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 Download PDFInfo
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- CN105628671B CN105628671B CN201410707332.3A CN201410707332A CN105628671B CN 105628671 B CN105628671 B CN 105628671B CN 201410707332 A CN201410707332 A CN 201410707332A CN 105628671 B CN105628671 B CN 105628671B
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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
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 sample
Reason can be used for quick, lossless sample component analysis.Have some portable Raman spectrometers, their bodies currently on the market
Product is small, and structure is simple, and working service is convenient.Excitation wavelength used by them is mostly 532nm-1064nm, used sensing
Device is mostly as sensor linear array, such as charge-coupled device (CCD), N-type metal-oxide-semiconductor field effect t (NMOS).In near-infrared wave
Section is conducive to reduce fluorescence background using longer excitation wavelength, can improve the letter of Raman scattering light detection to a certain extent
Make 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 with
High (generally being realized by reducing operating temperature and extending detection cycle).On the other hand, spectrum of the wave band in 1100nm or more
Detection generally uses indium gallium arsenic (InGaAs) photodiode linear array, and the manufacturing cost of current this device exists than applicable wave band
1100nm 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 portable
The 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 spectra
Long part) it is referred to as anti-Stokes spectrum (anti-Stokes spectrum), photon frequency is lower than the photon of exciting light
The 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 base
Electron state transition occurs, pole of molecule of the latter as caused by the former in higher base electronic state by exciting light photon
Change 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 pair
Claim distribution.Since the photon frequency of off-resonance fluorescence is generally below the photon frequency of exciting light, detection anti-Stokes spectrum has
Help exclude the interference of fluorescence background.On the other hand, the molecular number of each energy level is in Bridgman distribution, anti-Stokes line
Intensity is weaker than corresponding stokes line, and the two ratio increases with frequency displacement and reduced.Due to by volume size and performance
Limitation, 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、ν2
(ν1>ν2) 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 point
Son vibration, while being ν with frequency3A certain laser beam (can be the frequency be ν1Light laser light beam) mixing, generate
Frequency is ν3+ν1-ν2Anti-Stokes spectrum；Due to spectral line signal amplitude obtained and each physical quantity (including sample component
Concentration) 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 and
Method obtains high optics letter to inhibit the interference of fluorescence and bias light common in the generally use of portable Raman spectrometer
It 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 analysis
It sets, comprising: excitation light source, for generating excitation beam；Exciting light optical path, for the excitation beam to be oriented to be analyzed consolidate
State 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 more
The 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 signal
For analysis；Multiple dispersion means that the scattering light collects optical path and the detection device are connected, for institute based on the received
It states Raman scattered light and forms raman scattering spectra；At least one dispersion means in the multiple dispersion means are configured with spatial light
Modulator, the spatial modulator in the raman scattering spectra that corresponding dispersion means are formed for selecting corresponding different inspection
The space segment of measured frequency or frequency sub-band is gradually oriented to the detection device and is detected, wherein the raman scattering spectra
It is partly or entirely anti-Stokes spectrum.
Optionally, the detection device includes detector and detection circuit；The detector is photomultiplier tube or photoelectricity
Diode works in linearity test mode or photon counting mode；Under linear detection pattern, the electric current of the detector output
Signal amplitude is proportional to the received luminous flux of the detector；Under photon counting mode, effective letter of the detector output
The 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 described
The modulating device of excitation beam generates a string of modulated signals, and the excitation beam is modulated by the modulated signal, and the inspection
Slowdown 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 path
It 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 point
Beam device is assigned to each dispersion means, or is gradually oriented to each dispersion means by the light guide, with
The 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 scanning
The 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 platform
To.
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- reflections
Mirror 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 unit
The pivot swing, to control each space segment of the raman scattering spectra from matching with the spatial light modulator
Dispersion 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 modulation
Device includes: liquid crystal exposure mask and polarization optical element；The liquid crystal exposure mask includes multiple space cells；Regulated power supply device, is used for
The 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 means
The 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 control
Each 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 excitation
Light optical path includes beam shaping element and imaging optical system；The beam shaping element is for swashing the laser sending
Luminous 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 analysis
Method, comprising: excitation light source is provided, for generating excitation beam；There is provided exciting light optical path, for by the excitation beam guiding to
The 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 scattering
Light；The detection device containing one or more sense channels is provided, for receiving the Raman scattered light of each detection frequency or frequency sub-band
Signal is simultaneously converted into electric signal for analysis；Multiple dispersions that the connection scattering light collects optical path and the detection device are provided
Device collects the Raman scattered light formation raman scattering spectra collected by optical path with the scattering light for importing；It is described
At least one dispersion means in multiple dispersion means are configured with spatial light modulator, and the spatial light modulator is used in correspondence
The raman scattering spectra that is formed of dispersion means in selection corresponding different detection frequency or frequency sub-band space segment and gradually
It is oriented to the detection device to be detected, wherein some or all of described raman scattering spectra is anti-Stokes spectrum；Institute
It states excitation light source and generates the excitation beam, the excitation beam is directed to the sample by the exciting light optical path, described
Thus Raman scattering occurs for sample；Optical path is collected with the scattering light and collects Raman scattered light caused by the sample, and is led
To the dispersion means；It is described by controlling this when some described dispersion means configured with the spatial modulator works
Spatial light modulator, each section for being formed by corresponding dispersion means in raman scattering spectra are gradually collected into the detection
Device 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 path
It 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 point
Beam device is assigned to each dispersion means, or is gradually oriented to each dispersion means by the light guide, with
The 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 analyzed
Sample 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 logical
The 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 point
Analysis；Multiple dispersion means that the scattering light collects optical path and the detection device are connected, are received for importing with the scattering light
Collect the Raman scattered light collected by optical path and forms raman scattering spectra；At least one dispersion in the multiple dispersion means
Device is configured with spatial light modulator, and the spatial light modulator is used for the raman scattering spectra formed in corresponding dispersion means
The space segment of middle selection corresponding different detection frequency or frequency sub-band is gradually oriented to the detection device and is detected, wherein
Some 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 specification
Other 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 realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various 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 application
And 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 2
Excitation light source 1, exciting light optical path 3, sample 4, for collect from sample 4 scattering light 5 scattering light collect optical path 6, point
Beam 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 2
It 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 light
Optical path 6, which is collected, scatters light 5 caused by the sample, and is oriented to the dispersion means 1i, 1j；In other embodiments, dispersion
Device 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 1
The scattering light 5 of collection is assigned to each dispersion means 1i, 1j ..., or can substitute the beam splitting by providing light guide
The collected scattering light 5 is gradually oriented to each dispersion means by device 7, for each dispersion means (1i, 1j ...) and its
The 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') configured
Divide or entirely anti-Stokes spectrum, i.e. some or all of its corresponding wavelength are shorter than the wavelength of the excitation beam.Control
The spatial light modulator (1i' or 1j') makes the dispersion means (1i or 1j) be formed by each section in spectrum gradually
It is collected into the detection device 8 to be detected, for obtaining the loudspeaker in dispersion means (the 1i or 1j) working frequency range
Graceful scattering spectrum.Detection device contains one or more sense channels, for receiving the Raman scattering of each detection frequency or frequency sub-band
Optical 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. 1
Device (1i', 1j') processed, but in other embodiments, it can be with only a fraction dispersion means configuration space optical modulator, remaining color
In bulk set does not configure, and uses other way to detect spectrum, such as directly with common in general portable Raman spectrometer at present
Picture 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 width
Beam；The exciting light optical path includes beam shaping element and imaging optical system, and the beam shaping element is used to swash to described
The excitation beam that light device issues makees shaping；The imaging optical system by the excitation beam for transmitting and converging to the sample
On 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 galvanometer
The guiding of emergent light；(2) rotatable platform is fixed with reflecting mirror on the platform, passes through the rotation platform and changes emergent light
Guiding.It should be noted that above-mentioned several ways are only for example, it in other embodiments also can be by other manners (such as
Translation) it is realized.
In one embodiment, the working frequency range of the dispersion means (1i, 1j) configured with the spatial light modulator, until
Rare 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 2
Frequency range, i.e., spectrum detected include anti-Stokes line, can also simultaneously include stokes line and excitation beam
Spectral 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 certainly
The 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 sky
Between light modulator surface reflect light.
Further, the detection device 8 includes detector and detection circuit, and the detector is photomultiplier tube or light
Electric diode works in linearity test mode or photon counting mode；Under linear detection pattern, the electricity of the detector output
Stream signal amplitude is proportional to the received luminous flux of the detector；Under photon counting mode, the detector is exported effective
The frequency of signal pulse is proportional to the received luminous flux of the detector；Preferably, the detection device further includes the excitation
The modulating device of light beam and corresponding detection circuit, the modulating device of the excitation beam generates a string of modulated signals, described to swash
The beam that shines is modulated with the modulated signal, while the detection circuit is consistent with the frequency modulating signal by filtering output
Signal.
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 putting
Set 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 24
Face 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, they
Each 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 to
Collecting optical system 281, when the micro-reflector swings to other direction, the light for being irradiated to the micro-reflector is produced
Raw reflected light cannot be received by collecting optical system 281, and thus control is transferred to each spatial portion of the spectrum of detector 282
The on-off divided.
Detector 282 is photomultiplier tube or photodiode, works in linearity test mode or photon counting mode, In
Under linearity test mode, the current signal amplitude that detector 282 exports is proportional to the received luminous flux of institute, in photon counting mode
Under, 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 beam
The 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 splitter
90 ° 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 backward
Collimated 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, connect
By band resistance optical filter 29, ingredient of the medium wavelength near excitation wavelength significantly filtered out, and in the loudspeaker of required analysis
Ingredient on graceful scattering wave band is retained to the greatest extent, for reducing interference of the stray light to spectrum analysis.Thereafter, it scatters
Light light beam is accumulated some dispersion means after scanning galvanometer 27 and parabolic mirror (being 2i " in Fig. 2) two secondary reflections
Entrance 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 narrow
The light beam of seam, and band is formed on the micro reflector array of the other side by diffraction.By controlling micro reflector array
Each space segment of band is gradually oriented to collecting optical system 281 by (2i' or 2j').Collecting optical system 281 is collected
The signal light transmitted from micro reflector array (2i' or 2j'), converges on the receiving plane of detector 282.Each dispersion means
Service band is different, i.e., the Raman scattering optical frequencies corresponding to them is different, but may exist overlapped portion, is swept by activity
Galvanometer 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 beam
On high-resolution Raman spectrum, while eliminating resolution ratio of the spatial resolution to acquired spectrum of micro reflector array used
Limitation.
Typical design is to be used to analyze stokes spectrum by one of dispersion means, another for analyze it is anti-this
Lentor spectrum.Compared with current general use obtains the device of raman scattering spectra as sensor linear array, single inspection is used
The spectrum that survey device detects some frequency range is conducive to obtain higher sensitivity with lower cost, is conducive to obtain anti-Stokes
Spectrum, 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 to
The 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-band
Amplitude 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 select
The 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 example
Say, the dispersion means gated by slit 3i " ', imaging len (3i " " a, 3i " " b) and plane transmission grating 3i form, most
The off-axis astigmatism that dispersion means in embodiment 1 are eliminated in big degree, help to obtain higher spectral resolution.Meanwhile instead
The 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 382
Partial 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 basic
On perpendicular to paper direction, through transmission grating 3i diffraction and lens 3i " " b forms band, polarization direction is basically unchanged, In
Each space segment of transmission-type transmission liquid crystal light amplitude spatial modulator 3i'b control transmitted light is used under the premise of this
Polarization 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 inclined
Vibration direction remains perpendicular to paper, is substantially able to retain by linear polarizer 3i'c and be received by detection device 382, simultaneously
The transmission light polarization direction of remaining space cell of 3i'b is parallel to paper, by linear polarizer 3i'c be substantially filtered out without
It 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 to
Analyze sample area, the beam splitter 45, optically focused/collimation lens 46, band resistance optical filter 49, beam splitter 47, parabolic reflector of sample 44
Mirror (4i ", 4j ", 4ib, 4ic, 4jb, 4jc), slit (4i " ', 4j " '), plane reflection grating (4ia, 4ja), for selecting
The frequency of the raman scattering spectra of detection or micro reflector array (4i', 4j'), collecting optical system 481 and the spy of frequency sub-band
Survey 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' group
At 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 entrance
The 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 paraboloid
Reflecting 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 with
Generate 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-band
Raman 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 leading
Enter and collects the Raman scattered light formation raman scattering spectra collected by optical path with the scattering light；The multiple dispersion means
In at least one dispersion means be configured with spatial light modulator, the spatial light modulator be used in corresponding dispersion means shape
At raman scattering spectra in selection corresponding different detection frequency or frequency sub-band space segment and be gradually oriented to the detection
Device 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 quilt
It 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 guiding
Dispersion means；
Step S8: described by controlling this when some described dispersion means configured with the spatial modulator works
Spatial light modulator, each section for being formed by corresponding dispersion means in raman scattering spectra are gradually collected into the detection
Device 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 analyzed
Sample is to generate Raman scattered light；It scatters light and collects optical path, for collecting the Raman scattered light；Detection device, for receiving
The 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 light
Multiple dispersion means on road and the detection device are dissipated for importing the Raman collected by scattering light collection optical path
It 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 frequency
The 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 spectra
Or all anti-Stokes spectrum；Anti-Stokes Raman spectrum can detecte using the device of the invention and method, be used for
Sample 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 ripe
The 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.Cause
This, 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 as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (9)
1. a kind of device for sample component quantitative analysis characterized by comprising
Excitation light source, for generating excitation beam；
Exciting light optical path, for the excitation beam to be oriented to solid-state or liquid sample to be analyzed to generate Raman scattered light；
It scatters light and collects optical path, for collecting the Raman scattered light；
Detection device containing one or more sense channels, for receiving the Raman scattering optical signal of each detection frequency or frequency sub-band
And electric signal is converted into for analysis；
Multiple dispersion means that the scattering light collects optical path and the detection device are connected, are received for importing with the scattering light
Collect the Raman scattered light collected by optical path and forms raman scattering spectra；At least one dispersion in the multiple dispersion means
Device is configured with spatial light modulator, and the spatial light modulator is used for the raman scattering spectra formed in corresponding dispersion means
Middle 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 forming
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 light guides
To device；Collected Raman scattered light is assigned by the beam splitter to each dispersion means, or passes through the light guide
Each dispersion means are gradually oriented to device, so that each dispersion means are respectively formed the Raman scattered light of different frequency range
Spectrum, anti-Stokes spectrum therein is for carrying out sample component quantitative analysis.
2. being used for the device of sample component quantitative analysis as described in claim 1, which is characterized in that the detection device includes
Detector and detection circuit；The detector is photomultiplier tube or photodiode, works in linearity test mode or photon
Count mode；Under linear detection pattern, it is received that the current signal amplitude of the detector output is proportional to the detector
Luminous flux；Under photon counting mode, the frequency of the useful signal pulse of the detector output is proportional to the detector and connects
The luminous flux of receipts.
3. being used for the device of sample component quantitative analysis as claimed in claim 2, which is characterized in that further include the exciting light
The modulating device of the modulating device of beam and corresponding detection circuit, the excitation beam generates a string of modulated signals, the excitation
Light beam is modulated by the modulated signal, and the detection circuit passes through filtering output and the consistent letter of the frequency modulating signal
Number.
4. being used for the device of sample component quantitative analysis as described in claim 1, which is characterized in that the light guide includes
One of below:
(1) swingable micro reflector array or scanning galvanometer；By swinging the micro reflector array or the scanning galvanometer
Change the guiding of emergent light；
(2) mobilizable platform；It is fixed with reflecting mirror on the platform, changes the guiding of emergent light by the activity platform.
5. being used for the device of sample component quantitative analysis as described in claim 1, which is characterized in that the spatial light modulator
Including 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.
6. being used for the device of sample component quantitative analysis as claimed in claim 5, which is characterized in that the spatial light modulator
It is micro reflector array, the micro reflector array includes: multiple micro-reflector units；
Each micro-reflector unit includes: a face micro-reflector, a pivot being hinged with the micro-reflector, controls
Circuit unit；Drive the micro-reflector of some micro-reflector unit around connected institute by the control circuit unit
Pivot swing is stated, to control each space segment of the raman scattering spectra from the dispersion to match with the spatial light modulator
Device to the detection device on-off.
7. being used for the device of sample component quantitative analysis as claimed in claim 5, the spatial light modulator is liquid crystal light vibration
Width spatial modulator, the liquid crystal light amplitude spatial modulator include: liquid crystal exposure mask and polarization optical element；The liquid crystal exposure mask
Including multiple space cells；Regulated power supply device, for changing the voltage for each space cell for being applied to the liquid crystal exposure mask
Come change each space cell that the liquid crystal exposure mask is irradiated to from the dispersion means transmitted light polarization direction, with cooperation
Each space segment of the raman scattering spectra of corresponding different detection frequencies or frequency sub-band is controlled using the polarization optical element
From the dispersion means to the on-off of the detection device.
8. being used for the device of sample component quantitative analysis as described in claim 1, which is characterized in that the excitation light source is sharp
Light device, the excitation beam for being less than 0.3nm for generating line width；The exciting light optical path includes beam shaping element and imaging
Optical system, the excitation beam that the beam shaping element is used to issue the laser make shaping；The image optics system
System by the excitation beam for transmitting and converging to the sample.
9. a kind of method for sample component quantitative analysis characterized by comprising
Excitation light source is provided, for generating excitation beam；
Exciting light optical path is provided, for the excitation beam to be oriented to solid-state or liquid sample to be analyzed to generate Raman scattering
Light；
Scattering light is provided and collects optical path, for collecting the Raman scattered light；
The detection device containing one or more sense channels is provided, for receiving the Raman scattered light of each detection frequency or frequency sub-band
Signal is simultaneously converted into electric signal for analysis；
Multiple dispersion means that the connection scattering light collects optical path and the detection device are provided, for importing the scattering
Light collects the Raman scattered light collected by optical path and forms raman scattering spectra；At least one of the multiple dispersion means
Dispersion means are configured with spatial light modulator, and the spatial light modulator is used for the Raman scattering formed in corresponding dispersion means
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 spectrum,
Wherein, some or all of described raman scattering spectra is anti-Stokes spectrum；The multiple dispersion means, are respectively used to shape
At 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 light
Guider；Collected Raman scattered light is assigned by the beam splitter to each dispersion means, or passes through the light
Guider is gradually oriented to each dispersion means, so that each dispersion means are respectively formed the Raman scattering of different frequency range
Spectrum；
The excitation light source generates the excitation beam, and the excitation beam is directed to the sample by the exciting light optical path
Thus Raman scattering occurs for product, the sample；
Optical path is collected with the scattering light and collects Raman scattered light caused by the sample, and is oriented to the dispersion means；
When some described dispersion means configured with the spatial modulator works, by controlling the space light modulation
Device, each section for being formed by corresponding dispersion means in raman scattering spectra are gradually collected into the detection device and are examined
It surveys, for obtaining the raman scattering spectra in the dispersion means working frequency range, anti-Stokes spectrum therein is used for
Carry out sample component quantitative analysis.
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| CN201410707332.3A CN105628671B (en) | 2014-11-27 | 2014-11-27 | A kind of device and method for sample component quantitative analysis |
| PCT/CN2015/096451 WO2016082804A1 (en) | 2014-11-27 | 2015-12-04 | Device and method for obtaining raman scattering spectrum |
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| CN109557070B (en) * | 2018-10-27 | 2021-03-26 | 西安电子科技大学 | Raman imaging system based on space coded light |
| US11441948B2 (en) * | 2019-03-25 | 2022-09-13 | Mks Technology, Inc. | Multi-dispersive spectrometer |
| CN111272732A (en) * | 2020-03-03 | 2020-06-12 | 长春长光辰英生物科学仪器有限公司 | Raman spectrometer and Raman spectrum splicing method |
| CN113203727B (en) * | 2021-05-12 | 2023-04-28 | 华中科技大学 | Spectrum measuring device and method |
| CN113466179A (en) * | 2021-06-22 | 2021-10-01 | 杭州谱析光晶半导体科技有限公司 | Optical detection system and method |
| CN113983632A (en) * | 2021-11-16 | 2022-01-28 | 武汉工程大学 | Combined air conditioning unit purifying and sterilizing device and method |
| CN114152570A (en) * | 2021-11-26 | 2022-03-08 | 江苏师范大学 | Tunable spectral filtering device, use method and Raman spectrometer |
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