obtains
Calibration curve carries out division arithmetic, carries out intensity correction.
2. according to Raman spectrum wave number and intensity real-time correction method described in claim 1, it is characterised in that in step 1),
Using fiber multiplex, two-way raman spectral signal is alternately being obtained with a branch of optical fiber using photoswitch.
3. according to Raman spectrum wave number and intensity real-time correction method described in claim 1, it is characterised in that in step 1),
Two-way raman spectral signal is obtained using double fiber-optic probe systems simultaneously.
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| CN105737979B (en) * | 2016-03-30 | 2018-06-15 | 广西科技大学 | The method that the drift of array spectrometer dark noise is eliminated using photoswitch |
| CN106404743A (en) * | 2016-11-01 | 2017-02-15 | 北京华泰诺安技术有限公司 | Raman spectrum and near infrared spectrum combined detection method and detection device |
| CN108169200B (en) * | 2016-12-07 | 2020-12-22 | 同方威视技术股份有限公司 | Method for calibrating a Raman spectroscopy detection apparatus |
| CN107340547A (en) * | 2017-07-24 | 2017-11-10 | 山东省职业卫生与职业病防治研究院 | A kind of UAV system spectrum detection system and its control method for danger detection operation |
| CN108106732B (en) * | 2017-12-01 | 2020-06-09 | 中国计量科学研究院 | Method and device for calibrating wave number resolution of Raman spectrometer |
| FR3077640B1 (en) * | 2018-02-05 | 2023-06-30 | Elichens | METHOD FOR ANALYZING A GAS BY DOUBLE ILLUMINATION |
| CN111337446A (en) * | 2020-05-08 | 2020-06-26 | 宁波大学 | Biosensor based on chalcogenide glass optical fiber and preparation method thereof |
| CN112763436A (en) * | 2020-12-24 | 2021-05-07 | 中国原子能科学研究院 | Spectrum measuring system |
| CN113190915B (en) * | 2021-04-19 | 2022-07-22 | 东风柳州汽车有限公司 | Vehicle strength evaluation method and system |
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