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CN105628671B - A kind of device and method for sample component quantitative analysis - Google Patents

A kind of device and method for sample component quantitative analysis
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Publication number
CN105628671B
CN105628671BCN201410707332.3ACN201410707332ACN105628671BCN 105628671 BCN105628671 BCN 105628671BCN 201410707332 ACN201410707332 ACN 201410707332ACN 105628671 BCN105628671 BCN 105628671B
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light
dispersion means
raman
optical path
detection
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CN105628671A (en
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沈嘉祺
孙文剑
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Shimadzu Analytical Technology Research And Development (shanghai) Co Ltd
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Shimadzu Analytical Technology Research And Development (shanghai) Co Ltd
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Abstract

The present invention is provided to obtain the device and method of raman scattering spectra, device includes: the excitation light source for generating excitation beam;Exciting light optical path, by excitation beam guiding sample to be analysed to generate Raman scattered light;The scattering light for collecting Raman scattered light collects optical path;Detection device, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and being converted into electric signal to analyze;Connection scattering light collects one or more dispersion means of optical path and detection device, forms raman scattering spectra for importing the Raman scattered light that scattering light collection optical path is collected;At least one dispersion means is furnished with spatial light modulator, spatial light modulator selects the space segment of corresponding different detection frequency or frequency sub-band and the gradually detection of guiding detection device in the raman scattering spectra that place dispersion means are formed, wherein, some or all of raman scattering spectra is anti-Stokes spectrum.Anti-Stokes Raman spectrum can detecte for sample component quantitative analysis using the present invention.

Description

A kind of device and method for sample component quantitative analysis
Technical field
The present invention relates to the device and method for sample component quantitative analysis.
Background technique
Before the acquisition of raman scattering spectra (Raman scattering spectrum) is independent of complicated sampleReason can be used for quick, lossless sample component analysis.Have some portable Raman spectrometers, their bodies currently on the marketProduct is small, and structure is simple, and working service is convenient.Excitation wavelength used by them is mostly 532nm-1064nm, used sensingDevice is mostly as sensor linear array, such as charge-coupled device (CCD), N-type metal-oxide-semiconductor field effect t (NMOS).In near-infrared waveSection is conducive to reduce fluorescence background using longer excitation wavelength, can improve the letter of Raman scattering light detection to a certain extentMake an uproar ratio, but due to Raman scattering intensity is inversely proportional to the biquadratic of excitation wavelength, the requirement to detection unit performance used just compared withHigh (generally being realized by reducing operating temperature and extending detection cycle).On the other hand, spectrum of the wave band in 1100nm or moreDetection generally uses indium gallium arsenic (InGaAs) photodiode linear array, and the manufacturing cost of current this device exists than applicable wave band1100nm picture sensor linear array below is much higher, directly affects the production cost of complete machine.It is limited by above-mentioned factor, it is general portableThe sensitivity of formula Raman spectrometer and spectral resolution are fairly limited, and cost performance is also less high.
Photon frequency is higher than the part of photon frequency of exciting light (i.e. launch wavelength is longer than excitation wave in raman scattering spectraLong part) it is referred to as anti-Stokes spectrum (anti-Stokes spectrum), photon frequency is lower than the photon of exciting lightThe part (i.e. launch wavelength be shorter than excitation wavelength part) of frequency is referred to as stokes spectrum (Stokes spectrum),The former be from lower base electronic state molecule by after the polarization of exciting light photon immediately to some higher baseElectron state transition occurs, pole of molecule of the latter as caused by the former in higher base electronic state by exciting light photonChange effect after immediately to lower base electron state transition occur, the two spectral line relative to exciting light spectral line frequency displacement about zero point pairClaim distribution.Since the photon frequency of off-resonance fluorescence is generally below the photon frequency of exciting light, detection anti-Stokes spectrum hasHelp exclude the interference of fluorescence background.On the other hand, the molecular number of each energy level is in Bridgman distribution, anti-Stokes lineIntensity is weaker than corresponding stokes line, and the two ratio increases with frequency displacement and reduced.Due to by volume size and performanceLimitation, the design function of general portable Raman spectrometer, which does not include, obtains anti-Stokes spectrum.
The technology for being usually used in observing anti-Stokes Raman spectrum at present has coherent anti-Stokes analysis(coherentanti-Stokes Raman spectroscopy).It is respectively ν that this technology, which is by the sub- frequency of two-beam,1、ν212) light laser beam direction sample and its difference on the frequency be just equal to the Spontaneous Raman frequency displacement of sample, thus generate resonance pointSon vibration, while being ν with frequency3A certain laser beam (can be the frequency be ν1Light laser light beam) mixing, generateFrequency is ν312Anti-Stokes spectrum;Due to spectral line signal amplitude obtained and each physical quantity (including sample componentConcentration) relationship complexity, ambient noise is big, and this technology is difficult to use in general sample component quantitative analysis.
Summary of the invention
In view of the foregoing deficiencies of prior art, the present invention provide a kind of device for sample component quantitative analysis andMethod obtains high optics letter to inhibit the interference of fluorescence and bias light common in the generally use of portable Raman spectrometerIt makes an uproar and compares, while cost will not be excessively high.
To realize that above-mentioned target and other related objectives, the present invention provide a kind of dress for sample component quantitative analysisIt sets, comprising: excitation light source, for generating excitation beam;Exciting light optical path, for the excitation beam to be oriented to be analyzed consolidateState or liquid sample are to generate Raman scattered light;It scatters light and collects optical path, for collecting the Raman scattered light;Containing one or moreThe detection device of a sense channel, for receiving the Raman scattering optical signal of each detection frequency or frequency sub-band and being converted into electric signalFor analysis;Multiple dispersion means that the scattering light collects optical path and the detection device are connected, for institute based on the receivedIt states Raman scattered light and forms raman scattering spectra;At least one dispersion means in the multiple dispersion means are configured with spatial lightModulator, the spatial modulator in the raman scattering spectra that corresponding dispersion means are formed for selecting corresponding different inspectionThe space segment of measured frequency or frequency sub-band is gradually oriented to the detection device and is detected, wherein the raman scattering spectraIt is partly or entirely anti-Stokes spectrum.
Optionally, the detection device includes detector and detection circuit;The detector is photomultiplier tube or photoelectricityDiode works in linearity test mode or photon counting mode;Under linear detection pattern, the electric current of the detector outputSignal amplitude is proportional to the received luminous flux of the detector;Under photon counting mode, effective letter of the detector outputThe frequency of punching of feeling the pulse is proportional to the received luminous flux of the detector.
Optionally, the detection device further include the excitation beam modulating device and corresponding detection circuit;It is describedThe modulating device of excitation beam generates a string of modulated signals, and the excitation beam is modulated by the modulated signal, and the inspectionSlowdown monitoring circuit passes through filtering output and the consistent signal of the frequency modulating signal.
Optionally, the multiple dispersion means are for respectively forming the spectrum of different frequency range;The scattering light collects optical pathIt is additionally provided with one or more beam splitters or is equipped with one or more light guides;Collected Raman scattered light passes through described pointBeam device is assigned to each dispersion means, or is gradually oriented to each dispersion means by the light guide, withThe raman scattering spectra of different frequency range is respectively formed for each dispersion means.
Optionally, the light guide includes one of following:
(1) mobilizable micro reflector array or scanning galvanometer;By swinging the micro reflector array or the scanningThe guiding of galvanometer change emergent light;
(2) mobilizable platform;It is fixed with reflecting mirror on the platform, leading for emergent light is changed by the activity platformTo.
Optionally, the spatial light modulator includes one of following:
(1) transmitted light device;Detection device described in the light directing that the spatial light modulator transmits its back side;
(2) reflective optical device;Detection device described in light directing of the spatial light modulator by its surface reflection.
Optionally, the spatial light modulator is micro reflector array, and the micro reflector array includes: multiple micro- reflectionsMirror unit;Each micro-reflector unit include: a face micro-reflector, a pivot being hinged with the micro-reflector,Control circuit unit;Drive the micro-reflector of some micro-reflector unit around connecting by the control circuit unitThe pivot swing, to control each space segment of the raman scattering spectra from matching with the spatial light modulatorDispersion means to the detection device on-off.
Optionally, the spatial light modulator is liquid crystal light amplitude spatial modulator, the liquid crystal light amplitude spatial modulationDevice includes: liquid crystal exposure mask and polarization optical element;The liquid crystal exposure mask includes multiple space cells;Regulated power supply device, is used forThe voltage for changing each space cell for being applied to the liquid crystal exposure mask is irradiated to the liquid crystal to change from the dispersion meansThe polarization direction of the transmitted light of each space cell of exposure mask, with the use of the corresponding different inspections of polarization optical element controlEach space segment of the raman scattering spectra of measured frequency or frequency sub-band is from the dispersion means to the on-off of the detection device.
Optionally, the excitation light source is laser, the excitation beam for being less than 0.3nm for generating line width;The excitationLight optical path includes beam shaping element and imaging optical system;The beam shaping element is for swashing the laser sendingLuminous beam makees shaping;The imaging optical system by the excitation beam for transmitting and converging to the sample.
To realize that above-mentioned target and other related objectives, the present invention provide a kind of side for sample component quantitative analysisMethod, comprising: excitation light source is provided, for generating excitation beam;There is provided exciting light optical path, for by the excitation beam guiding toThe solid-state or liquid sample of analysis are to generate Raman scattered light;Scattering light is provided and collects optical path, for collecting the Raman scatteringLight;The detection device containing one or more sense channels is provided, for receiving the Raman scattered light of each detection frequency or frequency sub-bandSignal is simultaneously converted into electric signal for analysis;Multiple dispersions that the connection scattering light collects optical path and the detection device are providedDevice collects the Raman scattered light formation raman scattering spectra collected by optical path with the scattering light for importing;It is describedAt least one dispersion means in multiple dispersion means are configured with spatial light modulator, and the spatial light modulator is used in correspondenceThe raman scattering spectra that is formed of dispersion means in selection corresponding different detection frequency or frequency sub-band space segment and graduallyIt is oriented to the detection device to be detected, wherein some or all of described raman scattering spectra is anti-Stokes spectrum;InstituteIt states excitation light source and generates the excitation beam, the excitation beam is directed to the sample by the exciting light optical path, describedThus Raman scattering occurs for sample;Optical path is collected with the scattering light and collects Raman scattered light caused by the sample, and is ledTo the dispersion means;It is described by controlling this when some described dispersion means configured with the spatial modulator worksSpatial light modulator, each section for being formed by corresponding dispersion means in raman scattering spectra are gradually collected into the detectionDevice is detected, for obtaining the raman scattering spectra in the dispersion means working frequency range.
Optionally, the multiple dispersion means are for respectively forming the spectrum of different frequency range;The scattering light collects optical pathIt is additionally provided with one or more beam splitters or is equipped with one or more light guides;Collected Raman scattered light passes through described pointBeam device is assigned to each dispersion means, or is gradually oriented to each dispersion means by the light guide, withThe raman scattering spectra of different frequency range is respectively formed for each dispersion means.
As described above, the present invention provides a kind of device and method for sample component quantitative analysis, described device includes:Excitation light source, for generating excitation beam;Exciting light optical path, for the excitation beam to be oriented to solid-state or liquid to be analyzedSample is to generate Raman scattered light;It scatters light and collects optical path, for collecting the Raman scattered light;Detection containing one or more is logicalThe detection device in road, for receive it is each detection frequency or frequency sub-band Raman scattering optical signal and be converted into electric signal for pointAnalysis;Multiple dispersion means that the scattering light collects optical path and the detection device are connected, are received for importing with the scattering lightCollect the Raman scattered light collected by optical path and forms raman scattering spectra;At least one dispersion in the multiple dispersion meansDevice is configured with spatial light modulator, and the spatial light modulator is used for the raman scattering spectra formed in corresponding dispersion meansThe space segment of middle selection corresponding different detection frequency or frequency sub-band is gradually oriented to the detection device and is detected, whereinSome or all of described raman scattering spectra is anti-Stokes spectrum.
Detailed description of the invention
Fig. 1 is shown as the structural schematic diagram in one embodiment of the invention for the device of sample component quantitative analysis.
Fig. 2 is shown as the structural schematic diagram in further embodiment of this invention for the device of sample component quantitative analysis.
Fig. 3 is shown as the structural schematic diagram in further embodiment of this invention for the device of sample component quantitative analysis.
Fig. 4 is shown as the structural schematic diagram in further embodiment of this invention for the device of sample component quantitative analysis.
Fig. 5 is shown as the flow diagram in one embodiment of the invention for the method for sample component quantitative analysis.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specificationOther advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realitiesThe mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing fromVarious modifications or alterations are carried out under spirit of the invention.It should be noted that in the absence of conflict, the embodiment in the applicationAnd the feature in embodiment can be combined with each other.
As shown in Figure 1, the present invention provides the device of sample component quantitative analysis, described device includes: to generate excitation beam 2Excitation light source 1, exciting light optical path 3, sample 4, for collect from sample 4 scattering light 5 scattering light collect optical path 6, pointBeam device 7, dispersion means 1i, 1j ... and detection device 8 etc..
Specifically, the excitation light source 1 makes the excitation beam pass through exciting light optical path 3 for generating excitation beam 2It is accumulated on the sample 4 for being irradiated to and being placed on sample area, thus the sample 4, which is excited, to be scattered;It is collected with scattering lightOptical path 6, which is collected, scatters light 5 caused by the sample, and is oriented to the dispersion means 1i, 1j;In other embodiments, dispersionDevice can only have one, if the dispersion means are more than one, embodiment will can be received by beam splitter 7 as shown in Figure 1The scattering light 5 of collection is assigned to each dispersion means 1i, 1j ..., or can substitute the beam splitting by providing light guideThe collected scattering light 5 is gradually oriented to each dispersion means by device 7, for each dispersion means (1i, 1j ...) and itsThe spatial light modulator (1i', 1j' ...) matched is respectively formed the raman scattering spectra of different frequency range.
In the embodiment shown in fig. 1, as the dispersion means (1i that some is configured with spatial light modulator (1i' or 1j')Or 1j) work when, form raman scattering spectra, the spectrum portion in the spatial light modulator (1i' or 1j') configuredDivide or entirely anti-Stokes spectrum, i.e. some or all of its corresponding wavelength are shorter than the wavelength of the excitation beam.ControlThe spatial light modulator (1i' or 1j') makes the dispersion means (1i or 1j) be formed by each section in spectrum graduallyIt is collected into the detection device 8 to be detected, for obtaining the loudspeaker in dispersion means (the 1i or 1j) working frequency rangeGraceful scattering spectrum.Detection device contains one or more sense channels, for receiving the Raman scattering of each detection frequency or frequency sub-bandOptical signal is simultaneously converted into electric signal for analysis.
It should be noted that although each dispersion means (1i, 1j) are each equipped with spatial light tune in the embodiment shown in fig. 1Device (1i', 1j') processed, but in other embodiments, it can be with only a fraction dispersion means configuration space optical modulator, remaining colorIn bulk set does not configure, and uses other way to detect spectrum, such as directly with common in general portable Raman spectrometer at presentPicture sensor linear array detect raman scattering spectra.
In one embodiment, the excitation light source 1 is laser, the exciting light for being less than 0.3nm for generating line widthBeam;The exciting light optical path includes beam shaping element and imaging optical system, and the beam shaping element is used to swash to describedThe excitation beam that light device issues makees shaping;The imaging optical system by the excitation beam for transmitting and converging to the sampleOn product 4.
In one embodiment, the light guide for switching be oriented to dispersion means can include but is not limited to:(1) swingable micro reflector array or scanning galvanometer are changed by swinging the micro reflector array or the scanning galvanometerThe guiding of emergent light;(2) rotatable platform is fixed with reflecting mirror on the platform, passes through the rotation platform and changes emergent lightGuiding.It should be noted that above-mentioned several ways are only for example, it in other embodiments also can be by other manners (such asTranslation) it is realized.
In one embodiment, the working frequency range of the dispersion means (1i, 1j) configured with the spatial light modulator, untilRare a part is higher than the photon frequency of the excitation beam 2, can also cover the photon frequency or lower of the excitation beam 2Frequency range, i.e., spectrum detected include anti-Stokes line, can also simultaneously include stokes line and excitation beamSpectral line using multiple dispersion means detect Raman spectrum, be conducive to the performance for optimizing the dispersion means in each frequency range.
In one embodiment, the spatial light modulator can be transmission-type, and be oriented to the detection device 8 at this time is certainlyThe light of the spatial light modulator back side transmission;It is also possible to reflective, be oriented to the detection device 8 at this time is from the skyBetween light modulator surface reflect light.
Further, the detection device 8 includes detector and detection circuit, and the detector is photomultiplier tube or lightElectric diode works in linearity test mode or photon counting mode;Under linear detection pattern, the electricity of the detector outputStream signal amplitude is proportional to the received luminous flux of the detector;Under photon counting mode, the detector is exported effectiveThe frequency of signal pulse is proportional to the received luminous flux of the detector;Preferably, the detection device further includes the excitationThe modulating device of light beam and corresponding detection circuit, the modulating device of the excitation beam generates a string of modulated signals, described to swashThe beam that shines is modulated with the modulated signal, while the detection circuit is consistent with the frequency modulating signal by filtering outputSignal.
Multiple specific embodiments are given below to illustrate the working principle of the device of the invention:
Embodiment 1
Fig. 2 shows the embodiments 1 of apparatus of the present invention, comprising: laser 21, collimating and correcting optical element 23, for puttingSet sample area, the beam splitter 25, optically focused/collimation lens 26, band resistance optical filter 29, scanning galvanometer 27, parabolic of sample to be analysed 24Face reflecting mirror (2i ", 2j "), concave grating (2i, 2j), is used to select detected frequency or frequency sub-band slit (2i " ', 2j " ')Micro reflector array (2i', 2j'), collecting optical system 281 and detector 282.
Micro reflector array (2i', 2j') is the spatial light modulator for selecting detected frequency or frequency sub-band, theyEach space cell include a face micro-reflector, one be hinged with the micro-reflector pivot, control circuit unit,The micro-reflector of some space cell can be driven to swing around the connected pivot by the control circuit unit,When the micro-reflector swings to a direction, it is irradiated to reflected light caused by the light of the micro-reflector and is directed toCollecting optical system 281, when the micro-reflector swings to other direction, the light for being irradiated to the micro-reflector is producedRaw reflected light cannot be received by collecting optical system 281, and thus control is transferred to each spatial portion of the spectrum of detector 282The on-off divided.
Detector 282 is photomultiplier tube or photodiode, works in linearity test mode or photon counting mode, InUnder linearity test mode, the current signal amplitude that detector 282 exports is proportional to the received luminous flux of institute, in photon counting modeUnder, the frequency for the useful signal pulse that detector 282 exports is proportional to the received luminous flux of institute.
The course of work of the device is as follows: laser 21 generates the excitation beam that line width is less than 0.3nm, the excitation beamThe relatively uniform collimated light beam of wavefront Energy distribution is formed by collimating and correcting optical element 23, then passes through 25 part of beam splitter90 ° are turned to, then is converged on sample 24 through optically focused/collimation lens 26, thus sample 24 scatters.The part of sample 24 is backwardCollimated light beam is collected and formed to scattering light by optically focused/collimation lens 26, continues to advance along former direction by 25 part of beam splitter, connectBy band resistance optical filter 29, ingredient of the medium wavelength near excitation wavelength significantly filtered out, and in the loudspeaker of required analysisIngredient on graceful scattering wave band is retained to the greatest extent, for reducing interference of the stray light to spectrum analysis.Thereafter, it scattersLight light beam is accumulated some dispersion means after scanning galvanometer 27 and parabolic mirror (being 2i " in Fig. 2) two secondary reflectionsEntrance slit (being 2i " ' in Fig. 2).Each dispersion means are by one entrance slit (2i " ' or 2j " '), a concave grating(2i or 2j), micro reflector array (2i' or 2j') composition.The effect of concave grating is that receive the entrance from side narrowThe light beam of seam, and band is formed on the micro reflector array of the other side by diffraction.By controlling micro reflector arrayEach space segment of band is gradually oriented to collecting optical system 281 by (2i' or 2j').Collecting optical system 281 is collectedThe signal light transmitted from micro reflector array (2i' or 2j'), converges on the receiving plane of detector 282.Each dispersion meansService band is different, i.e., the Raman scattering optical frequencies corresponding to them is different, but may exist overlapped portion, is swept by activityGalvanometer 27 is retouched, scattering light is gradually transferred to each dispersion means, to obtain in wider frequency section by the guiding of switching scattering light light beamOn high-resolution Raman spectrum, while eliminating resolution ratio of the spatial resolution to acquired spectrum of micro reflector array usedLimitation.
Typical design is to be used to analyze stokes spectrum by one of dispersion means, another for analyze it is anti-thisLentor spectrum.Compared with current general use obtains the device of raman scattering spectra as sensor linear array, single inspection is usedThe spectrum that survey device detects some frequency range is conducive to obtain higher sensitivity with lower cost, is conducive to obtain anti-StokesSpectrum, to facilitate the interference of exclusion fluorescence background.
Embodiment 2
Fig. 3 shows the embodiment of the present invention 2, comprising: laser 31, collimating and correcting optical element 33, for place toThe sample area of analysis sample 34, beam splitter 35, optically focused/collimation lens 36, band resistance optical filter 39, scanning galvanometer 37, paraboloid are anti-Penetrate mirror (3i ", 3j "), slit (3i " ', 3j " '), plane transmission grating (3i, 3j), imaging len (3i " " a, 3i " " b, 3j " " a,3j " " b), linear polarizer (3i'a, 3i'c, 3j'a, 3j'c), the transmission liquid crystal light for selecting detected frequency or frequency sub-bandAmplitude spatial modulator (3i'b, 3j'b), collecting optical system 381 and detector 382.
The difference of the present embodiment and embodiment 1 shown in Fig. 2 is used dispersion means and that is matched is used to selectThe composition and working method of detected frequency or the spatial light modulator of frequency sub-band.Specifically come by taking state as shown in Figure 3 as an exampleSay, the dispersion means gated by slit 3i " ', imaging len (3i " " a, 3i " " b) and plane transmission grating 3i form, mostThe off-axis astigmatism that dispersion means in embodiment 1 are eliminated in big degree, help to obtain higher spectral resolution.Meanwhile insteadThe formula spatial light modulator of penetrating is no longer desirable for the detected frequency of selection or frequency sub-band, uses linear polarizer 3i'a, 3i'c, 3j'a instead,3j'c cooperates transmission liquid crystal light amplitude spatial light modulator 3i'b, 3j'b, and control is oriented to each of the spectrum of detection device 382Partial on-off.By taking state as shown in Figure 3 as an example specifically, in the dispersion means gated, pass through linear polarizer 3i'A significantly filters out the part that polarization direction in incident collimated light beams is parallel to paper direction, and the polarization direction of outgoing beam is basicOn perpendicular to paper direction, through transmission grating 3i diffraction and lens 3i " " b forms band, polarization direction is basically unchanged, InEach space segment of transmission-type transmission liquid crystal light amplitude spatial modulator 3i'b control transmitted light is used under the premise of thisPolarization direction, when selection detects some frequency sub-band, the transmitted light of the space cell of the corresponding 3i'b of spectrum frequency sub-band of gating is inclinedVibration direction remains perpendicular to paper, is substantially able to retain by linear polarizer 3i'c and be received by detection device 382, simultaneouslyThe transmission light polarization direction of remaining space cell of 3i'b is parallel to paper, by linear polarizer 3i'c be substantially filtered out withoutIt can be received by detection device 382.
Embodiment 3
Fig. 4 shows the embodiment of the present invention 3, comprising: laser 41, collimating and correcting optical element 43, for place toAnalyze sample area, the beam splitter 45, optically focused/collimation lens 46, band resistance optical filter 49, beam splitter 47, parabolic reflector of sample 44Mirror (4i ", 4j ", 4ib, 4ic, 4jb, 4jc), slit (4i " ', 4j " '), plane reflection grating (4ia, 4ja), for selectingThe frequency of the raman scattering spectra of detection or micro reflector array (4i', 4j'), collecting optical system 481 and the spy of frequency sub-bandSurvey device 482.
The difference of the present embodiment and embodiment 1 shown in Fig. 2 is the composition and working method of used dispersion means.Dispersion means are by entrance slit 4i " ', parabolic mirror 4ib, 4ic, plane reflection grating 4ia, micro reflector array 4i' groupAt dispersion means are by entrance slit 4j " ', parabolic mirror 4jb, 4jc, plane reflection grating 4ja, micro reflector array 4j'Composition.Collected Raman scattered light is divided into two parts by beam splitter 47, and a part continues to advance along former direction, and thrown object face is anti-It penetrates mirror 4i " to converge on the entrance slit 4i " ' of dispersion means, another part changes direction through beam splitter reflection, and thrown object face is anti-Mirror 4j " is penetrated to converge on the entrance slit 4j " ' of dispersion means.The effect of parabolic mirror 4ib, 4ic are will be narrow from entranceThe light beam of the linear light source of seam becomes collimated light beam, and the effect of plane reflection grating is to make incident collimated light beams diffraction, through paraboloidReflecting mirror 4ic, 4jc form band on micro reflector array (4i', 4j').
As shown in figure 5, a kind of method for sample component quantitative analysis can also be provided in the present invention in conjunction with above-mentioned apparatus,Include:
Step S1: excitation light source is provided, for generating excitation beam;
Step S2: provide exciting light optical path, for by the excitation beam be oriented to solid-state or liquid sample to be analyzed withGenerate Raman scattered light;
Step S3: scattering light is provided and collects optical path, for collecting the Raman scattered light;
Step S4: the detection device containing one or more sense channels is provided, for receiving each detection frequency or frequency sub-bandRaman scattering optical signal and be converted into electric signal for analysis;
Step S5: multiple dispersion means that the connection scattering light collects optical path and the detection device are provided, for leadingEnter and collects the Raman scattered light formation raman scattering spectra collected by optical path with the scattering light;The multiple dispersion meansIn at least one dispersion means be configured with spatial light modulator, the spatial light modulator be used in corresponding dispersion means shapeAt raman scattering spectra in selection corresponding different detection frequency or frequency sub-band space segment and be gradually oriented to the detectionDevice is detected, wherein some or all of described raman scattering spectra is anti-Stokes spectrum.
Step S6: the excitation light source generates the excitation beam, and the excitation beam passes through the exciting light optical path quiltIt is oriented to the sample, thus Raman scattering occurs for the sample;
Step S7: optical path is collected with the scattering light and collects Raman scattered light caused by the sample, and described in guidingDispersion means;
Step S8: described by controlling this when some described dispersion means configured with the spatial modulator worksSpatial light modulator, each section for being formed by corresponding dispersion means in raman scattering spectra are gradually collected into the detectionDevice is detected, for obtaining the raman scattering spectra in the dispersion means working frequency range.
In conclusion the present invention provides a kind of device and method for sample component quantitative analysis, described device includes:Excitation light source, for generating excitation beam;Exciting light optical path, for the excitation beam to be oriented to solid-state or liquid to be analyzedSample is to generate Raman scattered light;It scatters light and collects optical path, for collecting the Raman scattered light;Detection device, for receivingThe Raman scattering optical signal of each detection frequency or frequency sub-band is simultaneously converted into electric signal for analysis;It connects the scattering light and collects lightMultiple dispersion means on road and the detection device are dissipated for importing the Raman collected by scattering light collection optical pathIt penetrates light and forms raman scattering spectra;At least one dispersion means in the multiple dispersion means are configured with spatial light modulator,The spatial light modulator in the raman scattering spectra that corresponding dispersion means are formed for selecting corresponding different detection frequencyThe space segment of rate or frequency sub-band is gradually oriented to the detection device and is detected, wherein the part of the raman scattering spectraOr all anti-Stokes spectrum;Anti-Stokes Raman spectrum can detecte using the device of the invention and method, be used forSample component quantitative analysis.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripeThe personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.CauseThis, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such asAt all equivalent modifications or change, should be covered by the claims of the present invention.

Claims (9)

Multiple dispersion means that the scattering light collects optical path and the detection device are connected, are received for importing with the scattering lightCollect the Raman scattered light collected by optical path and forms raman scattering spectra;At least one dispersion in the multiple dispersion meansDevice is configured with spatial light modulator, and the spatial light modulator is used for the raman scattering spectra formed in corresponding dispersion meansMiddle selection corresponds to the space segment of different detection frequency or frequency sub-band and is gradually oriented to the detection device and detected,In, some or all of described raman scattering spectra is anti-Stokes spectrum;The multiple dispersion means, are for respectively formingThe spectrum of different frequency range;The scattering light collects optical path and is additionally provided with one or more beam splitters or is equipped with one or more light guidesTo device;Collected Raman scattered light is assigned by the beam splitter to each dispersion means, or passes through the light guideEach dispersion means are gradually oriented to device, so that each dispersion means are respectively formed the Raman scattered light of different frequency rangeSpectrum, anti-Stokes spectrum therein is for carrying out sample component quantitative analysis.
7. being used for the device of sample component quantitative analysis as claimed in claim 5, the spatial light modulator is liquid crystal light vibrationWidth spatial modulator, the liquid crystal light amplitude spatial modulator include: liquid crystal exposure mask and polarization optical element;The liquid crystal exposure maskIncluding multiple space cells;Regulated power supply device, for changing the voltage for each space cell for being applied to the liquid crystal exposure maskCome change each space cell that the liquid crystal exposure mask is irradiated to from the dispersion means transmitted light polarization direction, with cooperationEach space segment of the raman scattering spectra of corresponding different detection frequencies or frequency sub-band is controlled using the polarization optical elementFrom the dispersion means to the on-off of the detection device.
Multiple dispersion means that the connection scattering light collects optical path and the detection device are provided, for importing the scatteringLight collects the Raman scattered light collected by optical path and forms raman scattering spectra;At least one of the multiple dispersion meansDispersion means are configured with spatial light modulator, and the spatial light modulator is used for the Raman scattering formed in corresponding dispersion meansSelection corresponds to the space segment of different detection frequency or frequency sub-band and is gradually oriented to the detection device and detected in spectrum,Wherein, some or all of described raman scattering spectra is anti-Stokes spectrum;The multiple dispersion means, are respectively used to shapeAt the spectrum of different frequency range;The scattering light collects optical path and is additionally provided with one or more beam splitters or is equipped with one or more lightGuider;Collected Raman scattered light is assigned by the beam splitter to each dispersion means, or passes through the lightGuider is gradually oriented to each dispersion means, so that each dispersion means are respectively formed the Raman scattering of different frequency rangeSpectrum;
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