CN109856108A - A kind of Raman spectrum detection system and method - Google Patents
A kind of Raman spectrum detection system and method Download PDFInfo
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- CN109856108A CN109856108A CN201711237949.3A CN201711237949A CN109856108A CN 109856108 A CN109856108 A CN 109856108A CN 201711237949 A CN201711237949 A CN 201711237949A CN 109856108 A CN109856108 A CN 109856108A
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Abstract
The invention discloses a kind of Raman spectrum detection system and methods.The system comprises the first measuring device, the second measuring device, spectral analysis devices (8), first measuring device includes first laser device (1), optical path converter (3), the first smooth focalizer (4), photo-coupler (7), and second measuring device includes second laser (9), the second smooth focalizer (11), displacement guide rail (12).Raman spectrum detection system and method for the invention can get around the influence of container Raman spectrum when substance detects in opaque containers, and can also eliminate the influence of substance fluorescence itself.
Description
Technical field
The present invention relates to laser activated spectroscopic detection technique field more particularly to a kind of Raman spectrum detection system and sides
Method.
Background technique
When carrying out Raman spectrum detection to the substance inside container to carry out species analysis, it would be desirable to be able to around the drawing of container
The influence of graceful spectrum.But traditional Raman spectrum detection can only test sample superficial information, or can only penetrate transparent
Bottom is detected on surface layer.
However, many analysis applications need very high chemical specificity, and penetrate multilayer opaque sample or opaque
Counterfeit drug in the ability of packaging material, such as lossless decomposition skeletal diseases, the hidden explosive of search, identification packaging.Traditional drawing
Graceful spectral detection is backscattering form, it is easy to accomplish, but very shallow (such as biological group of several hundred microns thick of penetration depth
It knits).
In addition, fluorescence interference is one of disturbing factor common in Raman spectrum detection process.In Raman detection, laser
Other than stiff Raman scattering signal occurs in detection target, sample can also emit fluorescence after absorbing exciting light energy
Spectral signal, two kinds of mutual aliasings of signal, and the intensity of fluorescence signal is often required to stronger than Raman signal, or even floods Raman completely
Signal, this generates serious interference to Raman detection.In this case it just needs to interfere fluorescence and eliminate.
Therefore, it is necessary to a kind of detection system of Raman spectrum and methods, can carry out to the substance inside opaque containers
Analysis, or fluorescence interference can be eliminated when needed, to obtain more accurate testing result.
Summary of the invention
In order to solve the problems, such as in the prior art to detect substance in opaque containers and fluorescence interfere the problem of,
The present invention provides a kind of Raman spectrum detection system and methods.
According to an aspect of the invention, there is provided a kind of Raman spectrum detection system, comprising: the first measuring device,
Two measuring devices, spectral analysis device (8), first measuring device include first laser device (1), optical path converter (3),
One smooth focalizer (4), photo-coupler (7), second measuring device include second laser (9), the second smooth focalizer (11),
Displacement guide rail (12);Wherein,
The first laser device (1) is set to the first side of the optical path converter (3), for exporting collimated light beam;
The optical path converter (3) is used to reflect the collimated light beam of the first laser device (1) output;
The first smooth focalizer (4) is set to the first side of the optical path converter (3), and turns perpendicular to the optical path
The light beam setting of parallel operation (3) reflection, for the reflected beams to be focused to and are transmitted to detection target (5);
The photo-coupler (7) is set to second side of the optical path converter (3), and perpendicular to the optical path converter
(3) the light beam setting transmitted, for being transmitted to the spectral analysis device (8) after coupling transmitted light beam;
The spectral analysis device (8) is used to receive the light beam of the photo-coupler (7) transmission, and carries out light to the light beam
Spectrum analysis;
The second laser (9) is set on the displacement guide rail (12), for exporting collimated light beam;
The second smooth focalizer (11) is arranged perpendicular to the light beam that the second laser (9) exports, for this is defeated
Light beam focuses and is transmitted to detection target (5) out;
The displacement guide rail (12) is for making the second laser (9) horizontal translation.
Wherein,
The first laser device (1) is arranged to export the collimated light beam of first frequency;
The collimated light beam of output second frequency is set in the second laser (9);
Wherein, the frequency difference Δ v range of the first frequency and the second frequency is 3-20cm-1。
Wherein, the spectral analysis device (8) is used for:
Obtain the spectral signal S that the first laser device (1) excites generation in detection target (5)0;
Obtain the spectral signal S that the second laser (9) excites generation in detection target (5)1..., SN, N is big
In be equal to 1 positive integer, wherein the output beam of the second laser (9) detection target (5) on focus point with it is described
When detecting the distance of focus point of target (5) is i × d, the spectral signal of acquisition is the output beam of first laser device (1)
Si, i=1,2 ..., N;
Obtain spectral signal S0,S1,...,SNSpectrum peak position and intensity value be (P0j,Y0j)、(P1j,Y1j)……(Pij,
Yij), wherein j=1,2 ..., M, M are the spectral peak sum in spectral signal;
It is calculated as follows subtractive factor C1j,C2j,...,CNj,
When N=1, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0jIf C1j≤ 1, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j,
When N=2, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0j, C2j=Y2j/Y0jIf C2j≤
C1j, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=
C1j, C2=C2j, and so on;
Sample signal R is calculated,
Wherein, the spectral analysis device (8) is also used to:
Obtain the spectral signal S that the first laser device (1) excites generation in detection target (5)0, and described in acquisition
The light beam of second laser (9) output beam and focus point and the first laser device (1) in detection target (5) is detecting
The focus point of target (5) collected spectral signal S ' when being overlapped0;
Obtain poor spectrum signal D, D=S0-S′0, and calculate integral K, the K=∫ Ddv of poor spectrum signal D;
Boxcar function Rect is constructed,
It calculates mirror image raman spectral signal R (- v), R (- v)=ifft [fft (K)/fft (Rect)];
R (- v) mirror image is negated, acquisition filters out the Raman spectrum R (v) after fluorescence.
Wherein, the system also includes the first optical filter (2), the second optical filter (6), third optical filters (10), wherein
First optical filter (2) is set to the optical path between the first laser device (1) and the optical path converter (3)
On;
Second optical filter (6) is set to the optical path between the optical path converter (3) and the photo-coupler (7)
On;
The third optical filter (10) is set between the second laser (9) and the second smooth focalizer (11)
In optical path.
According to another aspect of the present invention, a kind of Raman spectra detection process is provided, comprising:
Step 1, article to be detected is placed at detection target (5);
Step 2, one of operations described below is executed:
Mode one makes first laser device (1) to export first frequency collimated light beam, and the first frequency collimated light beam is by optical path
Converter (3) reflects and is transmitted to the described first smooth focalizer (4), wherein making the described first smooth focalizer (4) perpendicular to described
The light beam received is focused and is transmitted to detection target by the light beam setting of optical path converter (3) reflection, the first smooth focalizer (4)
(5), the light beam for being detected target (5) scattering Raman signal is excited to be transmitted through the optical path converter (3) and pass through optical coupling
Spectral analysis device (8) are transmitted to after device (7) coupling, wherein transmiting the photo-coupler (7) perpendicular to optical path converter (3)
Light beam,
Second laser (9) is set on displacement guide rail (12), so that second laser (9) is exported collimated light beam, and make
Second smooth focalizer (11) is arranged perpendicular to the collimated light beam that the second laser (9) exports to focus simultaneously the output beam
It is transmitted to detection target (5), so that displacement guide rail (12) translation is changed focus position, detected target (5) is excited to scatter Raman
The light beam of signal is transmitted through the optical path converter (3) and is transmitted to the spectrum analysis after coupling by photo-coupler (7)
Device (8),
Spectrum analysis is carried out to the received light beam of the above process by the spectral analysis device (8);
Mode two makes first laser device (1) to export first frequency collimated light beam, and the first frequency collimated light beam is by optical path
Converter (3) reflects and is transmitted to the described first smooth focalizer (4), wherein making the described first smooth focalizer (4) perpendicular to described
The light beam received is focused and is transmitted to detection target by the light beam setting of optical path converter (3) reflection, the first smooth focalizer (4)
(5), the light beam for being detected target (5) scattering Raman signal is excited to be transmitted through the optical path converter (3) and pass through optical coupling
Spectral analysis device (8) are transmitted to after device (7) coupling, wherein transmiting the photo-coupler (7) perpendicular to optical path converter (3)
Light beam,
Second laser (9) is set on displacement guide rail (12), second laser (9) is made to export second frequency collimated light
Beam, and the second smooth focalizer (11) is set to incite somebody to action perpendicular to the second frequency collimated light beam that the second laser (9) exports
The output beam focuses and is transmitted to detection target (5), translates displacement guide rail (12) and light beam is made to pass through second light
Focalizer (11) focuses to the convergent point of detection target (5) and the first frequency collimated light beam passes through the described first smooth focalizer
(4) convergent point for focusing to detection target (5) is overlapped, and the light beam for being detected target (5) scattering Raman signal is excited to be transmitted through
The optical path converter (3) and by photo-coupler (7) couple after be transmitted to the spectral analysis device (8),
Spectrum analysis is carried out to the received light beam of the above process by the spectral analysis device (8);
Wherein, the frequency difference Δ v range of the first frequency and the second frequency is 3-20cm-1。
Wherein, in aforesaid way one, spectrum point is carried out to the received light beam of the above process by the spectral analysis device (8)
Analysis includes:
It obtains the first laser device (1) output beam and excites the spectral signal S of generation in detection target (5)0;
It obtains the second laser (9) output beam and excites the spectral signal of generation in detection target (5)
S1,...,SN, N is the positive integer more than or equal to 1, wherein the output beam of the second laser (9) is in detection target (5)
Focus point and the first laser device (1) output beam detect target (5) focus point at a distance from be i × d when, acquisition
Spectral signal be Si, i=1,2 ..., N;
Obtain spectral signal S0,S1,...,SNSpectrum peak position and intensity value (P0j,Y0j)、(P1j,Y1j)、……(Pij,
Yij), wherein j=1,2 ..., M, M are the spectral peak sum in spectral signal;
It is calculated as follows subtractive factor C1j,C2j,...,CNj,
When N=1, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0jIf C1j≤ 1, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j,
When N=2, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0j, C2j=Y2j/Y0jIf C2j≤
C1j, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=
C1j, C2=C2j, and so on;
Sample signal R is calculated,
Wherein, in aforesaid way two, spectrum point is carried out to the received light beam of the above process by the spectral analysis device (8)
Analysis includes:
It obtains the first laser device (1) output beam and excites the spectral signal S of generation in detection target (5)0, with
And obtain second laser (9) output beam and focus point and the first laser device (1) in detection target (5)
Light beam collected spectral signal S ' when the focus point for detecting target (5) is overlapped0;
Obtain poor spectrum signal D, D=S0-S′0, and calculate integral K, the K=∫ Ddv of poor spectrum signal D;
Boxcar function Rect is constructed,
It calculates mirror image raman spectral signal R (- v), R (- v)=ifft [fft (K)/fft (Rect)];
R (- v) mirror image is negated, acquisition filters out the Raman spectrum R (v) after fluorescence.
Wherein,
The mode one further include: the first optical filter (2) is set to the first laser device (1) and the light path converting
In optical path between device (3), the second optical filter (6) is set between the optical path converter (3) and the photo-coupler (7)
Optical path on, third optical filter (10) is set between the second laser (9) and the second smooth focalizer (11)
In optical path;
The mode two further include: the first optical filter (2) is set to the first laser device (1) and the light path converting
In optical path between device (3), the second optical filter (6) is set between the optical path converter (3) and the photo-coupler (7)
Optical path on, third optical filter (10) is set between the second laser (9) and the second smooth focalizer (11)
In optical path.
Raman spectrum detection system and method in the present invention carry out SORS detection technique with SERDS detection technique ingenious
In conjunction with the influence of container Raman spectrum can be got around when substance detects in opaque containers, and can also eliminate
The influence of substance fluorescence itself.In this way, container only can be got around respectively by a set of detection system influences and eliminates substance sheet
Body fluorescence influences, so that detection process is more easy.
Using method and system of the invention, it is able to achieve the continuously adjustable spatial offset Raman Measurement of spatial offset, together
When by two lasers of certain frequency difference realize that shift frequency excitation disappears the detection of fluorescence Raman spectrum.In turn, it is capable of providing sample depth
The information of layer has huge and broad application prospect, can be widely used in non-intruding bone Raman spectrum, cancer diagnosis tool
Exploitation, detection diffusing scattering plastic bottle in counterfeit drug, mail safety check, detection the fields such as liquid and solid-state explosive.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the schematic diagram for the SORS detection technique that the present invention uses;
Fig. 2 is the schematic diagram of Raman spectrum detection system according to the present invention;
Fig. 3 is the flow chart of mode one in Raman spectra detection process according to the present invention;
Fig. 4 is signal S according to the present invention0,S1,S2Raman spectrogram;
Fig. 5 is the Raman spectrogram of tank signal according to the present invention and sample signal;
Fig. 6 is the flow chart of mode two in Raman spectra detection process according to the present invention;
Fig. 7 is signal S according to the present invention0、S′0Raman spectrogram;
Fig. 8 is the sample Raman spectrogram after removal fluorescence according to the present invention.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.It needs
Illustrate, in the absence of conflict, the features in the embodiments and the embodiments of the present application can mutual any combination.
For at present can not to the substance in opaque containers carry out spectral detection, and there are substance fluorescence interference asking
Topic, the present invention are innovatively proposed space displacement Raman detection technology (Spatially offset Raman
Spectroscopy, abbreviation SORS) and frequency displacement excitation disappear fluorescence Raman spectrum detection technique (Shifted Excitation
Raman Difference Spectroscopy, abbreviation SERDS) system and method that combine.
Space displacement Raman spectrum detection technique SORS can detect the Raman spectrum of high quality through thick coating
Signal.It can explicitly distinguish the Raman spectrum of material and container, identify while realizing material and container.Space displacement is drawn
Graceful spectrum can obtain the layer-by-layer Raman spectrum of diffusing scattering sample appropriate, and laser power is lower.SORS technology can be with
Go deep into several millimeters of test sample, to analyze the chemical information of opaque sample interior.Fig. 1 shows the principle of SORS technology
Figure.SORS Method And Principle is to leave collection Raman signal at illuminated laser spot certain displacement in sample surfaces (see Fig. 1).Upper rheme
Shifting is bigger, and the contribution of deeper sample is more in gained Raman signal.
Shift frequency excitation-detection technology SERDS is a kind of detection means for effectively overcoming fluorescence to interfere.Shift frequency excitation-detection
Technology excites measured matter using laser similar in two or more wavelength respectively, and the Raman spectrum of acquisition is carried out
Difference spectrum.Since the fluorescence background excited twice is identical, and Raman signatures summit generates translation, therefore can effectively eliminate fluorescence back
The interference of scape, and then raman characteristic peak is restored using certain algorithm.
Raman spectrum transmitting be specific frequency shift relative to excitation wavelength discrete fingerprint spectral peak, spectral peak it is exhausted
It is the variation with excitation wavelength to wavelength location and changes;Fluorescence spectrum is the relatively continuous spoke of substance stimulated emission
Spectral signal is penetrated, what the shape of spectrogram and position did not changed with excitation wavelength variation.The machine generated according to two kinds of signals
The difference of reason and feature, can detect its spectral signal by the close excitation light source of two or more wavelength respectively,
By calculate, by spectral signal with the raman spectral signal of excitation wavelength frequency displacement and not with the glimmering of excitation wavelength frequency displacement
Optical signal is separated, and the interference that fluorescence detects Raman spectrum can be eliminated.
The present invention innovatively combines SORS technology and SERDS technology, proposes a kind of Raman spectrum detection system,
As shown in Fig. 2, the system includes:
First measuring device, the second measuring device, spectral analysis device 8, the first measuring device include first laser device 1,
Optical path converter 3, the first smooth focalizer 4, photo-coupler 7, the second measuring device include second laser 9, the second smooth focalizer
11, displacement guide rail 12;Wherein,
First laser device 1 is set to the first side of optical path converter 3, for exporting collimated light beam;
Optical path converter 3 is used to reflect the collimated light beam of the output of first laser device 1;
First smooth focalizer 4 is set to the first side of optical path converter 3, and perpendicular to the light beam that optical path converter 3 reflects
Setting, for the reflected beams to be focused to and are transmitted to detection target 5;
Photo-coupler 7 is set to second side of optical path converter 3, and the light beam transmitted perpendicular to optical path converter 3 is arranged,
For being transmitted to spectral analysis device 8 after coupling transmitted light beam;
Spectral analysis device 8 is used to receive the light beam of the transmission of photo-coupler 7, and carries out spectrum analysis to the light beam;
Second laser 9 is set on displacement guide rail 12, for exporting collimated light beam;
Second smooth focalizer 11 is arranged perpendicular to the light beam that second laser 9 exports, for focusing simultaneously the output beam
It is transmitted to detection target 5;
Displacement guide rail 12 is for making 9 horizontal translation of second laser.
First laser device 1 is arranged to export the collimated light beam of first frequency;Second laser 9 is arranged to output second
The collimated light beam of frequency;Wherein, the frequency difference Δ v range of first frequency and second frequency is 3-20cm-1。
Optical path converter 3 can be dichroism edge filter, for reflecting the laser of the sending of first laser device 1, thoroughly
Penetrate signal light.Laser is converged to sample and gone out by the first smooth focalizer 4, while being acquired signal light and being collimated into directional light.Optical coupling
Device 7 is used to collected signal light being coupled into rear end spectroscopic analysis system.Second smooth focalizer 11 emits second laser 9
Laser beam converge at sample.Displacement guide rail 12 drives laser 9 and its projection system mobile, to realize different spaces
The measurement of offset.And target 5 is detected in Fig. 1 and divides two layers inside and outside, outer layer signal packaging or container, internal layer signal sample.
The measuring system that the output beam of above-mentioned first laser device 1 and second laser 9 convergence hot spot forms when not being overlapped
For separation vessel signal and sample signal, realize that getting around bottle wall measures the raman spectral signal of inner sample.At this
In mode, the frequency of first laser device 1 and 9 output beam of second laser can be identical or not identical.
Above-mentioned first laser device 1 exports the collimated light beam of first frequency and second laser 9 exports the light beam of second frequency
The measuring system that convergence hot spot forms when being overlapped is used to eliminate the fluorescence interference of sample itself, to obtain the sample copy for being free of fluorescence
The raman spectral signal of body.
Spectral analysis device 8 is used for:
Obtain the spectral signal S that first laser device 1 excites generation in detection target 50;
Obtain the spectral signal S that second laser 9 excites generation in detection target 51,...,SN, N is more than or equal to 1
Positive integer, wherein the output beam of second laser 9 is in the output beam for detecting focus point and first laser device 1 in target 5
When detecting the distance of focus point of target 5 is i × d, the spectral signal of acquisition is Si, i=1,2 ..., N;
Obtain spectral signal S0,S1,...,SNSpectrum peak position and intensity value be (P0j,Y0j)、(P1j,Y1j)、……(Pij,
Yij), wherein j=1,2 ..., M, M are the spectral peak sum in spectral signal;
It is calculated as follows subtractive factor C1j,C2j,...,CNj,
When N=1, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0jIf C1j≤ 1, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j,
When N=2, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0j, C2j=Y2j/Y0jIf C2j≤
C1j, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=
C1j, C2=C2j, and so on;
Sample signal R is calculated,
The signal of bottle wall can be removed by the above process, extract sample signal.
Spectral analysis device 8 is also used to:
Obtain the spectral signal S that first laser device 1 excites generation in detection target 50, and obtain second laser 9
Output beam and detecting target 5) on focus point and the light beam of first laser device 1 when the focus point of detection target 5 is overlapped
Collected spectral signal S '0;
Obtain poor spectrum signal D, D=S0-S′0, and calculate integral K, the K=∫ Ddv of poor spectrum signal D;
Boxcar function Rect is constructed,Wherein Δ v is 3-20cm above-1;
It calculates mirror image raman spectral signal R (- v), R (- v)=ifft [fft (K)/fft (Rect)];
R (- v) mirror image is negated, acquisition filters out the Raman spectrum R (v) after fluorescence.
By the above process, the fluorescence interference of sample itself can be eliminated.
Here the range for the frequency difference Δ v being arranged is related with the characteristic of Raman spectrum and fluorescence spectrum, is in order to ensure twice
The fluorescence background of excitation is identical, and the translation that raman characteristic peak generates can be identified.Two exciting lights within the scope of this frequency difference
Source, the frequency difference of the Raman spectrum excited also within this range, can quilts within the scope of the spectral resolution of normal Raman spectrometer
Instrument is differentiated;The fluorescence spectrum signal that two excitation light sources are excited simultaneously, which can ensure that, to reach unanimity;So that it is guaranteed that number can be passed through
Fluorescence spectrum and Raman spectrum are separated according to Processing Algorithm.
In addition, above system further includes the first optical filter 2, the second optical filter 6, third optical filter 10, wherein first filters
Piece 2 is set in the optical path between first laser device 1 and optical path converter 3;Second optical filter 6 is set to 3 He of optical path converter
In optical path between photo-coupler 7;Third optical filter 10 is set to the optical path between second laser 9 and the second smooth focalizer 11
On.
First optical filter 2 is that Laser Purification optical filter for purifying optical maser wavelength ingredient filters out light disturbance.Second filter
Mating plate 6 is notch filtering light piece, for obstructing rayleigh scattering light, eliminates the spuious optical signal of jammr band.Third optical filter 10 is
Laser Purification optical filter purifies optical maser wavelength ingredient, filters out light disturbance.
The course of work of the detailed description the system according to the present invention under two kinds of measurement patterns separately below.
The first measurement pattern: separation vessel signal and sample signal.
Fig. 3 shows operating process of the system under the first detection pattern.In this process, by first laser device 1,
Optical path converter 3, the first smooth focalizer 4, photo-coupler 7, second laser 9, the second smooth focalizer 11, spectral analysis device 8
Form detection system.First laser device 1 is coaxial with Raman detection optical path, realizes the Raman detection of the kernel offset to sample,
Its signal measured is as reference signal S0, and the ratio of tank signal is great in S0 at this time, and the signal of inner sample is weak or even complete
Buried entirely by tank signal.Second laser 9 and Raman detection optical path are not coaxial, and can be realized to sample not by adjusting slide unit
Raman detection in the case where isospace offset, obtains spatial offset Raman signal, with the increase of spatial offset, container letter
Number specific gravity reduce, the signal specific gravity of inner sample increases.Finally, by S0With Si(i >=1) carries out algorithm calculation process, can
Tank signal and sample signal are isolated, gets around bottle wall to the raman spectroscopy measurement of inner sample to realize.Specifically such as Fig. 3 institute
Show.
In the embodiment, it is assumed that N=2, steps are as follows for the concrete analysis of spectral analysis device 8:
(1) by S0,S1,S2Normalization, the intensity after extracting raman spectra position and normalization;
(2) spectral signal S is obtained0,S1,...,SNSpectrum peak position and intensity value (P0j,Y0j)、(P1j,Y1j)、(Pij,
Yij), wherein j=1,2 ..., M, M are the spectral peak sum in spectral signal, S1、S2In corresponding spectral peak be (P1j,Y1j) and
(P2j,Y2j), if without spectral peak Y1j、Y2jTake zero;
(3) j={ 1 ..., M } is successively taken, subtractive factor C is sought1j=Y1j/Y0j, C2j=Y2j/Y0jIf C2j≤C1j, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j, C2=
C2j;
(4) sample signal R is calculated1,And calculate the R after normalization1For Rg=R/max
(R)。
Above-mentioned the case where being N=2, as N > 2 and so on.
Fig. 4 and Fig. 5 respectively illustrate S0,S1,S2Raman spectrogram and isolated tank signal R0With sample signal R1's
Raman spectrogram.
Second of measurement pattern: fluorescent interference is eliminated.
Fig. 6 shows operating process of the system under second of detection pattern.In this process, surface sample can be removed
The fluorescence of product itself interferes, and wherein first laser device 1 and second laser 9 have certain frequency difference Δ ν to realize that shift frequency excites, and
Seek Δ ν=3~20cm-1。
By first laser device 1, optical path converter 3, the first smooth focalizer 4, photo-coupler 7, second laser 9, the second light
Focalizer 11,12 spectral analysis device 8 of displacement guide rail form detection system.First laser device 1 is coaxial with Raman detection optical path,
The signal S measured0.Adjusting displacement guide rail 12 makes second laser 9 issue convergent point and first of the light beam in detection target 5
Laser 1 issues convergent point of the light beam in detection target 5 and is overlapped, and the signal measured at this time is S '0.By to S0、S′0It carries out
Standardization, poor spectrum processing can eliminate fluorescence spectrum signal, then handled using algorithm difference frequency signal, be can be obtained
Sample is free of the original raman spectral signal R of fluorescence.It is specific as shown in Figure 6.
In the embodiment, steps are as follows for the concrete analysis of spectral analysis device 8:
(1) to S0、S′0After being normalized, poor spectrum signal D, D=S are obtained0-S′0, and calculate poor spectrum signal D's
Integrate K, K=∫ Ddv;
(2) boxcar function Rect is constructed,
(3) mirror image raman spectral signal R (- v) is calculated, R (- v)=ifft [fft (K)/fft (Rect)];
(4) R (- v) mirror image is negated, acquisition filters out the Raman spectrum R (v) after fluorescence.
Fig. 7 and Fig. 8 respectively illustrate S0、S′0Raman spectrogram and removal fluorescence after sample Raman spectrogram.
The present invention also provides a kind of Raman spectra detection process, which is characterized in that the described method includes:
Step 1, article to be detected is placed at detection target 5;
Step 2, one of operations described below is executed:
Mode one, makes first laser device 1 export first frequency collimated light beam, and the first frequency collimated light beam is turned by optical path
Parallel operation 3 reflects and is transmitted to the described first smooth focalizer 4, wherein making the described first smooth focalizer 4 perpendicular to the light path converting
The light beam received is focused and is transmitted to detection target 5 by the light beam setting that device 3 reflects, the first smooth focalizer 4, and excitation is detected
The light beam that target 5 generates spectral signal is transmitted through the optical path converter 3 and is transmitted to spectrum after coupling by photo-coupler 7
Analytical equipment 8, wherein the light beam for transmiting the photo-coupler 7 perpendicular to optical path converter 3,
Second laser 9 is set on displacement guide rail 12, so that second laser 9 is exported collimated light beam, and make the second light
Focalizer 11 is arranged perpendicular to the collimated light beam that the second laser 9 exports to focus the output beam and be transmitted to detection
Target 5 makes the translation of displacement guide rail 12 to realize the different spatial offset of convergence hot spot, excites and is detected the generation spectrum letter of target 5
Number light beam be transmitted through the optical path converter 3 and by photo-coupler 7 couple after be transmitted to the spectral analysis device 8,
Spectrum analysis is carried out to the received light beam of the above process by the spectral analysis device 8;
Mode two, makes first laser device 1 export first frequency collimated light beam, and the first frequency collimated light beam is turned by optical path
Parallel operation 3 reflects and is transmitted to the described first smooth focalizer 4, wherein making the described first smooth focalizer 4 perpendicular to the light path converting
The light beam received is focused and is transmitted to detection target 5 by the light beam setting that device 3 reflects, the first smooth focalizer 4, and excitation is detected
The light beam that target 5 generates spectral signal is transmitted through the optical path converter 3 and is transmitted to spectrum after coupling by photo-coupler 7
Analytical equipment 8, wherein the light beam for transmiting the photo-coupler 7 perpendicular to optical path converter 3,
Second laser 9 is set on displacement guide rail 12, second laser 9 is made to export second frequency collimated light beam, and
The second frequency collimated light beam setting for exporting the second smooth focalizer 11 perpendicular to the second laser 9 is with by the output beam
Detection target 5 is focused and be transmitted to, displacement guide rail 12 is translated and light beam is focused to by the described second smooth focalizer 11
The convergent point and the first frequency collimated light beam for detecting target 5 are focused to by the described first smooth focalizer 4 detects target 5
Convergent point is overlapped, and the light beam for being detected the generation spectral signal of target 5 is excited to be transmitted through the optical path converter 3 and pass through optocoupler
Clutch 7 is transmitted to the spectral analysis device 8 after coupling,
Spectrum analysis is carried out to the received light beam of the above process by the spectral analysis device 8;
Wherein, the frequency difference Δ v range of the first frequency and the second frequency is 3-20cm-1。
In aforesaid way one, carrying out spectrum analysis to the received light beam of the above process by the spectral analysis device 8 includes:
Obtain the spectral signal S that the first laser device 1 excites generation in detection target 50;
Obtain the spectral signal S that the second laser 9 excites generation in detection target 51,...,SN, N be greater than etc.
In 1 positive integer, wherein focus point and the first laser of the output beam of the second laser 9 in detection target 5
For the output beam of device 1 when detecting the distance of focus point of target 5 is i × d, the spectral signal of acquisition is Si, i=1,2 ...,
N;
Obtain spectral signal S0,S1,...,SNSpectrum peak position and intensity value (P0j,Y0j)、(P1j,Y1j)、……(Pij,
Yij), wherein j=1,2 ..., M, M are the spectral peak sum in spectral signal;
It is calculated as follows subtractive factor C1j,C2j,...,CNj,
When N=1, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0jIf C1j≤ 1, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j,
When N=2, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0j, C2j=Y2j/Y0jIf C2j≤
C1j, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=
C1j, C2=C2j, and so on;
Sample signal R is calculated,
In aforesaid way two, carrying out spectrum analysis to the received light beam of the above process by the spectral analysis device 8 includes:
Obtain the spectral signal S that the first laser device 1 excites generation in detection target 50, and obtain described second
The light beam of 9 output beam of laser and focus point and the first laser device 1 in detection target 5 is in the poly- of detection target 5
Collected spectral signal S ' when focus is identical0;
Obtain poor spectrum signal D, D=S0-S′0, and calculate integral K, the K=∫ Ddv of poor spectrum signal D;
Boxcar function Rect is constructed,
It calculates mirror image raman spectral signal R (- v), R (- v)=ifft [fft (K)/fft (Rect)];
R (- v) mirror image is negated, acquisition filters out the Raman spectrum R (v) after fluorescence.
In addition, the mode one further include: the first optical filter 2 is set to the first laser device 1 and the optical path turns
In optical path between parallel operation 3, the second optical filter 6 is set to the optical path between the optical path converter 3 and the photo-coupler 7
On, third optical filter 10 is set in the optical path between the second laser 9 and the second smooth focalizer 11;
The mode two further include: the first optical filter 2 is set to the first laser device 1 and the optical path converter 3
Between optical path on, the second optical filter 6 is set in the optical path between the optical path converter 3 and the photo-coupler 7, will
Third optical filter 10 is set in the optical path between the second laser 9 and the second smooth focalizer 11.
Raman spectrum detection system and method in the present invention carry out SORS detection technique with SERDS detection technique ingenious
In conjunction with the influence of container Raman spectrum can be got around when substance detects in opaque containers, and can also eliminate
The influence of substance fluorescence itself.In this way, container only can be got around respectively by a set of detection system influences and eliminates substance sheet
Body fluorescence influences, so that detection process is more easy.
Using method and system of the invention, it is able to achieve the continuously adjustable spatial offset Raman Measurement of spatial offset, together
When by two lasers of certain frequency difference realize that shift frequency excitation disappears the detection of fluorescence Raman spectrum.In turn, it is capable of providing sample depth
The information of layer has huge and broad application prospect, can be widely used in non-intruding bone Raman spectrum, cancer diagnosis tool
Exploitation, detection diffusing scattering plastic bottle in counterfeit drug, mail safety check, detection the fields such as liquid and solid-state explosive.
Descriptions above can combine implementation individually or in various ways, and these variants all exist
Within protection scope of the present invention.
It should be noted that, in this document, the terms "include", "comprise" or its any other variant are intended to non-row
His property includes, so that including the article of a series of elements or equipment not only includes those elements, but also including not having
There is the other element being expressly recited, or further includes for this article or the intrinsic element of equipment.Do not limiting more
In the case where system, the element that is limited by sentence " including ... ", it is not excluded that in the article or equipment for including the element
There is also other identical elements.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, reference only to preferred embodiment to this hair
It is bright to be described in detail.Those skilled in the art should understand that can modify to technical solution of the present invention
Or equivalent replacement should all cover in claim model of the invention without departing from the spirit and scope of the technical solution of the present invention
In enclosing.
Claims (9)
1. a kind of Raman spectrum detection system, which is characterized in that the system comprises the first measuring device, the second measuring device,
Spectral analysis device (8), first measuring device include first laser device (1), optical path converter (3), the first smooth focalizer
(4), photo-coupler (7), second measuring device include second laser (9), the second smooth focalizer (11), displacement guide rail
(12);Wherein,
The first laser device (1) is set to the first side of the optical path converter (3), for exporting collimated light beam;
The optical path converter (3) is used to reflect the collimated light beam of the first laser device (1) output;
The first smooth focalizer (4) is set to the first side of the optical path converter (3), and perpendicular to the optical path converter
(3) the light beam setting reflected, for the reflected beams to be focused to and are transmitted to detection target (5);
The photo-coupler (7) is set to second side of the optical path converter (3), and perpendicular to the optical path converter (3)
The light beam of transmission is arranged, for being transmitted to the spectral analysis device (8) after coupling transmitted light beam;
The spectral analysis device (8) is used to receive the light beam of the photo-coupler (7) transmission, and carries out spectrum point to the light beam
Analysis;
The second laser (9) is set on the displacement guide rail (12), for exporting collimated light beam;
The second smooth focalizer (11) is arranged perpendicular to the light beam that the second laser (9) exports, and is used for the output light
Beam focuses and is transmitted to detection target (5);
The displacement guide rail (12) is for making the second laser (9) horizontal translation.
2. Raman spectrum detection system as described in claim 1, which is characterized in that
The first laser device (1) is arranged to export the collimated light beam of first frequency;
The collimated light beam of output second frequency is set in the second laser (9);
Wherein, the frequency difference Δ v range of the first frequency and the second frequency is 3-20cm-1。
3. Raman spectrum detection system as claimed in claim 2, which is characterized in that the spectral analysis device (8) is used for:
Obtain the spectral signal S that the first laser device (1) excites generation in detection target (5)0;
Obtain the spectral signal S that the second laser (9) excites generation in detection target (5)1,...,SN, N be greater than etc.
In 1 positive integer, wherein focus point and described first of the output beam of the second laser (9) in detection target (5)
For the output beam of laser (1) when detecting the distance of focus point of target (5) is i × d, the spectral signal of acquisition is Si, i=
1,2,...,N;
Obtain spectral signal S0,S1,...,SNSpectrum peak position and intensity value be (P0j,Y0j)、(P1j,Y1j)……(Pij,Yij),
Wherein j=1,2 ..., M, M are the spectral peak sum in spectral signal;
It is calculated as follows subtractive factor C1j,C2j,...,CNj,
When N=1, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0jIf C1j≤ 1, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j,
When N=2, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0j, C2j=Y2j/Y0jIf C2j≤C1j, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j, C2=
C2j, and so on;
Sample signal R is calculated,
4. Raman spectrum detection system as claimed in claim 2 or claim 3, which is characterized in that the spectral analysis device (8) is also used
In:
Obtain the spectral signal S that the first laser device (1) excites generation in detection target (5)0, and obtain described second
The light beam of laser (9) output beam and focus point and the first laser device (1) in detection target (5) is in detection target
(5) focus point collected spectral signal S ' when being overlapped0;
Obtain poor spectrum signal D, D=S0-S′0, and calculate integral K, the K=∫ Ddv of poor spectrum signal D;
Boxcar function Rect is constructed,
It calculates mirror image raman spectral signal R (- v), R (- v)=ifft [fft (K)/fft (Rect)];
R (- v) mirror image is negated, acquisition filters out the Raman spectrum R (v) after fluorescence.
5. Raman spectrum detection system as described in claim 1, which is characterized in that the system also includes the first optical filters
(2), the second optical filter (6), third optical filter (10), wherein
First optical filter (2) is set in the optical path between the first laser device (1) and the optical path converter (3);
Second optical filter (6) is set in the optical path between the optical path converter (3) and the photo-coupler (7);
The third optical filter (10) is set to the optical path between the second laser (9) and the second smooth focalizer (11)
On.
6. a kind of Raman spectra detection process, which is characterized in that the described method includes:
Step 1, article to be detected is placed at detection target (5);
Step 2, one of operations described below is executed:
Mode one makes first laser device (1) to export first frequency collimated light beam, and the first frequency collimated light beam is by light path converting
Device (3) reflects and is transmitted to the described first smooth focalizer (4), wherein making the described first smooth focalizer (4) perpendicular to the optical path
The light beam received is focused and is transmitted to detection target (5) by the light beam setting of converter (3) reflection, the first smooth focalizer (4),
The light beam for being detected target (5) scattering Raman signal is excited to be transmitted through the optical path converter (3) and by photo-coupler (7)
Spectral analysis device (8) are transmitted to after coupling, wherein the light for transmiting the photo-coupler (7) perpendicular to optical path converter (3)
Beam,
Second laser (9) is set on displacement guide rail (12), so that second laser (9) is exported collimated light beam, and make second
Light focalizer (11) is arranged perpendicular to the collimated light beam that the second laser (9) exports to focus and transmit the output beam
To detection target (5), so that displacement guide rail (12) translation is changed focus position, detected target (5) is excited to scatter Raman signal
Light beam be transmitted through the optical path converter (3) and by photo-coupler (7) couple after be transmitted to the spectral analysis device
(8),
Spectrum analysis is carried out to the received light beam of the above process by the spectral analysis device (8);
Mode two makes first laser device (1) to export first frequency collimated light beam, and the first frequency collimated light beam is by light path converting
Device (3) reflects and is transmitted to the described first smooth focalizer (4), wherein making the described first smooth focalizer (4) perpendicular to the optical path
The light beam received is focused and is transmitted to detection target (5) by the light beam setting of converter (3) reflection, the first smooth focalizer (4),
The light beam for being detected target (5) scattering Raman signal is excited to be transmitted through the optical path converter (3) and by photo-coupler (7)
Spectral analysis device (8) are transmitted to after coupling, wherein the light for transmiting the photo-coupler (7) perpendicular to optical path converter (3)
Beam,
Second laser (9) is set on displacement guide rail (12), second laser (9) is made to export second frequency collimated light beam,
And the second smooth focalizer (11) is set with this is defeated perpendicular to the second frequency collimated light beam that the second laser (9) exports
Light beam focuses and is transmitted to detection target (5) out, translates displacement guide rail (12) and light beam is focused by second light
Device (11) focuses to the convergent point of detection target (5) and the first frequency collimated light beam passes through the described first smooth focalizer (4)
The convergent point for focusing to detection target (5) is overlapped, and excites the light beam for being detected target (5) scattering Raman signal to be transmitted through described
Optical path converter (3) and by photo-coupler (7) couple after be transmitted to the spectral analysis device (8),
Spectrum analysis is carried out to the received light beam of the above process by the spectral analysis device (8);
Wherein, the frequency difference Δ v range of the first frequency and the second frequency is 3-20cm-1。
7. Raman spectra detection process as claimed in claim 6, which is characterized in that in aforesaid way one, by the spectrum point
Analysis apparatus (8) carries out spectrum analysis to the received light beam of the above process
It obtains the first laser device (1) output beam and excites the spectral signal S of generation in detection target (5)0;
It obtains the second laser (9) output beam and excites the spectral signal S of generation in detection target (5)1,...,SN,
N is positive integer more than or equal to 1, wherein focus point of the output beam of the second laser (9) in detection target (5) with
The output beam of the first laser device (1) is when detecting the distance of focus point of target (5) is i × d, the spectral signal of acquisition
For Si, i=1,2 ..., N;
Obtain spectral signal S0,S1,...,SNSpectrum peak position and intensity value (P0j,Y0j)、(P1j,Y1j)、……(Pij,Yij),
Middle j=1,2 ..., M, M are the spectral peak sum in spectral signal;
It is calculated as follows subtractive factor C1j,C2j,...,CNj,
When N=1, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0jIf C1j≤ 1, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j,
When N=2, j={ 1 ..., M } is successively taken, seeks subtractive factor C1j=Y1j/Y0j, C2j=Y2j/Y0jIf C2j≤C1j, andMeet simultaneously, then subtractive factor solution terminates, and takes C1=C1j, C2=
C2j, and so on;
Sample signal R is calculated,
8. Raman spectra detection process as claimed in claim 6, which is characterized in that in aforesaid way two, by the spectrum point
Analysis apparatus (8) carries out spectrum analysis to the received light beam of the above process
It obtains the first laser device (1) output beam and excites the spectral signal S of generation in detection target (5)0, and obtain
Take the light beam of the second laser (9) output beam and focus point and the first laser device (1) in detection target (5)
The collected spectral signal S ' when the focus point for detecting target (5) is overlapped0;
Obtain poor spectrum signal D, D=S0-S′0, and calculate integral K, the K=∫ Ddv of poor spectrum signal D;
Boxcar function Rect is constructed,
It calculates mirror image raman spectral signal R (- v), R (- v)=ifft [fft (K)/fft (Rect)];
R (- v) mirror image is negated, acquisition filters out the Raman spectrum R (v) after fluorescence.
9. Raman spectra detection process as claimed in claim 6, which is characterized in that
The mode one further include: the first optical filter (2) is set to the first laser device (1) and the optical path converter
(3) in the optical path between, the second optical filter (6) is set between the optical path converter (3) and the photo-coupler (7)
In optical path, third optical filter (10) is set to the light between the second laser (9) and the second smooth focalizer (11)
On the road;
The mode two further include: the first optical filter (2) is set to the first laser device (1) and the optical path converter
(3) in the optical path between, the second optical filter (6) is set between the optical path converter (3) and the photo-coupler (7)
In optical path, third optical filter (10) is set to the light between the second laser (9) and the second smooth focalizer (11)
On the road.
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