CN105628671A - Apparatus and method for obtaining Raman scattering spectrum - Google Patents
Apparatus and method for obtaining Raman scattering spectrum Download PDFInfo
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- CN105628671A CN105628671A CN201410707332.3A CN201410707332A CN105628671A CN 105628671 A CN105628671 A CN 105628671A CN 201410707332 A CN201410707332 A CN 201410707332A CN 105628671 A CN105628671 A CN 105628671A
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Abstract
The invention provides an apparatus and a method for obtaining a Raman scattering spectrum. The apparatus comprises an excitation light source for generating an excitation light beam; an excitation light path for guiding the excitation light beam to a sample to be analyzed in order to generate Raman scattered light; a scattered light collecting path for collecting the Raman scattered light; a detection device for receiving a Raman scattered light signal corresponding to all detection frequencies or frequency sub-bands and converting the signal into an electric signal for analysis; and one or more chromatic dispersion devices connected with the scattered light collecting path and the detection device and used for importing the Raman scattered light collected by the scattered light collecting path to form a Raman scattering spectrum, wherein at least one chromatic dispersion device is provided with a spatial light modulator, the spatial light modulator selects spatial parts corresponding to different detection frequencies or frequency sub-bands in the Raman scattering spectrum formed in the corresponding chromatic dispersion device, and parts or all of the Raman scattered spectrum is an anti-stokes spectrum. The apparatus and the method are adopted to detect the anti-stokes Raman spectrum in order to realize quantified analysis of components of the sample.
Description
Technical field
The present invention relates to for obtaining raman scattering spectra to analyze the apparatus and method of sample component.
Background technology
The acquisition of raman scattering spectra (Ramanscatteringspectrum) does not rely on the sample pre-treatments of complexity, it is possible to for quick, lossless sample component analysis. More existing portable Raman spectrometers in the market, they volumes are little, simple in construction, and working service is convenient. The excitation wavelength that they adopt mostly is 532nm-1064nm, and the sensor adopted mostly is as sensor linear array, such as charge-coupled image sensor (CCD), N-type metal-oxide-semiconductor field effect t (NMOS). At near infrared band, longer excitation wavelength is adopted to be conducive to reducing fluorescence background, the signal to noise ratio of Raman scattered light detection can be improved to a certain extent, but due to Raman scattering intensity is inversely proportional to the biquadratic of excitation wavelength, the requirement of detection unit performance used is just higher (realizing with extending the detection cycle typically via reducing operating temperature). On the other hand, wave band generally uses indium gallium arsenic (InGaAs) photodiode linear array in the spectral detection of more than 1100nm, the manufacturing cost of current this device is more much higher in the picture sensor linear array of below 1100nm than being suitable for wave band, directly affects the production cost of complete machine. Being limited by above-mentioned factor, sensitivity and the spectral resolution of general portable Raman spectrometer are fairly limited, and cost performance is also less high.
In raman scattering spectra, photon frequency is referred to as anti-Stokes spectrum (anti-Stokesspectrum) higher than the part (namely launch wavelength and be longer than the part of excitation wavelength) of the photon frequency of exciting light, photon frequency is referred to as stokes spectrum (Stokesspectrum) lower than the part (namely transmitted wave length is in the part of excitation wavelength) of the photon frequency of exciting light, the former immediately occurs to certain higher base electron state transition be subject to the polarization of exciting light photon by the molecule being in relatively low base electronic state after, the latter system is in produced by the former after the molecule of higher base electronic state is subject to the polarization of exciting light photon and immediately occurs to relatively low base electron state transition, both spectral lines are symmetrical about zero point relative to the frequency displacement of exciting light spectral line. owing to the photon frequency of off-resonance fluorescence is generally below the photon frequency of exciting light, detection anti-Stokes spectrum contributes to getting rid of the interference of fluorescence background. on the other hand, the molecular number of each energy level is Bridgman distribution, and the intensity of anti-Stokes line is weaker than the stokes line of correspondence, and both ratios increase with frequency displacement and reduce. owing to being subject to the restriction of volume size and performance, the design function of general portable Raman spectrometer does not comprise acquisition anti-Stokes spectrum.
The technology being usually used in observation anti-Stokes Raman spectrum at present has coherent anti-Stokes analysis (coherentanti-StokesRamanspectroscopy). This technology is by sub-for two-beam frequency respectively ��1����2(��1>��2) light laser beam direction sample and its difference on the frequency just equal to the Spontaneous Raman frequency displacement of sample, thus producing the molecular vibration of resonance, be �� with frequency simultaneously3A certain laser beam (frequency that can be described is ��1Light laser light beam) mixing, generation frequency is ��3+��1-��2Anti-Stokes spectrum; Spectral line signal amplitude owing to obtaining is complicated with each physical quantity (including sample component concentration) relation, and background noise is big, and this technology is difficult to use in general sample component quantitative analysis.
Summary of the invention
The shortcoming of prior art in view of the above, the present invention provides a kind of device and method for obtaining raman scattering spectra, to suppress the interference of common fluorescence and bias light in the use of general portable Raman spectrometer, it is thus achieved that high optical s/n ratio, cost will not be too high simultaneously.
For realizing above-mentioned target and other related objective, the present invention provides a kind of device for obtaining raman scattering spectra, including: excitation source, it is used for producing excitation beam; Exciting light light path, for leading solid-state to be analyzed or liquid sample to produce Raman scattered light by described excitation beam; Scattering light collects light path, is used for collecting described Raman scattered light; Containing the detecting device of one or more sense channels, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and converting the signal of telecommunication to for analysis; Connect described scattering light and collect one or more dispersion means of light path and described detecting device, for forming raman scattering spectra according to the described Raman scattered light received; At least one of which dispersion means is configured with spatial light modulator, described spatial modulator detects for selecting the space segment of corresponding different detection frequency or the frequency sub-band described detecting device that gradually leads in the raman scattering spectra that place dispersion means is formed, wherein, described raman scattering spectra is partly or entirely anti-Stokes spectrum.
Optionally, described detecting device includes detector and testing circuit; Described detector is photomultiplier tube or photodiode, works in linearity test pattern or photon counting mode; Under linearity test pattern, the current signal amplitude of described detector output is proportional to the luminous flux that described detector receives; Under photon counting mode, the frequency of the useful signal pulse of described detector output is proportional to the luminous flux that described detector receives.
Optionally, described detecting device also includes the modulating device of described excitation beam and corresponding testing circuit; The modulating device of described excitation beam produces a string modulation signal, and described excitation beam is modulated by described modulation signal, and the signal that described testing circuit is consistent with described frequency modulating signal by filtering output.
Optionally, described dispersion means has multiple, is for respectively forming the spectrum of different frequency range; Described scattering light is collected light path and is additionally provided with one or more beam splitter or is provided with one or more light guide; Collected Raman scattered light is assigned to each described dispersion means by described beam splitter, or is gradually led each described dispersion means by described light guide, forms the raman scattering spectra of different frequency range respectively for each described dispersion means.
Optionally, described light guide include following in one:
(1) mobilizable micro reflector array or scanning galvanometer; By swinging described micro reflector array or the guiding of described scanning galvanometer change emergent light;
(2) mobilizable platform; Described platform is fixed with reflecting mirror, is changed the guiding of emergent light by movable described platform.
Optionally, described spatial light modulator include following in one:
(1) transmitted light device; Described spatial light modulator is by detecting device described in the light directing of its back side transmission;
(2) reflective optical device; Detecting device described in the light directing that its surface is reflected by described spatial light modulator.
Optionally, described spatial light modulator is micro reflector array, and described micro reflector array includes: multiple micro-reflector unit; Each described micro-reflector unit includes: micro-reflector, the pivot being hinged with described micro-reflector, a control circuit unit; The described micro-reflector being driven certain described micro-reflector unit by described control circuit unit is swung around connected described pivot, to control each space segment of described raman scattering spectra from the dispersion means matched with described spatial light modulator to the break-make of described detecting device.
Optionally, described spatial light modulator is liquid crystal light amplitude spatial modulator, and described liquid crystal light amplitude spatial modulator includes: liquid crystal mask and polarization optical element; Described liquid crystal mask includes multiple space cell; Regulated power supply device, voltage for changing each space cell being applied to described liquid crystal mask changes the polarization direction of the transmission light of each space cell being irradiated to described liquid crystal mask from described dispersion means, with each space segment of the raman scattering spectra with the use of the corresponding different detection frequencies of described polarization optical element control or frequency sub-band from described dispersion means to the break-make of described detecting device.
Optionally, described excitation source is laser instrument, for producing the live width excitation beam less than 0.3nm; Described exciting light light path comprises beam shaping element and imaging optical system; Described beam shaping element does shaping for the excitation beam that described laser instrument is sent; Described imaging optical system is for transmitting and converge to described sample by described excitation beam.
For realizing above-mentioned target and other related objective, the present invention provides a kind of method for obtaining raman scattering spectra, including: excitation source is provided, is used for producing excitation beam; There is provided exciting light light path, for described excitation beam is led solid-state to be analyzed or liquid sample to produce Raman scattered light; There is provided scattering light to collect light path, be used for collecting described Raman scattered light; There is provided the detecting device containing one or more sense channels, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and converting the signal of telecommunication to for analysis; The one or more dispersion means connecting described scattering light collection light path and described detecting device are provided, form raman scattering spectra for importing with the described Raman scattered light collected by described scattering light collection light path; At least one of which dispersion means is configured with spatial light modulator, described spatial light modulator detects for selecting space segment the described detecting device that gradually leads of corresponding different detection frequency or frequency sub-band in the raman scattering spectra that place dispersion means is formed, wherein, described raman scattering spectra is partly or entirely anti-Stokes spectrum; Described excitation source produces described excitation beam, and described excitation beam is directed to described sample by described exciting light light path, and Raman scattering thus occurs described sample; Collect light path with described scattering light and collect Raman scattered light produced by described sample the described dispersion means that leads; When certain is configured with the described dispersion means work of described spatial modulator, the described spatial light modulator configured is formed raman scattering spectra, by controlling this described spatial light modulator, make each several part in the spectrum that this described dispersion means formed gradually be collected into described detecting device to detect, be used for the raman scattering spectra obtained in dispersion means working frequency range at this described.
Optionally, described dispersion means has multiple, is for respectively forming the spectrum of different frequency range; Described scattering light is collected light path and is additionally provided with one or more beam splitter or is provided with one or more light guide; Collected Raman scattered light is assigned to each described dispersion means by described beam splitter, or is gradually led each described dispersion means by described light guide, forms the raman scattering spectra of different frequency range respectively for each described dispersion means.
As it has been described above, the present invention provides a kind of device and method for obtaining raman scattering spectra, described device includes: excitation source, is used for producing excitation beam; Exciting light light path, for leading solid-state to be analyzed or liquid sample to produce Raman scattered light by described excitation beam; Scattering light collects light path, is used for collecting described Raman scattered light; Containing the detecting device of one or more sense channels, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and converting the signal of telecommunication to for analysis; Connect described scattering light and collect one or more dispersion means of light path and described detecting device, collect the described Raman scattered light formation raman scattering spectra collected by light path for importing with described scattering light; At least one of which dispersion means is configured with spatial light modulator, described spatial light modulator detects for selecting the space segment of corresponding different detection frequency or the frequency sub-band described detecting device that gradually leads in the raman scattering spectra that place dispersion means is formed, wherein, described raman scattering spectra is partly or entirely anti-Stokes spectrum.
Accompanying drawing explanation
Fig. 1 is shown as in one embodiment of the invention for obtaining the structural representation of the device of raman scattering spectra.
Fig. 2 is shown as in further embodiment of this invention for obtaining the structural representation of the device of raman scattering spectra.
Fig. 3 is shown as in further embodiment of this invention for obtaining the structural representation of the device of raman scattering spectra.
Fig. 4 is shown as in further embodiment of this invention for obtaining the structural representation of the device of raman scattering spectra.
Fig. 5 is shown as in one embodiment of the invention for obtaining the schematic flow sheet of the method for raman scattering spectra.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art the content disclosed by this specification can understand other advantages and effect of the present invention easily. The present invention can also be carried out by additionally different detailed description of the invention or apply, and the every details in this specification based on different viewpoints and application, can also carry out various modification or change under the spirit without departing from the present invention. It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can be mutually combined.
As shown in Figure 1, the present invention provides the device obtaining raman scattering spectra, described device includes: produce the excitation source 1 of excitation beam 2, exciting light light path 3, sample 4, for collect the scattering light 5 from sample 4 scattering light collect light path 6, beam splitter 7, dispersion means 1i, 1j ... and detecting device 8 etc.
Concrete, described excitation source 1, it is used for producing excitation beam 2, makes described excitation beam be accumulated by exciting light light path 3 and be irradiated on the sample 4 being placed on sample area, described sample 4 is subject to exciting scattering thus occurs; Collect light path 6 with scattering light and collect scattering light 5 produced by described sample lead described dispersion means 1i, 1j; In other embodiments, dispersion means can only have one, if described dispersion means is more than one, then by beam splitter 7, collected described scattering light 5 can be assigned to each dispersion means 1i by embodiment illustrated in fig. 1,1j, ..., maybe collected described scattering light 5 gradually can be led each dispersion means by providing light guide to substitute described beam splitter 7, for each described dispersion means (1i, 1j, ...) and its spatial light modulator joined (1i ', 1j ' ...) form the raman scattering spectra of different frequency range respectively.
In the embodiment shown in fig. 1, when certain described dispersion means (1i or 1j) being configured with spatial light modulator (1i ' or 1j ') works, the described spatial light modulator (1i ' or 1j ') configured forms raman scattering spectra, described spectra part or be entirely anti-Stokes spectrum, namely its corresponding wavelength is part or all of shorter than the wavelength of described excitation beam. Control each several part in the spectrum that described spatial light modulator (1i ' or 1j ') makes this described dispersion means (1i or 1j) be formed gradually to be collected into described detecting device 8 and detect, be used for the raman scattering spectra obtained in dispersion means (1i or 1j) working frequency range at this described. Detecting device is containing one or more sense channels, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and converting the signal of telecommunication to for analysis.
It should be noted that, although each dispersion means (1i in the embodiment shown in fig. 1,1j) it is each equipped with spatial light modulator (1i ', 1j '), but in other embodiments, it is possible to only a fraction dispersion means configuration space photomodulator, all the other dispersion means do not configure, and adopt alternate manner detection spectrum, for instance directly with picture sensor linear array detection raman scattering spectra common in current general portable Raman spectrometer.
In one embodiment, described excitation source 1 is laser instrument, for producing the line width excitation beam less than 0.3nm; Described exciting light light path comprises beam shaping element and imaging optical system, and described beam shaping element does shaping for the excitation beam that described laser instrument is sent; Described imaging optical system is for transmitting described excitation beam and converge to described sample 4.
In one embodiment, the described light guide for switching the dispersion means led can include but not limited to: micro reflector array that (1) is swingable or scanning galvanometer, by swinging described micro reflector array or described scanning galvanometer changes the guiding of emergent light; (2) rotatable platform, described platform is fixed with reflecting mirror, changes the guiding of emergent light by rotating described platform. It should be noted that, above-mentioned several ways is only for example, and also can pass through other model of action (such as translation) in other embodiments and be realized.
In one embodiment, it is configured with the described dispersion means (1i of described spatial light modulator, working frequency range 1j), the at least part of photon frequency higher than described excitation beam 2, the photon frequency of described excitation beam 2 or less frequency range can also be covered, namely the spectrum detected comprises anti-Stokes line, the spectral line of stokes line and excitation beam can also be comprised simultaneously. use multiple dispersion means detection Raman spectrum, be conducive to optimizing the performance of described dispersion means in each frequency range.
In one embodiment, described spatial light modulator can be transmission-type, and what now lead described detecting device 8 is the light from described spatial light modulator back side transmission; Can also being reflective, what now lead described detecting device 8 be the light reflected from described spatial light modulator surface.
Further, described detecting device 8 includes detector and testing circuit, and described detector is photomultiplier tube or photodiode, works in linearity test pattern or photon counting mode; Under linearity test pattern, the current signal amplitude of described detector output is proportional to the luminous flux that described detector receives; Under photon counting mode, the frequency of the useful signal pulse of described detector output is proportional to the luminous flux that described detector receives; Preferably, described detecting device also includes the modulating device of described excitation beam and corresponding testing circuit, the modulating device of described excitation beam produces a string modulation signal, described excitation beam is modulated with described modulation signal, the signal that described testing circuit is consistent with described frequency modulating signal by filtering output simultaneously.
Multiple specific embodiment given below illustrates the operation principle of assembly of the invention:
Embodiment 1
Fig. 2 illustrates the embodiment 1 of apparatus of the present invention, including: laser instrument 21, collimating and correcting optical element 23, be used for placing the sample area of sample 24 to be analyzed, beam splitter 25, optically focused/collimating lens 26, band resistance optical filter 29, scanning galvanometer 27, parabolic mirror (2i "; 2j "), slit (2i " '; 2j " '), concave grating (2i, 2j), for selecting the micro reflector array (2i ', 2j ') of detected frequency or frequency sub-band, collecting optical system 281 and detector 282.
Micro reflector array (2i ', 2j ') it is the spatial light modulator for selecting detected frequency or frequency sub-band, their each space cell all comprises a micro-reflector, article one, the pivot being hinged with described micro-reflector, control circuit unit, the described micro-reflector of certain described space cell can be driven to swing around connected described pivot by described control circuit unit, when this described, micro-reflector swings to a direction, the light produced reflection light being irradiated to this described micro-reflector is directed to collecting optical system 281, when this described, micro-reflector swings to other direction, the light produced reflection light being irradiated to this described micro-reflector can not be received by collecting optical system 281, thus control to be transferred to the break-make of each space segment of the spectrum of detector 282.
Detector 282 is photomultiplier tube or photodiode, work in linearity test pattern or photon counting mode, under linearity test pattern, the current signal amplitude of detector 282 output is proportional to the luminous flux received, under photon counting mode, the frequency of the useful signal pulse of detector 282 output is proportional to the luminous flux received.
The work process of this device is as follows: laser instrument 21 produces the live width excitation beam less than 0.3nm, described excitation beam forms, by collimating and correcting optical element 23, the collimated beam that wavefront Energy distribution is relatively uniform, then pass through beam splitter 25 part and turn to 90 ��, converging on sample 24 then through optically focused/collimating lens 26, thus there is scattering in sample 24. The part rear orientation light of sample 24 is collected by optically focused/collimating lens 26 and forms collimated beam, continue to advance along former direction by beam splitter 25 part, it is then passed through band resistance optical filter 29, its medium wavelength composition near excitation wavelength is significantly filtered, and the composition on the Raman scattering wave band of required analysis is able to maximum reservation, for reducing the veiling glare interference to spectrum analysis. Thereafter, the scanned galvanometer of scattering light light beam 27 and parabolic mirror (be after 2i ") two secondary reflection in Fig. 2, are accumulated the entrance slit (be 2i in Fig. 2 " ') of certain dispersion means. Each dispersion means is made up of one entrance slit (2i " ' or 2j " '), concave grating (2i or 2j), a micro reflector array (2i ' or 2j '). The effect of concave grating is the light beam receiving the entrance slit from side, and forms band on the micro reflector array of opposite side by diffraction. By controlling micro reflector array (2i ' or 2j '), gradually lead collecting optical system 281 by each space segment of band. Collecting optical system 281 is collected from the flashlight that micro reflector array (2i ' or 2j ') transmits, and converges on the receiving plane of detector 282. The service band of each dispersion means is different, namely they corresponding Raman scattering optical frequenciess are different, but can there is overlapped portion, by activity scanning galvanometer 27, the guiding of switching scattering light light beam, scattering light is gradually transferred to each dispersion means, to obtain the high-resolution Raman spectrum in wider frequency section, the spatial resolution of the micro reflector array restriction to the resolution of acquired spectrum used by simultaneously eliminating.
Typical design is to be used for analyzing stokes spectrum by one of them dispersion means, and another is used for analyzing anti-Stokes spectrum. With at present general use the device obtaining raman scattering spectra as sensor linear array compared with, the spectrum that single detector detects certain frequency range is used to be conducive to obtaining higher sensitivity with relatively low cost, be conducive to obtaining anti-Stokes spectrum, thus contributing to getting rid of the interference of fluorescence background.
Embodiment 2
Fig. 3 illustrates embodiments of the invention 2, including: laser instrument 31, collimating and correcting optical element 33, it is used for placing the sample area of sample 34 to be analyzed, beam splitter 35, optically focused/collimating lens 36, band resistance optical filter 39, scanning galvanometer 37, parabolic mirror (3i ", 3j "), slit (3i " ', 3j " '), plane transmission grating (3i, 3j), imaging len (3i " " a, 3i " " b, 3j " " a, 3j " " is b), linear polarizer (3i ' a, 3i ' c, 3j ' a, 3j ' is c), for selecting the transmission liquid crystal light amplitude spatial modulator (3i ' b of detected frequency or frequency sub-band, 3j ' is b), collecting optical system 381, and detector 382.
The present embodiment and the embodiment 1 shown in Fig. 2 are distinctive in that the dispersion means used and the composition of the spatial light modulator for selecting detected frequency or frequency sub-band joined and working method. for state as shown in Figure 3 specifically, the dispersion means of institute's gating is by slit 3i " ', imaging len (3i " " a, 3i " " is b) and plane transmission grating 3i composition, eliminates the off-axis astigmatism of dispersion means in embodiment 1 to the full extent, is conducive to obtaining higher spectral resolution. meanwhile, reflective spatial light modulator is no longer applicable to select detected frequency or frequency sub-band, uses linear polarizer 3i ' a instead, 3i ' c, 3j ' a, 3j ' c coordinates transmission liquid crystal light amplitude spatial light modulator 3i ' b, 3j ' b, controls the break-make of the various piece of the spectrum of guiding detecting device 382. for state as shown in Figure 3 specifically, in the dispersion means of institute's gating, significantly filter polarization direction in incident collimated light beams by linear polarizer 3i ' a and be parallel to the part in paper direction, the polarization direction of outgoing beam is substantially perpendicular to paper direction, band is formed through transmission grating 3i diffraction and lens 3i " " b, its polarization direction is basically unchanged, the polarization direction of each space segment of transmission-type transmission liquid crystal light amplitude spatial modulator 3i ' b control transmission light is used under this premise, when selecting to detect certain frequency sub-band, the transmission light polarization direction of the space cell of the 3i ' b that the spectrum frequency sub-band of gating is corresponding remains perpendicular to paper, substantially retained by linear polarizer 3i ' c and received by detecting device 382, the transmission light polarization direction of all the other space cells of 3i ' b is parallel to paper simultaneously, substantially it is filtered out by linear polarizer 3i ' c and can not be received by detecting device 382.
Embodiment 3
Fig. 4 illustrates embodiments of the invention 3, including: laser instrument 41, collimating and correcting optical element 43, it is used for placing the sample area of sample 44 to be analyzed, beam splitter 45, optically focused/collimating lens 46, band resistance optical filter 49, beam splitter 47, parabolic mirror (4i ", 4j ", 4ib, 4ic, 4jb, 4jc), slit (4i " ', 4j " '), plane reflection grating (4ia, 4ja), for selecting the micro reflector array (4i ' of the frequency of raman scattering spectra or the frequency sub-band detected, 4j '), collecting optical system 481, and detector 482.
The present embodiment and the embodiment 1 shown in Fig. 2 are distinctive in that composition and the working method of the dispersion means used. Dispersion means is by entrance slit 4i " ', parabolic mirror 4ib; 4ic, plane reflection grating 4ia, micro reflector array 4i ' composition; dispersion means is 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, a part continues to advance along former direction, by parabolic mirror 4i " converge to the entrance slit 4i of dispersion means " ' on, another part changes direction through beam splitter reflection, by parabolic mirror 4j " converge to the entrance slit 4j of dispersion means " ' on. Parabolic mirror 4ib, the effect of 4ic is that the light beam of the line source from entrance slit is become collimated beam, and the effect of plane reflection grating is to make incident collimated light beams diffraction, through parabolic mirror 4ic, 4jc forms band on micro reflector array (4i ', 4j ').
As it is shown in figure 5, in conjunction with said apparatus, the present invention may also provide a kind of method for obtaining raman scattering spectra, including:
Step S1: excitation source is provided, is used for producing excitation beam;
Step S2: provide exciting light light path, for leading solid-state to be analyzed or liquid sample to produce Raman scattered light by described excitation beam;
Step S3: provide scattering light to collect light path, be used for collecting described Raman scattered light;
Step S4: provide the detecting device containing one or more sense channels, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and converting the signal of telecommunication to for analysis;
Step S5: provide the one or more dispersion means connecting described scattering light collection light path and described detecting device, forms raman scattering spectra for importing with the described Raman scattered light collected by described scattering light collection light path; At least one of which dispersion means is configured with spatial light modulator, described spatial light modulator detects for selecting space segment the described detecting device that gradually leads of corresponding different detection frequency or frequency sub-band in the raman scattering spectra that place dispersion means is formed, wherein, described raman scattering spectra is partly or entirely anti-Stokes spectrum.
Step S6: described excitation source produces described excitation beam, and described excitation beam is directed to described sample by described exciting light light path, and Raman scattering thus occurs described sample;
Step S7: collect light path with described scattering light and collect Raman scattered light produced by described sample the described dispersion means that leads;
Step S8: when certain is configured with the described dispersion means work of described spatial modulator, the described spatial light modulator configured is formed raman scattering spectra, by controlling this described spatial light modulator, make each several part in the spectrum that this described dispersion means formed gradually be collected into described detecting device to detect, be used for the raman scattering spectra obtained in dispersion means working frequency range at this described.
In sum, the present invention provides a kind of device and method for obtaining raman scattering spectra, and described device includes: excitation source, is used for producing excitation beam; Exciting light light path, for leading solid-state to be analyzed or liquid sample to produce Raman scattered light by described excitation beam; Scattering light collects light path, is used for collecting described Raman scattered light; Detecting device, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and converting the signal of telecommunication to for analysis; Connect described scattering light and collect one or more dispersion means of light path and described detecting device, collect the described Raman scattered light formation raman scattering spectra collected by light path for importing with described scattering light; At least one of which dispersion means is configured with spatial light modulator, described spatial light modulator detects for selecting the space segment of corresponding different detection frequency or the frequency sub-band described detecting device that gradually leads in the raman scattering spectra that place dispersion means is formed, wherein, described raman scattering spectra is partly or entirely anti-Stokes spectrum; Adopt assembly of the invention and method can detect anti-Stokes Raman spectrum, for sample component quantitative analysis.
Above-described embodiment is illustrative principles of the invention and effect thereof only, not for the restriction present invention. Above-described embodiment all under the spirit and category of the present invention, can be modified or change by any those skilled in the art. Therefore, art has usually intellectual such as modifying without departing from all equivalences completed under disclosed spirit and technological thought or change, must be contained by the claim of the present invention.
Claims (11)
1. the device being used for obtaining raman scattering spectra, it is characterised in that including:
Excitation source, is used for producing excitation beam;
Exciting light light path, for leading solid-state to be analyzed or liquid sample to produce Raman scattered light by described excitation beam;
Scattering light collects light path, is used for collecting described Raman scattered light;
Containing the detecting device of one or more sense channels, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and converting the signal of telecommunication to for analysis;
Connect described scattering light and collect one or more dispersion means of light path and described detecting device, collect the described Raman scattered light formation raman scattering spectra collected by light path for importing with described scattering light; At least one of which dispersion means is configured with spatial light modulator, described spatial light modulator detects for selecting space segment the described detecting device that gradually leads of corresponding different detection frequency or frequency sub-band in the raman scattering spectra that place dispersion means is formed, wherein, described raman scattering spectra is partly or entirely anti-Stokes spectrum.
2. the device for obtaining raman scattering spectra as claimed in claim 1, it is characterised in that described detecting device includes detector and testing circuit; Described detector is photomultiplier tube or photodiode, works in linearity test pattern or photon counting mode; Under linearity test pattern, the current signal amplitude of described detector output is proportional to the luminous flux that described detector receives; Under photon counting mode, the frequency of the useful signal pulse of described detector output is proportional to the luminous flux that described detector receives.
3. the device for obtaining raman scattering spectra as claimed in claim 2, it is characterized in that, also include the modulating device of described excitation beam and corresponding testing circuit, the modulating device of described excitation beam produces a string modulation signal, described excitation beam is modulated by described modulation signal, and the signal that described testing circuit is consistent with described frequency modulating signal by filtering output.
4. the device for obtaining raman scattering spectra as claimed in claim 1, it is characterised in that described dispersion means has multiple, is for respectively forming the spectrum of different frequency range; Described scattering light is collected light path and is additionally provided with one or more beam splitter or is provided with one or more light guide; Collected Raman scattered light is assigned to each described dispersion means by described beam splitter, or is gradually led each described dispersion means by described light guide, forms the raman scattering spectra of different frequency range respectively for each described dispersion means.
5. the device for obtaining raman scattering spectra as claimed in claim 4, it is characterised in that described light guide include following in one:
(1) swingable micro reflector array or scanning galvanometer; By swinging described micro reflector array or the guiding of described scanning galvanometer change emergent light;
(2) mobilizable platform; Described platform is fixed with reflecting mirror, is changed the guiding of emergent light by movable described platform.
6. the device for obtaining raman scattering spectra as claimed in claim 1, it is characterised in that described spatial light modulator include following in one:
(1) transmitted light device; Described spatial light modulator is by detecting device described in the light directing of its back side transmission;
(2) reflective optical device; Detecting device described in the light directing that its surface is reflected by described spatial light modulator.
7. the device for obtaining raman scattering spectra as claimed in claim 6, it is characterised in that described spatial light modulator is micro reflector array, and described micro reflector array includes: multiple micro-reflector unit;
Each described micro-reflector unit includes: micro-reflector, the pivot being hinged with described micro-reflector, a control circuit unit; The described micro-reflector being driven certain described micro-reflector unit by described control circuit unit is swung around connected described pivot, to control each space segment of described raman scattering spectra from the dispersion means matched with described spatial light modulator to the break-make of described detecting device.
8. the device for obtaining raman scattering spectra as claimed in claim 6, described spatial light modulator is liquid crystal light amplitude spatial modulator, and described liquid crystal light amplitude spatial modulator includes: liquid crystal mask and polarization optical element; Described liquid crystal mask includes multiple space cell; Regulated power supply device, voltage for changing each space cell being applied to described liquid crystal mask changes the polarization direction of the transmission light of each space cell being irradiated to described liquid crystal mask from described dispersion means, with each space segment of the raman scattering spectra with the use of the corresponding different detection frequencies of described polarization optical element control or frequency sub-band from described dispersion means to the break-make of described detecting device.
9. the device for obtaining raman scattering spectra as claimed in claim 1, it is characterised in that described excitation source is laser instrument, for producing the line width excitation beam less than 0.3nm; Described exciting light light path comprises beam shaping element and imaging optical system, and described beam shaping element does shaping for the excitation beam that described laser instrument is sent; Described imaging optical system is for transmitting and converge to described sample by described excitation beam.
10. the method for obtaining raman scattering spectra, it is characterised in that including:
Excitation source is provided, is used for producing excitation beam;
There is provided exciting light light path, for described excitation beam is led solid-state to be analyzed or liquid sample to produce Raman scattered light;
There is provided scattering light to collect light path, be used for collecting described Raman scattered light;
There is provided the detecting device containing one or more sense channels, for receiving the Raman scattering optical signal of corresponding each detection frequency or frequency sub-band and converting the signal of telecommunication to for analysis;
The one or more dispersion means connecting described scattering light collection light path and described detecting device are provided, form raman scattering spectra for importing with the described Raman scattered light collected by described scattering light collection light path; At least one of which dispersion means is configured with spatial light modulator, described spatial light modulator detects for selecting space segment the described detecting device that gradually leads of corresponding different detection frequency or frequency sub-band in the raman scattering spectra that place dispersion means is formed, wherein, described raman scattering spectra is partly or entirely anti-Stokes spectrum;
Described excitation source produces described excitation beam, and described excitation beam is directed to described sample by described exciting light light path, and Raman scattering thus occurs described sample;
Collect light path with described scattering light and collect Raman scattered light produced by described sample the described dispersion means that leads;
When certain is configured with the described dispersion means work of described spatial modulator, the described spatial light modulator configured is formed raman scattering spectra, by controlling this described spatial light modulator, make each several part in the spectrum that this described dispersion means formed gradually be collected into described detecting device to detect, be used for the raman scattering spectra obtained in dispersion means working frequency range at this described.
11. the method for obtaining raman scattering spectra as claimed in claim 10, it is characterised in that described dispersion means has multiple, is for respectively forming the spectrum of different frequency range; Described scattering light is collected light path and is additionally provided with one or more beam splitter or is provided with one or more light guide; Collected Raman scattered light is assigned to each described dispersion means by described beam splitter, or is gradually led each described dispersion means by described light guide, forms the raman scattering spectra of different frequency range respectively for each described dispersion means.
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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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| CN109557070A (en) * | 2018-10-27 | 2019-04-02 | 西安电子科技大学 | A kind of Raman Imaging System based on space encoding light |
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| CN114402182A (en) * | 2019-03-25 | 2022-04-26 | Mks技术(贸易用名雪域仪器) | Multi-chromatic dispersion 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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