CN104990908A - Laser biax confocal induced breakdown-Raman spectrum imaging detection method and device - Google Patents
Laser biax confocal induced breakdown-Raman spectrum imaging detection method and device Download PDFInfo
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- CN104990908A CN104990908A CN201510350355.8A CN201510350355A CN104990908A CN 104990908 A CN104990908 A CN 104990908A CN 201510350355 A CN201510350355 A CN 201510350355A CN 104990908 A CN104990908 A CN 104990908A
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Abstract
The invention belongs to the technical field of spectrum measurement and imaging and relates to a laser biax confocal induced breakdown-Raman spectrum imaging detection method and device. The method and device can be used for high spatial discrimination imaging and detection for microcell component and shape parameters of a sample. According to the method and device, elementary composition information of sample components is detected by utilizing the laser-induced breakdown spectrum; chemical bond and molecular structure information of the sample is detected by utilizing the Raman spectrum; surface appearance information of the sample is detected by utilizing the biax confocal technology. A biax structure has the advantages of being large in view field and working distance, the back scattering influence can be effectively restrained, and the spectrum detection signal-to-noise ratio is raised; the three elements are combined, the structural sharing and functional complementation can be achieved, and the comprehensive measurement about the appearance and component information of the sample can be achieved. The method and device have the advantages of being high in spatial discrimination, rich in material component information, controllable in measured focusing spot size and the like, and the wide prospect of application in fields such as mineral products, metallurgy, space exploration, environment monitoring, biology and medical treatment can be achieved.
Description
Technical field
The invention belongs to spectral measurement and technical field of imaging, relate to a kind of laser twin shaft confocal induced breakdown-Raman spectrum imaging detection method and device, confocal laser imaging technique is combined with spectrographic detection technology, form the high-resolution spectra imaging of a kind of " collection of illustrative plates unification " and detection method and device, the microcell form component multi-spectrum synthesis that can be used for sample is tested and high-resolution imaging.
Technical background
LIBS (Laser Induced Breakdown Spectroscopy, be called for short LIBS), it is a kind of material composition in-situ investigation technology, it utilizes the laser excitation sample surfaces of high power density, produce laser induced plasma, by the atom in exploring laser light induced plasma and ion line, determine the component composition of sample, its outstanding advantage is that detectable atom and Small molecular element form.
Since being born from 1962, LIBS is widely used in minute manufacturing, mineral products are analyzed, environmental monitoring, multiple field such as biologic medical, and " chemistry and the video camera instrument system (ChemCam) " of carrying in " curious number " Marsokhod of U.S.'s transmitting in 2011 is used to carry out remote probe to Mars surface rock sample, show its great ability in the material composition detection of space, therefore after " curious number " Marsokhod ChemCam system, Venus probe instrument is chosen as again, extensively employing is studied by the multiple National Airspace structure in the world.
But there is following outstanding problem in existing LIBS:
1) owing to utilizing collimated laser beam to produce plasma to irradiate excited sample, thus still there is the problems such as laser excitation hot spot is large, spectrographic detection spatial resolution is not high in it;
2) cannot detect parameters such as the chemical bond in molecule, molecular structures, its result constrains the accurate complete acquisition of sample material component information;
3) cannot effectively suppress back-scattering light to disturb, constrain the lifting of system signal noise ratio, and and then limit the improvement of spectrographic detection resolving power;
3) the sample component information obtained cannot combine with the shape information of sample, and the original position high-resolution that cannot realize sample morphology-component integrated information obtains.
And the Obtaining Accurate of " microcell " complete component information of mineral products, space material and biological sample is all extremely important for scientific research and production testing.In fact, how detecting micro-area composition information is with sensitivity the common technology problem that the fields such as current mineral products analysis, space exploration and environment measuring are urgently studied.
The intense pulse laser of Laser-induced Breakdown Spectroscopy focuses on sample surfaces can make sample ionization, excited sample can produce plasma, the atom of sample can be obtained and Small molecular element forms information by the fail spectrum that gives off of detection energy of plasma, but chemical bond and the molecular structure information of sample molecule cannot be obtained, how complete the element composition of acquisition sample molecule and molecular structure information, the component for high accuracy analysis sample is significant.
Utilize laser Raman spectroscopy technology can measure the molecule excitation spectrum of sample, obtain the chemical bond in sample and molecular structure information.Laser Raman spectroscopy technology is combined with Laser-induced Breakdown Spectroscopy (LIBS) technology, can the deficiency that cannot obtain molecular structure and chemical bond information in LIBS be made up.
Laser twin shaft confocal technology utilizes illumination to detect with detection light path non-co-line structure, not only significantly improve azimuthal resolution and the Focus accuracy of light path, realize the high-resolution imaging detection of sample topography, and can effectively suppress backscattering to disturb, improve spectrographic detection signal to noise ratio (S/N ratio).
Based on this, the present invention proposes a kind of laser twin shaft confocal induced breakdown spectroscopy-Raman spectrum micro imaging method and device, its innovation is: will have laser twin shaft confocal detection light path first and merge mutually with Laser-induced Breakdown Spectroscopy (LIBS) technology and laser Raman spectroscopy Detection Techniques, and can realize imaging and the detection of sample microcell high-resolution and highly sensitive pattern and component.
A kind of laser twin shaft confocal induced breakdown spectroscopy-Raman spectrum micro imaging method that the present invention proposes and device can be material composition high-resolution imaging and detect and provide a brand-new effective technical way.
Summary of the invention
The object of the invention is the high-resolution spectra imaging of " collection of illustrative plates is unified " in order to realize material composition and shape information, a kind of laser twin shaft confocal induced breakdown-Raman spectrum imaging detection method and device are proposed, to obtaining the test of microcell form component multi-spectrum synthesis and the high-resolution imaging of sample simultaneously.
The object of the invention is to be achieved through the following technical solutions.
Twin shaft confocal laser induced breakdown-Raman spectrum imaging detection method of the present invention, light path lighting optical axis becomes angle to distribute with detection optical axis, exciting light irradiation is irradiated to sample surfaces along illumination path and inspires Reyleith scanttering light and the Laser-induced Breakdown Spectroscopy and the Raman spectrum that are loaded with sample component information, Reyleith scanttering light, Laser-induced Breakdown Spectroscopy is become the detection light path of angle to receive with Raman spectrum with illumination path, the element composition information that Laser-induced Breakdown Spectroscopy detection system obtains sample is entered through a light splitting part, Raman scattering light transmission dichroic optical system in another part enters chemical bond and the molecular structure information that Raman spectrum detection system obtains sample, Reyleith scanttering light and Laser-induced Breakdown Spectroscopy enter confocal detection system through dichroic optical system reflection and carry out light intensity detection acquisition sample surfaces height and topographical information.Laser-induced Breakdown Spectroscopy detection, Raman spectrum detection and laser twin shaft confocal topographical information detection triplicity can realize structure and share and have complementary functions, and realize light spectrum image-forming and the detection of high-space resolution, the specific implementation step of the method is as follows:
1) illumination objective lens is symmetrically distributed in measuring surface normal both sides with collection object lens, and the angle of lighting optical axis and measuring surface normal is θ
1, the angle gathering optical axis and measuring surface normal is θ
2, with measuring surface normal direction for measuring axis, set up system coordinate system (x, y, z), wherein θ
1=θ
2;
2) exciting light focuses on sample via illumination objective lens, inspire Reyleith scanttering light and the Raman spectrum and the Laser-induced Breakdown Spectroscopy that are loaded with sample spectral characteristic, the Reyleith scanttering light be inspired and be loaded with the Raman spectrum of sample material composition information and Laser-induced Breakdown Spectroscopy is entered collection object lens by reflection, and collected object lens converge to beam splitting system, light beam is divided into transmittance and reflectance two bundle after beam splitting system light splitting, and transmitted light path enters Laser-induced Breakdown Spectroscopy detection system and obtains Laser-induced Breakdown Spectroscopy signal I (λ
l); Folded light beam is through dichroic optical system light splitting, and the Raman spectrum in reflected light enters Raman spectrum detection system through dichroic optical system and obtains raman spectral signal I (λ
r), the Reyleith scanttering light in folded light beam and Laser-induced Breakdown Spectroscopy are entered confocal detection system by dichroic optical system reflection;
3) light intensity detection is carried out to the light signal entering confocal detection system, measuring beam converges on point probe through measuring lens, point probe detection focused light spot near central regions light intensity signal, the distance that moves axially in conjunction with sample 3 obtains confocal curves, obtains confocal signal I (x, y, z), utilize the characteristic that confocal curves peak point is corresponding with focal position, come localized excitation beam focus O position by peak point position, realize the focus location of sample;
4) control laser beam according to confocal signal I (x, y, z) accurately to focus on sample, again obtain the spectral signal I (λ of sample
l) and I (λ
r);
5) utilize data handling system by the confocal signal I (x, y, z) of acquisition, spectral signal I (λ
l) and I (λ
r) carry out Data Fusion, with four-dimensional metrical information I (x, y, z, the λ of the topographical information and material composition information that obtain sample
l, λ
r);
6) after completing above-mentioned steps, control light beam and scanning probe carried out to sample, step 2 is repeated to the next point in sample surface), 3), 4), 5) until scanned;
7), when processing separately confocal signal I (x, y, z), the three-dimensional appearance information of the high-space resolution of sample is obtained; Independent process raman spectral signal I (λ
r) time, obtain chemical bond and the molecular structure information of sample; Independent process Laser-induced Breakdown Spectroscopy signal I (λ
l) time, obtain the element composition information of sample; Process confocal signal I (x, y, z), spectral signal I (λ simultaneously
l) and I (λ
r) time, obtain the high-space resolution pattern of sample and the imaging detection of microcell material composition " collection of illustrative plates unification ".
Point probe in the present invention in confocal detection system can also be image capturing system, data handling system obtains after focal spot pattern from image capturing system, calculate the center of now focal spot pattern, and get focal spot pattern center near zone and carry out light intensity detection, form confocal dummy pinhole, when sample carry out axial scan move time, data handling system calculates pixel grey scale summation within the scope of confocal dummy pinhole, obtain confocal axial strength response.
Measure focused spot size for compression in the present invention and improve system transverse resolution, described excitation beam is light beam, comprises line polarisation, rotatory polarization, radial polarisation light; Or the structure light beam to be generated by pupil filtering technology.
In the present invention, system can also detect the scattering spectrum such as fluorescence, Compton scattering light.
The invention provides a kind of twin shaft confocal laser induced breakdown-Raman spectrum imaging sniffer, comprise light source, illumination objective lens and collection object lens, it is characterized in that: also comprise collimator and extender mirror, light-beam scanner, beam splitting system, dichroic optical system, confocal detection device, Raman spectrum detection system and Laser-induced Breakdown Spectroscopy detection system; Wherein, layout is in measuring surface normal both sides symmetrically for illumination objective lens and collection object lens, and the angle of lighting optical axis and measuring surface normal is θ
1, the angle gathering optical axis and measuring surface normal is θ
2, wherein θ
1=θ
2collimator and extender mirror, light-beam scanner and illumination objective lens are successively placed on the emergent ray direction of light source, collection object lens and beam splitting system are successively placed on the reflection ray direction of sample, Laser-induced Breakdown Spectroscopy detection system is placed on dichroic light-dividing device transmission direction, dichroic optical system and Raman spectrum detection system are placed on the reflection direction of beam splitting system, and confocal detection device is placed on the reflection direction to look beam splitting system.
It is raising system transverse resolution in apparatus of the present invention, system also can add illumination end iris filter between collimator and extender mirror and illumination objective lens, or between dichroism beam splitting system and measurement lens, add collection terminal iris filter, or add illumination end iris filter and collection terminal iris filter between collimator and extender mirror and illumination objective lens and between dichroic optical system and measurement lens simultaneously.
Be raising system transverse resolution in apparatus of the present invention, also can add polarization modulating arrangement between collimator and extender mirror and light-beam scanner, or add polarization modulating arrangement between illumination objective lens and illumination end iris filter.
In apparatus of the present invention, the sniffer of confocal detection device can point probe or ccd detector.
The data handling system of finally carrying out Data Fusion is also comprised in apparatus of the present invention.
In apparatus of the present invention, Raman spectrum sniffer can be confocal spectroscopic sniffer, comprise the first condenser, be positioned at the pin hole at the first condenser focus place, second condenser lens, the spectrometer being positioned at second condenser lens focus place and spectrometer after the second detector; Second detector that can also be common spectral detection device, comprise second condenser lens, be positioned at after the spectrometer at second condenser lens focus place and spectrometer; Laser-induced Breakdown Spectroscopy sniffer comprises laser-induced breakdown condenser, is positioned at the pin hole of laser-induced breakdown condenser focal position, the spectrometer after pin hole and the 3rd detector.
Beneficial effect
The inventive method, contrast prior art has following innovative point:
1) laser twin shaft confocal technology and spectrographic detection technology organically combine by the present invention, the high precision axial tracking having merged laser twin shaft confocal technology focuses ability, accurately can focus sample and ensure that focused activating light spot is minimum, and then obtain the minimum spectrum parameter exciting focal beam spot region of sample, realize the high-space resolution detection of sample microscopic spectrum, this is one of innovative point being different from existing spectrographic detection technology;
2) the present invention can be detected the raman scattering spectrum and Laser-induced Breakdown Spectroscopy containing different information by appropriate design simultaneously, realize structure share and have complementary functions, achieve the high-resolution detection to sample element composition and chemical bond and molecular structure, obtain the integrated information of sample material component, this is the innovative point two being different from existing spectrographic detection technology;
3) laser twin shaft confocal microscope system is merged on 26S Proteasome Structure and Function mutually with spectrum imaging system, both the imaging of sample microcell geometry appearance can have been realized, the spectrographic detection of sample microcell can be realized again, namely realize the multiple imaging patterns such as microscale tomography, collection of illustrative plates tomography and spectrum test, this is the innovative point three being different from existing spectrographic detection technology simultaneously;
4) laser cross-compound arrangement effectively can avoid the system parasitic light that excitation beam backscattering is introduced, and reduces spectrographic detection noise, and improve detection signal to noise ratio (S/N ratio) and Spectral resolution, this is the innovative point four being different from existing spectrographic detection technology;
The inventive method has following features:
1) merge laser twin shaft confocal technology and spectrographic detection technology, utilize the accurate location of confocal system focusing, significantly improve the spatial resolution of spectrographic detection;
2) by Laser-induced Breakdown Spectroscopy and laser Raman spectroscopy coupling, realize exciting the complementation with function that shares with detecting structure, obtain the integrated informations such as the element composition of sample component, chemical bond and molecular structure;
3) adopt the mode of cross-compound arrangement oblique incidence throw light on and detect, effectively inhibit the interference of sample back-scattering light, improve spectrographic detection signal to noise ratio (S/N ratio);
4) twin shaft confocal arrangement can utilize small value aperture object lens to realize high resolution axially to focus, take into account range ability and resolution characteristic.
Accompanying drawing explanation
Fig. 1 is the confocal induced breakdown of laser twin shaft-Raman spectrum imaging detection method schematic diagram;
Fig. 2 is the confocal induced breakdown of laser twin shaft-Raman spectrum imaging sniffer schematic diagram;
Fig. 3 is the confocal induced breakdown of the laser twin shaft-Raman spectrum imaging sniffer schematic diagram of band Polarization Modulation;
Fig. 4 is the confocal induced breakdown of the laser twin shaft-Raman spectrum imaging sniffer schematic diagram with detection focal spot amplification system;
Fig. 5 is laser twin shaft confocal induced breakdown-Raman spectrum imaging detection method and device embodiment schematic diagram;
Wherein, 1-light source, 2-illumination objective lens, 3-sample, 4-lighting optical axis, 5-measuring surface normal, 6-θ
1, 7-gathers object lens, 8-beam splitting system, 9-measures lens, 10-focal spot amplification system, 11-point probe, the confocal dummy pinhole of 12-, 13-measures optical axis, the confocal Raman curve of 14-, 15-confocal detection system, 16-focal spot pattern, 17-first condenser, 18-pin hole, 19-Raman spectrum detection system, 20-gathers optical axis, 21-data handling system, 22-second condenser lens, 23-spectrometer, 24-detector, 25-collimating and beam expanding system, 26-optical beam scanning system, 27-confocal curves, 28-illumination end iris filter, 29-Polarization Modulation system, 30-collection terminal iris filter, 31-θ
2, 32-dichroic optical system, 33-Laser-induced Breakdown Spectroscopy detection system, 34-Laser-induced Breakdown Spectroscopy gathers optical axis, 35-Laser-induced Breakdown Spectroscopy condenser, 36-pin hole, 37-spectrometer, 38-detector.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment
In the present embodiment, light source 1 is laser instrument, image enhancement system 10 is enlarging objective, image capturing system 11 is ccd detector, data handling system 21 is computing machine, detector 24 is ccd detector, and Polarization Modulation system 29 is radial polarisation photogenerator, and dichroic optical system 32 is Notch filter.
As shown in Figure 1, Figure 2 with shown in Fig. 5, illumination objective lens 2 is symmetrically distributed in measuring surface normal 5 both sides with collection object lens 7, and lighting optical axis 4 is θ with the angle of measuring surface normal 5
16, gathering optical axis 20 with the angle of measuring surface normal 5 is θ
231, wherein θ
1=θ
2, twin shaft confocal laser induced breakdown-method for measuring Raman spectrum, its measuring process is:
First, the light beam that laser instrument 1 sends is after collimating and beam expanding system 25, the directional light equal with illumination objective lens 2 Entry pupil diameters is become after carrying out expanding outgoing, radial polarisation light is become after radial polarisation photogenerator 29, radial polarisation light light beam after illumination end iris filter 28 is modulated, after optical beam scanning system 26, illuminated object lens 2 form compression hot spot and focus on sample 3 surface, and inspire Reyleith scanttering light and the Raman diffused light and the Laser-induced Breakdown Spectroscopy that are loaded with sample 3 spectral characteristic, sample 3 strengthens technology by spectrum such as enhanced spectrum nano particles and processes, to improve the intensity of scattered light.
Axially (namely in figure z to) mobile sample 3, the raman scattering spectrum of Reyleith scanttering light and corresponding sample 3 zones of different and Laser-induced Breakdown Spectroscopy are entered by reflection and gathers object lens 7, the light beam system 8 that is split of collecting through gathering object lens 7 carries out light splitting, wherein transmitted light beam enters Laser-induced Breakdown Spectroscopy detection system 33, reflected light is by Notch filter 32 light splitting again, wherein Raman diffused light enters Raman spectrum detection system 19 transmitted through Notch filter32, Reyleith scanttering light and Laser-induced Breakdown Spectroscopy are reflexed to confocal detection system 15 by Notch filter32.
The light beam entering Laser-induced Breakdown Spectroscopy detection system 33 is assembled by Laser-induced Breakdown Spectroscopy condenser 35 and is entered spectrometer 37 through pin hole 36, is finally detected device 38 and receives the Laser-induced Breakdown Spectroscopy I (λ obtaining sample 3
l) (λ is wavelength);
The Raman diffused light entering Raman spectrum detection system 19 is converged to pin hole 18 by the first condenser 17, assembles and enters spectrometer 23, finally incide ccd detector 24, obtain the Raman spectrum I (λ of sample 3 through second condenser lens 22
r) (λ is wavelength), as shown in confocal Raman curve 14;
The light beam entering confocal detection system 15, after collection terminal iris filter 30 is modulated, enters confocal detection system 15, and assemble through measuring lens 9, focused light spot is amplified through enlarging objective 10 and is imaged on ccd detector 11;
Computing machine 21 obtains after focal spot pattern 16 from ccd detector 11, calculates the center of now focal spot pattern 16, using this center as true origin, sets up the coordinate system (x in CCD image planes
d', y
d'), a circle confocal dummy pinhole 12 focal spot pattern 16 is set at initial point place and detects; When sample 3 scans, computing machine 21 calculates pixel grey scale summation in confocal dummy pinhole 12 scope, obtain confocal intensity response I (x, y, z), as shown in confocal curves 27, obtained the elevation information of sample surfaces by " extreme point " of confocal curves 27, reconstruct the three-dimensional surface shape of sample 3.
According to the characteristic that the extreme point of confocal curves 27 is accurately corresponding with system focus, accurately obtain system focus position, sample 3 is moved to focus O position, again obtain the spectral signal I (λ of focus O position
r) and I (λ
l).
After completing above-mentioned steps, transversal scanning (x, y direction namely in figure) is carried out to sample 3, after moving to next point, repeats the more lower confocal intensity response I (x that above-mentioned steps obtains sample 3, y, z) and spectral signal I (λ
r), I (λ
l).
By I (λ
r) and I (λ
l), I (x, y, z) is sent to computing machine 21 and carries out data processing, thus obtains four-dimensional metrical information I (x, y, z, the λ that comprise sample 3 topographical information and spectral information
r, λ
l).
Only process is carried out to the confocal detection system 15 acquisition detection hot spot receiving Reyleith scanttering light and obtain confocal response I (x, y, z), accurately catch by its " extreme point " focal position exciting hot spot, system can carry out the three dimension scale tomography of high-space resolution; Spectral response I (the λ that the Raman spectrum detection system 19 that only Raman diffused light is received in docking obtains
r) 14 when processing, system can carry out Raman spectrum detection; Spectral response I (the λ that the Laser-induced Breakdown Spectroscopy detection system 33 of docking laser induced breakdown spectroscopy obtains
l) 39 when processing, system can carry out Laser-induced Breakdown Spectroscopy detection; Simultaneously to receiving the confocal response I (x, y, z) of ccd detector 11 acquisition of Reyleith scanttering light, the spectral signal I (λ of Raman spectrum detection system 19 acquisition of Raman diffused light
r) and Laser-induced Breakdown Spectroscopy Laser-induced Breakdown Spectroscopy detection system 33 obtain spectral response I (λ
l) when processing, the integrated information to reflection sample 3 pattern and component that system is passable, namely realizes " collection of illustrative plates unification " Effect on Detecting of the high-space resolution of sample 3 topographical information and spectral information.
As shown in Figure 5, twin shaft confocal laser induced breakdown-raman spectroscopy measurement device comprises laser instrument 1, collimating and beam expanding system 25, radial polarisation photogenerator 29, illumination end iris filter 28, optical beam scanning system 26, illumination objective lens 2, the sample 3 placed successively along light path, and the collection object lens 7 of light path reflection direction, beam splitting system 8, is positioned at the Laser-induced Breakdown Spectroscopy detection system 33 of beam splitting system 8 transmission direction; Be positioned at the Notch filter 32 of beam splitting system 8 reflection direction, Raman spectrum detection system 19, be positioned at the confocal detection system 15 of Notch filter 32 reflection direction, and connect the computing machine 21 of confocal detection system 15, Raman spectrum detection system 19 and Laser-induced Breakdown Spectroscopy detection system 33; Wherein, Raman spectrum detection system 19 comprise the first condenser 17 placed successively along light path, the pin hole 18 being positioned at the first condenser 17 focal position, be positioned at pin hole 18 after second condenser lens 22, be positioned at second condenser lens 22 focal position spectrometer 23 and be positioned at the ccd detector after spectrometer 24; Laser-induced Breakdown Spectroscopy detection system 33 comprise the Laser-induced Breakdown Spectroscopy condenser 35 placed successively along light path, the pin hole 36 being positioned at Laser-induced Breakdown Spectroscopy condenser 35 focal position, be positioned at pin hole 36 after spectrometer 37 and detector 38 after being positioned at spectrometer 37; Confocal detection system 15 comprises the enlarging objective 10 being positioned at and measuring lens 9 focus place, and is positioned at the ccd detector 22 at enlarging objective 10 focus place.
Radial polarisation photogenerator 29, light-beam scanner 26, illumination end iris filter 28 is added in collimator and extender device 25 in fig. 2 and illumination objective lens 2, collection terminal iris filter 30 is added between Notch filter32 and measurement lens 9, i.e. pie graph 3, add radial polarisation photogenerator 29, illumination end iris filter 28, collection terminal iris filter 30 for carrying out structure and polarization state modulation to light beam, improve transverse resolution.
As shown in Figure 4, in the confocal detection device 15 of Fig. 2, increase focal spot amplification system 10 measurement by magnification lens 9 focus on the Aili spot formed, be convenient to utilize ccd detector 13 to receive.
Below by reference to the accompanying drawings the specific embodiment of the present invention is described; but these explanations can not be understood to limit scope of the present invention; protection scope of the present invention is limited by the claims of enclosing, and any change on the claims in the present invention basis is all protection scope of the present invention.
Claims (10)
1. laser twin shaft confocal induced breakdown-Raman spectrum imaging detection method, it is characterized in that: light path lighting optical axis becomes angle to distribute with detection optical axis, exciting light irradiation is irradiated to sample surfaces along illumination path and inspires Reyleith scanttering light and the Laser-induced Breakdown Spectroscopy and the Raman spectrum that are loaded with sample component information, Reyleith scanttering light, Laser-induced Breakdown Spectroscopy is become the detection light path of angle to receive with Raman spectrum with illumination path, the element composition information that Laser-induced Breakdown Spectroscopy detection system obtains sample is entered through a light splitting part, Raman scattering light transmission dichroic optical system in another part enters chemical bond and the molecular structure information that Raman spectrum detection system obtains sample, Reyleith scanttering light and Laser-induced Breakdown Spectroscopy enter confocal detection system through dichroic optical system reflection and carry out light intensity detection acquisition sample surfaces height and topographical information.Laser-induced Breakdown Spectroscopy detection, Raman spectrum detection and laser twin shaft confocal topographical information detection triplicity can realize structure and share and have complementary functions, and realize light spectrum image-forming and the detection of high-space resolution, the specific implementation step of the method is as follows:
1) illumination objective lens (2) is symmetrically distributed in measuring surface normal (5) both sides with collection object lens (7), and lighting optical axis (4) is θ with the angle of measuring surface normal (5)
1(6), gathering optical axis (20) with the angle of measuring surface normal (5) is θ
2(37), with measuring surface normal (5) direction for measuring axis, system coordinate system (x, y, z) is set up, wherein θ
1=θ
2;
2) exciting light focuses on sample (3) via illumination objective lens (2), inspire Reyleith scanttering light and the Raman spectrum and the Laser-induced Breakdown Spectroscopy that are loaded with sample spectral characteristic, the Reyleith scanttering light be inspired and be loaded with the Raman spectrum of sample (3) material composition information and Laser-induced Breakdown Spectroscopy and entered by reflection and gather object lens (7), and collected object lens (7) converge to beam splitting system (8), light beam is divided into transmittance and reflectance two bundle after beam splitting system (8) light splitting, transmitted light path enters Laser-induced Breakdown Spectroscopy detection system (19) and obtains Laser-induced Breakdown Spectroscopy signal I (λ
l), folded light beam is through dichroic optical system (32) light splitting, and the Raman spectrum in reflected light enters Raman spectrum detection system (19) through dichroic optical system (32) and obtains raman spectral signal I (λ
r), the Reyleith scanttering light in folded light beam and Laser-induced Breakdown Spectroscopy are entered confocal detection system (15) by dichroic optical system (38) reflection,
3) light intensity detection is carried out to the light signal entering confocal detection system (15), measuring beam converges on point probe (11) through measuring lens (9), point probe (11) detection focused light spot near central regions light intensity signal, the distance that moves axially in conjunction with sample (3) obtains confocal curves (27), obtain confocal signal I (x, y, z,), utilize the characteristic that confocal curves peak point is corresponding with focal position, come localized excitation beam focus O position by peak point position, realize the focus location of sample;
4) control laser beam according to confocal signal I (x, y, z) accurately to focus on sample (3), again obtain the spectral signal I (λ of sample (3)
l) and I (λ
r);
5) utilize data handling system (21) by the confocal signal I (x, y, z) of acquisition, spectral signal I (λ
l) and I (λ
r) carry out Data Fusion, with four-dimensional metrical information I (x, y, z, the λ of the topographical information and material composition information that obtain sample
l, λ
r);
6) after completing above-mentioned steps, control light beam and scanning probe carried out to sample (3), step 2 is repeated to the next point in sample (3) surface), 3), 4), 5) until scanned;
7), when processing separately confocal signal I (x, y, z), the three-dimensional appearance information of the high-space resolution of sample (3) is obtained; Independent process raman spectral signal I (λ
r) time, obtain chemical bond and the molecular structure information of sample (3); Independent process Laser-induced Breakdown Spectroscopy signal I (λ
l) time, obtain the element composition information of sample (3); Process confocal signal I (x, y, z), spectral signal I (λ simultaneously
l) and I (λ
r) time, obtain the high-space resolution pattern of sample (3) and the imaging detection of microcell material composition " collection of illustrative plates unification ".
2. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection method according to claim 1, it is characterized in that: the point probe (11) in confocal detection system (15) can also be image capturing system, data handling system (21) obtains after focal spot pattern (16) from image capturing system, calculate the center of now focal spot pattern (16), and get focal spot pattern (16) immediate vicinity region and carry out light intensity detection, form confocal dummy pinhole (12), when sample (3) carry out axial scan move time, data handling system (21) calculates pixel grey scale summation in confocal dummy pinhole (12) scope, obtain the response of confocal axial strength.
3. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection method according to claim 1, it is characterized in that: measure focused spot size for compression and improve system transverse resolution, described excitation beam is light beam, comprises line polarisation, rotatory polarization, radial polarisation light; Or the structure light beam to be generated by pupil filtering technology.
4. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging detection method according to claim 1, is characterized in that: this system can also detect the scattering spectrum such as fluorescence, Compton scattering light.
5. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging sniffer, comprise light source (1), illumination objective lens (2) and collection object lens (7), it is characterized in that: also comprise collimator and extender mirror (25), light-beam scanner (26), beam splitting system (8), dichroic optical system (32), confocal detection device (15), Raman spectrum detection system (19) and Laser-induced Breakdown Spectroscopy detection system (33), wherein, layout is in measuring surface normal (5) both sides symmetrically for illumination objective lens (2) and collection object lens (7), and lighting optical axis (4) is θ with the angle of measuring surface normal (5)
1(6), gathering optical axis (20) with the angle of measuring surface normal (5) is θ
2(37), wherein θ
1=θ
2, collimator and extender mirror (25), light-beam scanner (26) and illumination objective lens (2) are successively placed on the emergent ray direction of light source (1), collection object lens (7) and beam splitting system (8) are successively placed on the reflection ray direction of sample (3), Laser-induced Breakdown Spectroscopy detection system (33) is placed on dichroic light-dividing device (8) transmission direction, dichroic optical system (32) and Raman spectrum detection system (19) are placed on the reflection direction of beam splitting system (8), confocal detection device (15) is placed on the reflection direction to look beam splitting system (32).
6. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging sniffer according to claim 5, it is characterized in that: for improving system transverse resolution, system also can add illumination end iris filter (28) between collimator and extender mirror (25) and illumination objective lens (2), or between dichroism beam splitting system (32) and measurement lens (9), add collection terminal iris filter (30), or between collimator and extender mirror (25) and illumination objective lens (2) and between dichroic optical system (32) and measurement lens (9), add illumination end iris filter (28) and collection terminal iris filter (30) simultaneously.
7. the laser dual-axis differential confocal induced breakdown-Raman spectrum imaging sniffer according to claim 5 or 6, it is characterized in that: for improving system transverse resolution, also can add polarization modulating arrangement (29) between collimator and extender mirror (25) and light-beam scanner (26), or add polarization modulating arrangement (29) between illumination objective lens (2) and illumination end iris filter (28).
8. the laser dual-axis differential confocal induced breakdown-Raman spectrum imaging sniffer according to claim 5 or 6 or 7, is characterized in that: the sniffer of confocal detection device (15) can point probe or ccd detector.
9. laser dual-axis differential confocal induced breakdown-Raman spectrum imaging sniffer according to claim 5, is characterized in that: also comprise the data handling system (21) of finally carrying out Data Fusion.
10. the laser dual-axis differential confocal induced breakdown-Raman spectrum imaging sniffer according to claim 5 or 6, the second detector (24) that it is characterized in that: Raman spectrum sniffer (19) can be confocal spectroscopic sniffer, comprise the first condenser (17), be positioned at after the pin hole (18) at the first condenser focus place, second condenser lens (22), the spectrometer (23) being positioned at second condenser lens (22) focus place and spectrometer (23); Second detector (24) that can also be common spectral detection device, comprise second condenser lens (22), be positioned at after the spectrometer (23) at second condenser lens (22) focus place and spectrometer (23); Laser-induced Breakdown Spectroscopy sniffer (33) comprises laser-induced breakdown condenser (35), be positioned at the pin hole (36) of laser-induced breakdown condenser (35) focal position, the spectrometer (37) after pin hole (36) and the 3rd detector (38).
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