CN109254072A - A kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method and device - Google Patents
A kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method and device Download PDFInfo
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Abstract
The present invention relates to a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method and devices, belong to confocal microscopic imaging, light spectrum image-forming and mass spectrum imaging field of measuring technique.Postposition is divided pupil laser differential confocal micro-imaging technique and spectrum by the present invention, mass spectrometry detection technology combines, the imaging of high-space resolution form is carried out to sample using the small focal beam spot of the postposition light splitting pupil differential confocal microscope handled through super resolution technology, microscopic spectrum detection is carried out to focal beam spot excitation spectrum using spectrum investigating system, using mass spectrometry detection system to sample microcell charged molecule, atom etc. carries out mass spectrometry detection, utilize the high-space resolution and highly sensitive imaging and detection of the mutual supplement with each other's advantages of the multispectral detection of laser and the complete component information of structure fusion realization sample microcell and morphological parameters.The present invention can be imaged for the fields form such as biomedicine, material science, mineral products, minute manufacturing and material composition detection provides a completely new effective technical way.
Description
Technical field
The invention belongs to confocal microscopic imaging technology, spectral imaging technology and mass spectrum imaging technical fields, and postposition is divided
Pupil laser differential confocal micro-imaging technique, Raman spectrum imaging technology, laser induced breakdown spectroscopy imaging technique and mass spectrum at
As technology combines, it is related to a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method and device, in biology
The fields such as medicine, material science, physical chemistry, mineral products, minute manufacturing have wide practical use.
Background technique
The method of material composition high-space resolution detection at present mainly has laser Raman spectroscopy Detection Techniques (Raman
Spectroscopy), laser induced breakdown spectroscopy Detection Techniques (LIBS, Laser Induced Breakdown
) and laser mass spectrometry Detection Techniques (Mass spectrometry) Spectroscopy.
Laser Raman spectroscopy Detection Techniques are a kind of Noninvasives based on raman scattering spectrum, obtain substance with no damage
The Detection Techniques of molecular characterization and ingredient go out the Raman different from laser wavelength of incidence using laser irradiation sample excitation
Spectrum detects sample chemical key and molecule knot by information such as spectral peak frequency displacement, spectral strength and the width of detection Raman spectrum
Structure information, and then material molecule component and form are obtained, outstanding advantage is detectable molecular chemical bond, molecular structure and molecule
Component information.
Laser induced breakdown spectroscopy Detection Techniques are a kind of based on atomic emission spectrum and Laser Plasma Emission Spectrum
Element detection technology produce the few some materials of sample surfaces using the laser action of high power density in sample surfaces
Raw laser induced plasma obtains substance by the atom and ion emission spectroscopy in exploring laser light induced plasma
Atom and small molecule element form information, and then determine that the group of sample is grouped as, and outstanding advantage is detectable atom and small point
The element composition of son.
Laser mass spectrometry Detection Techniques are a kind of high specific based on plasma exciatiaon and highly sensitive microelement
Detection Techniques realize that substance ionizes using laser irradiation sample, and to the ion acceleration after ionization, by detecting different ions
Charge-mass ratio and quantity determine sample component, and outstanding advantage is the elements such as detectable charged ion, molecular fragment composition, can be real
The accurate detection of existing complex sample component information.
In above-mentioned three kinds of laser component Detection Techniques, laser Raman spectroscopy technology can identify material composition but not be capable of measuring
Element in sample, laser induced breakdown spectroscopy can measure material element but be not capable of measuring sample molecule structure, laser matter
Although spectral technology detectivity is high but can only identify the elements such as charged ion, molecular fragment after ionization.
With deepening continuously for the researchs such as life science, material science, physical chemistry, environmental science and deep space exploration, such as
What realizes that the complete component information high-resolution of sample microcell substance, highly sensitive detection are that current laser component field of detecting is urgently ground
The significant problem studied carefully has great background demand in fields such as biomedicine, physical chemistry, material engineering and deep space explorations.
In recent years, with the fast development of pulsed laser technique, only by adusting the wavelength of focusing pulse light beam, pulsewidth and
(excitating surface plasma is than needed for excitation scattering spectrum for the scattering spectrum and surface plasmons that intensity can inspire sample
Luminous intensity it is big), sample can be made to scatter Raman spectrum, induced breakdown spectroscopy, and atom, the molecule, molecular fragment of electrification
With neutral atom, molecule, intermediate ion etc..Currently, how completely to obtain sample microcell with location point Raman spectrum, induction
Breakdown spectral, and the atom of electrification, molecule, molecular fragment and neutrality the information such as atom, molecule, intermediate ion, for sample
The complete acquisition of component information plays an important role.
Can good fortune, laser Raman spectroscopy, laser induced breakdown spectroscopy and laser mass spectrometry homologous (laser) excitation with
The complementary detection of multispectral (laser Raman spectroscopy, laser induced breakdown spectroscopy and laser mass spectrometry) component information, is complete group of sample
The detection of point information provides possibility.This is possible to laser Raman spectroscopy technology, laser induced breakdown spectroscopy Detection Techniques
It is organically combined with laser mass spectrometry Detection Techniques, detects sample material molecular structure and chemistry using laser Raman spectroscopy detection system
Key information utilizes matter using the atom spectrum of laser induced breakdown spectroscopy system detecting material element and part small molecule information
The charged ion and molecular radical information that detection system detection breakdown ionization sample plasma generates are composed, and then it is micro- to reach substance
The high-space resolution of the complete component information in area detects.Meanwhile the imaging of laser scanning confocal microscopy " point illumination " and " point detection " is visited
Survey mechanism not only makes its transverse resolution improve 1.4 times compared with the optical microscopy of equivalent parameters, but also makes confocal microscope pole
Convenient for, in conjunction with focal beam spot is compressed, being further realized with super-resolution pupil filtering technique, radial polarisation light tightly focused technology etc.
The high spatial excitation of sample micro-area information and high-resolution detection etc..
Based on above-mentioned analysis, the present invention proposes the micro- one kind for focusing excitation and detection of postposition light splitting pupil laser differential confocal
Laser differential confocal Raman-LIBS- mass spectrometry micro imaging method and device, innovation are: will have high spatial for the first time
The postposition light splitting pupil laser differential confocal microtechnic and laser Raman spectroscopy technology, laser induced breakdown spectroscopy of resolution capability
(LIBS) technology and mass spectrometry detection technology blend, it can be achieved that sample microcell high-space resolution and highly sensitive pattern and component
Imaging and detection.
A kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method of the present invention and device can be biology doctor
The pattern component imaging detection in the fields such as, material science, physical chemistry, mineral products, minute manufacturing provide one it is completely new effective
Technological approaches.
Summary of the invention
The purpose of the invention is to improve the spatial resolving power of mass spectrum imaging, inhibit focal beam spot phase in imaging process
Drift to sample proposes a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method and device, to same
When obtain sample micro-raman spectra information and component information.The present invention focuses postposition light splitting pupil laser differential confocal microscope
The detecting function of hot spot focuses desorption ionization function with laser and blends, and is swashed using the postposition light splitting pupil handled through super resolution technology
The small focal beam spot of light differential confocal microscope carries out the imaging of high-space resolution pattern to sample, utilizes Raman spectroscopic detection system
The Raman spectrum generated to postposition light splitting pupil confocal microscope system focal beam spot excitation sample of uniting detects, and utilizes mass spectrograph pair
Charged molecule, the atom etc. that postposition is divided pupil laser differential confocal microscopic system focal beam spot desorption ionization sample and generates carry out
Microcell mass spectrum imaging focuses postposition light splitting pupil laser differential confocal microscopic system using laser induced breakdown spectroscopy detection system
Hot spot desorption ionization sample and the plasma emission spectroscopy information that generates carries out laser induced breakdown spectroscopy imaging, then lead to again
The fusion of detection data information and the sample composition information for comparing acquisition completion are crossed, then realizes sample microcell high spatial point
Distinguish the imaging and detection with highly sensitive pattern, component.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method of the invention utilizes high spatial point
It distinguishes that the focal beam spot of postposition light splitting pupil laser differential confocal microscopic system carries out axial fixed-focus and imaging to sample, utilizes Raman light
The Raman spectrum that detection system generates postposition light splitting pupil laser differential confocal microscopic system focal beam spot excitation sample is composed to carry out
Detection desorbs postposition light splitting pupil laser differential confocal microscopic system focal beam spot using laser induced breakdown spectroscopy detection system
Ionized sample and the plasma emission spectroscopy generated is detected, it is aobvious to postposition light splitting pupil laser differential confocal using mass spectrograph
Micro-system focal beam spot desorption ionization sample and charged molecule, atom for generating etc. carry out microcell mass spectrum imaging, then pass through again
The fusion of detection data information then realizes sample microcell high-space resolution and highly sensitive pattern and component with analysis is compared
Imaging and detection, comprising the following steps:
Step 1: the excitation beam of point light source outgoing, is collimated light beam by collimation lens collimation, collimated light beam passes through pressure
Polycondensation coke spot system, successively through Amici prism transmission, dichroscope A reflection after, focused on sample by measurement object lens, excite
It is loaded with the Raman diffused light of sample microcell characterisitic parameter information out, while reflecting Rayleigh scattering light；
Step 2: making computer control precise three-dimensional working platform that sample be driven to measure near object focal point along measuring surface
Lower movement；The Raman diffused light and Rayleigh scattering light for being loaded with sample message are collected by measurement object lens, are by dichroscope A points
Two beams, wherein the Rayleigh scattering light reflected by dichroscope A is divided pupil laser differential after Amici prism reflects, by postposition
Confocal detection system acquisition, after collecting object lens and collecting pupil focusing, hot spot is amplified by relaying amplifying lens, light intensity letter
It number is acquired by dual-quadrant detector；The the first detection quadrant and the second detection quadrant of dual-quadrant detector are about acquisition optical axis pair
Claim；Dual-quadrant detector amplification Airy amplified to relayed amplifying lens is split detection, respectively obtains Airy
The strength characteristics of the second microcell of first microcell and Airy, i.e., the first off-axis axial strength curve and the second off-axis axial direction are strong
It writes music line；
Step 3: the first off-axis axial strength curve and the second off-axis axial strength curve, which are subtracted each other processing, obtains postposition point
Pupil laser differential confocal axial strength curve can accurately be determined using postposition light splitting pupil laser differential confocal axial strength curve
The microcell axial height information of position sample；
Step 4: " zero crossing " position control of computer according to postposition light splitting pupil laser differential confocal axial strength curve
Precision three-dimensional workbench drives sample to move along measuring surface normal direction, focuses on the focal beam spot for measuring object lens on sample；
Step 5: at the same time, entering after dichroscope B reflection by the Raman diffused light of dichroscope A transmission
Into Raman spectroscopic detection system, the sample chemical key and molecular structure information in corresponding focal beam spot region are measured；
Step 6: changing the operating mode of point light source, illumination intensity is improved, the microcell desorption ionization of sample is excited to generate etc.
Ion body feathers, part plasma plume are detected by ion suction pipe by mass spectrograph, and the mass spectrum letter in corresponding focal beam spot region is measured
Breath；
Step 7: plasma plume, which is buried in oblivion, issues LIBS spectrum, LIBS spectrum is saturating by dichroscope A and dichroscope B
It after penetrating, is detected by LIBS spectrum investigating system, measures the sample element composition information that sample corresponds to focal beam spot region；
Step 8: the laser focal beam spot position sample that computer measures postposition light splitting pupil laser differential confocal detection system
Product elevation information, the Raman spectral information of the laser focusing microcell of Raman spectroscopic detection system detection, LIBS spectrum investigating system
The Information in Mass Spectra that the laser that LIBS spectral information, the mass spectrograph that the laser of detection focuses microcell measure focuses microcell carries out at fusion
Reason, then obtains height, spectrum and the Information in Mass Spectra of focal beam spot microcell；
Step 9: computer control precise three-dimensional working platform makes the next area to be measured for measuring object focal point alignment sample
Then domain is operated by step 1~step 8, obtain height, spectrum and the Information in Mass Spectra of next focal zone to be measured；
Measured Step 10: repeating step 9 until all tested points on sample, then using computer at
Sample morphology information and complete component information can be obtained in reason.
The method of the present invention includes can be to make collimated light beam by being shaped as after vector beam generating system, iris filter
Annular beam, the annular beam are measured object lens again and focus on desorption ionization generation plasma plume on sample.
In method of the invention, D type collects pupil can be by circular collection pupil or the pupil of other shapes come complete
At.
In the method for the present invention, that the object lens of the measurement to different NA can be realized only is handled by computer system software
Match, without carrying out any hardware adjustment to system.
The present invention provides a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging devices, comprising: point light
Source, measurement object lens, precision three-dimensional workbench, Amici prism, dichroscope A, dichroscope B, postposition light splitting pupil laser differential are total
Burnt detection system, Raman spectroscopic detection system, LIBS spectrum investigating system, mass spectrograph and computer.
In apparatus of the present invention, postposition is divided pupil laser differential confocal detection system can be by collection object lens, collection pupil, relaying
Amplifying lens and dual-quadrant detector are constituted, wherein the first detection quadrant on dual-quadrant detector test surface and the second detection as
It limits symmetrical about optical axis.
In apparatus of the present invention, postposition be divided pupil laser differential confocal detection system can also by collection object lens, collect pupil, in
It is constituted after amplifying lens and ccd detector, the first microcell of Airy and Airy second that wherein ccd detector detects are micro-
Area, it is symmetrical about optical axis.
Apparatus of the present invention include that compression focal beam spot system can use the generation vector beam placed along incident light axis direction
Vector beam generator and iris filter substitution.
The point light source of apparatus of the present invention can be replaced by the Optic transmission fiber of pulse laser, collector lens and collector lens focal point
Generation；Meanwhile outgoing beam attenuator is introduced in laser focusing system, in postposition light splitting pupil laser differential confocal detection system
Introduce detection beam attenuator；Light intensity regulating system is constituted by outgoing beam attenuator and detection beam attenuator, to adapt to sample
Light intensity demand when product surface positions.
Beneficial effect
The present invention, which compares existing technology, has following remarkable advantage:
1) " zero crossing " and high-acruracy survey object lens of pupil laser differential confocal axial response curve are divided by postposition
Focus accurately corresponds to this characteristic, realizes accurate fixed-focus to sample, can inhibit existing mass spectrograph because of long-time mass spectrum imaging
Drifting problem of the middle focal beam spot with respect to sample；
2) detection of Raman spectrum and laser induced breakdown spectroscopy is combined, overcoming existing laser mass spectrometry instrument can not be to neutrality
The deficiency that atom, molecule, intermediate ion and group etc. are detected, realization laser is multispectral, and (mass spectrum, Raman spectrum and induced with laser are hit
Wear spectrum) mutual supplement with each other's advantages of component imaging detection and structure function fusion, more comprehensively microcell component information can be obtained；
3) the preparatory fixed-focus of sample is carried out using " zero crossing " of postposition light splitting pupil laser differential confocal curve, makes minimum focusing
Hot spot focuses on sample surfaces, it can be achieved that sample microcell high-space resolution mass spectrometry detection and microcell micro-imaging, effectively play
The potential differentiated between postposition light splitting pupil laser differential confocal system altitude；
4) using compression focal beam spot technology, the spatial resolving power of laser mass spectrometry instrument is improved；
5) signal is obtained due to the method using division focal spot, it can be set micro- on system detection focal plane by changing
The parameter of zonule is to match the reflectivity of different samples, so as to extend its application field；Computer can also only be passed through
System software processing realizes that the matching of the measurement object lens to different NA values has without carrying out any hardware adjustment to system again
Conducive to the versatility for realizing instrument.
Detailed description of the invention
Fig. 1 is a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method schematic diagram of the present invention；
Fig. 2 is a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging device schematic diagram of the present invention；
Fig. 3 is a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging device schematic diagram of the present invention；
Fig. 4 is that postposition is divided pupil laser differential confocal axial strength simulation curve；
Fig. 5 is that postposition is divided pupil laser differential confocal axial strength measured curve；
Wherein: 1- point light source, 2- collimation lens, 3- collimated light beam, 4- compress focal beam spot system, 5- Amici prism, 6-
Dichroscope A, 7- measure object lens, 8- sample, 9- plasma plume, 10- precision three-dimensional workbench, 11- and collect object lens, 12-D type
Collect pupil, 13- postposition light splitting pupil laser differential confocal detection system, 14- relaying amplifying lens, 15- dual-quadrant detector,
16- first detects quadrant, 17- second detects quadrant, 18- amplifies Airy, the first microcell of 19- Airy, 20- Airy second
Microcell, the off-axis axial strength curve of 21- first, the off-axis axial strength curve of 22- second, 23- postposition light splitting pupil laser differential are total
Focal axis is visited to intensity curve, 24- dichroscope B, 25- Raman spectroscopic detection system, 26- Raman-Coupled lens, 27- Raman spectrum
Survey device, 28-LIBS spectrum investigating system, 29-LIBS coupled lens, 30-LIBS spectral detector, 31- ion suction pipe, 32- matter
Spectrometer, 33- computer, 34- vector optical generator, 35- iris filter, 36- circular collection pupil, 37-CCD detector, 38-
Pulse laser, 39- collector lens, 40- Optic transmission fiber, 41- outgoing beam attenuator, 42- detection beam attenuator, 43- the
One off-axis axial strength measured curve, the off-axis axial strength measured curve of 44- second, 45- postposition are divided pupil laser differential confocal
Axial strength measured curve.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and examples.
Embodiment 1
As shown in Figure 1, the excitation beam that point light source 1 is emitted, is collimated light beam 3, collimated light beam by the collimation of collimation lens 2
3, by compression focal beam spot system 4, successively after the transmission of Amici prism 5, dichroscope A6 reflection, are focused on by measurement object lens 7
On sample 8, the Raman diffused light for being loaded with sample microcell characterisitic parameter information is inspired, while reflecting Rayleigh scattering light；
So that computer 33 is controlled precision three-dimensional workbench 10 drives sample 8 along measuring surface on measurement 7 near focal point of object lens
Lower movement；The Raman diffused light and Rayleigh scattering light for being loaded with 8 information of sample are collected by measurement object lens 7, by dichroscope A6
It is divided into two bundles, wherein the Rayleigh scattering light reflected by dichroscope A6 after the reflection of Amici prism 5, is swashed by postposition light splitting pupil
The equation of light is moved confocal detection system 13 and is acquired, and after collecting object lens 11 and the collection focusing of pupil 12 of D type, hot spot is amplified by relaying
Lens 14 amplify；Light intensity signal is acquired by dual-quadrant detector 15；First detection quadrant 16 and second of dual-quadrant detector 15
It is symmetrical about acquisition optical axis to detect quadrant 17；Dual-quadrant detector 15 is to the amplified amplification Airy of relayed amplifying lens 14
18 are split detection, the x in amplification Airyd' tiny area, the first microcell of Airy 19 and Airy are set on axis
Two microcells 20, two microcells are about yd' axle offset vM, the strength characteristics for measuring the two regions are respectively the first off-axis axis
To intensity curve 21IA(u,vM) and the second off-axis axial strength curve 22IB(u,-vM), two curves are differential to be subtracted each other, after obtaining
Set light splitting pupil laser differential confocal axial strength curve 23I (u, v)；
I(u,vM)=IA(u,vM)-IB(u,-vM)；
Wherein, u is axial normalization optical coordinate, vMFor pin hole axial offset.Pupil laser differential is divided using postposition
Confocal axial strength curve 23 can be accurately positioned the microcell axial height information of sample 8.Fig. 5 is that postposition is divided pupil laser differential
Confocal axial strength measured curve, wherein 43 be the first off-axis axial strength measured curve, 44 be that the second off-axis axial strength is real
Survey curve, 45 are divided pupil laser differential confocal axial strength measured curve for postposition；
" zero crossing " position control essence of the computer 33 according to postposition light splitting pupil laser differential confocal axial strength curve 23
Close three-dimensional working platform 10 drives sample 8 to move along measuring surface normal direction, and the focal beam spot for measuring object lens 7 is made to focus on sample 8
On；
At the same time, drawing is entered after dichroscope B24 reflection by the Raman diffused light of dichroscope A6 transmission
In graceful spectrum investigating system 25, the sample chemical key and molecular structure information in corresponding focal beam spot region are measured；
Change the operating mode of point light source 1, improve illumination intensity, the microcell desorption ionization of excitation sample 8 generates plasma
Body feathers 9, part plasma plume 9 are detected by ion suction pipe 31 by mass spectrograph 32, and the mass spectrum in corresponding focal beam spot region is measured
Information；
Plasma plume, which is buried in oblivion, issues LIBS spectrum, and LIBS spectrum is by dichroscope A6 transmission, dichroscope B24 transmission
Afterwards, it is detected by LIBS spectrum investigating system 28, measures the sample element composition information in the corresponding focal beam spot region of sample 8；
The laser focal beam spot position sample that computer 33 measures postposition light splitting pupil laser differential confocal detection system 13
The laser that elevation information, Raman spectroscopic detection system 25 detect focuses the Raman spectral information of microcell, LIBS spectrum investigating system
The Information in Mass Spectra that the laser that LIBS spectral information, the mass spectrograph 32 that the laser of 28 detections focuses microcell measure focuses microcell is melted
Conjunction processing, then obtains height, spectrum and the Information in Mass Spectra of focal beam spot microcell；
Embodiment 2
As shown in Figure 2: in a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging device, compression is focused
Spot system 4 is substituted by vector beam generating system 34 and iris filter 35, and D type collects pupil 12 can be by circular collection pupil
36 substitutions, dual-quadrant detector 15 are substituted by ccd detector 37, the first microcell of Airy 19 that wherein ccd detector 37 detects
It is symmetrical about optical axis with the second microcell of Airy 20.
Remaining imaging method and process are same as Example 1.
Embodiment 3
It is as shown in Figure 3: in a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging device, point light source 1 by
Pulse laser 38, collector lens 39 and Optic transmission fiber 40 substitute；Optic transmission fiber 40 is located at the focal point of collector lens 39, is used for
Light conduction.Meanwhile outgoing beam attenuator 41 is introduced in laser focusing system, it is visited in postposition light splitting pupil laser differential confocal
Detection beam attenuator 42 is introduced in examining system.Light intensity regulating is constituted by outgoing beam attenuator 41 and detection beam attenuator 42
System, to adapt to light intensity demand when sample surfaces positioning.
Remaining imaging method and process are same as Example 1.
A specific embodiment of the invention is described in conjunction with attached drawing above, but these explanations cannot be understood to limit
The scope of the present invention.Protection scope of the present invention is limited by appended claims, any in the claims in the present invention base
Change on plinth is all protection scope of the present invention.
Claims (9)
1. a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method, it is characterised in that: utilize high spatial point
It distinguishes that the focal beam spot of postposition laser differential confocal microscopic system carries out axial fixed-focus and imaging to sample, utilizes Raman spectroscopic detection
The Raman spectrum that system generates confocal microscope system focal beam spot excitation sample detects, using mass spectrometry detection system to sharp
The equation of light move confocal microscope system focal beam spot desorption ionization sample and charged molecule, atom for generating etc. carry out microcell mass spectrum at
Picture is divided pupil laser differential confocal microscopic system focal beam spot to postposition using laser-induced breakdown (LIBS) spectrum investigating system
Desorption ionization sample and the plasma emission spectroscopy generated is detected, then again by the fusion of detection data information with than
The imaging and detection of sample microcell high-space resolution and highly sensitive form and component are then realized to analysis.
The following steps are included:
Step 1: the excitation beam of light source outgoing, is collimated light beam (3) by collimation lens (2) collimation, collimated light beam (3) is logical
Overcompression focal beam spot system (4), successively through Amici prism (5) transmission, dichroscope A (6) reflection after, by measurement object lens (7)
It focuses on sample (8), inspires the Raman diffused light for being loaded with sample microcell characterisitic parameter information, while reflecting Rayleigh scattering
Light；
Step 2: computer (33) control precision three-dimensional workbench (10) is made to drive sample (8) along measuring surface in measurement object lens (7)
Near focal point moves up and down；The Raman diffused light and Rayleigh scattering light for being loaded with sample (8) information are collected by measurement object lens (7),
It is divided into two bundles by dichroscope A (6), wherein passing through Amici prism (5) by the Rayleigh scattering light that dichroscope A (6) are reflected
After reflection, by postposition light splitting pupil laser differential confocal detection system (13) acquisition, light is collected by collecting object lens (11) and D type
After pupil (12) focuses, hot spot is amplified by relaying amplifying lens (14), and light intensity signal is acquired by dual-quadrant detector (15)；Two quadrant
The first detection quadrant (16) and the second detection quadrant (17) of detector (15) are symmetrical about acquisition optical axis；Dual-quadrant detector
(15) detection is split to the amplified amplification Airy of relayed amplifying lens (14) (18), respectively obtains Airy first
The strength characteristics of the off-axis axial strength curve (21) of strength characteristics first of microcell (19), the second microcell of Airy (20) is bent
The off-axis axial strength curve (22) of line second；
Step 3: the first off-axis axial strength curve (21) and the second off-axis axial strength curve (22) are subtracted each other after processing obtains
Light splitting pupil laser differential confocal axial strength curve (23) is set, is divided pupil laser differential confocal axial strength curve using postposition
(23) it can be accurately positioned the microcell axial height information of sample (8)；
Step 4: " zero crossing " position of computer (33) according to postposition light splitting pupil laser differential confocal axial strength curve (23)
Control precision three-dimensional workbench (10) drives sample (8) to move along measuring surface normal direction, makes the focal beam spot for measuring object lens (7)
It focuses on sample (8)；
Step 5: at the same time, the Raman diffused light by dichroscope A (6) transmission reflects laggard by dichroscope B (24)
Enter in Raman spectroscopic detection system (25), measures the sample chemical key and molecular structure information in corresponding focal beam spot region；
Step 6: changing the operating mode of point light source (1), illumination intensity is improved, the microcell desorption ionization of excitation sample (8) generates
Plasma plume (9), part plasma plume (9) are detected by ion suction pipe (31) by mass spectrograph (32), and corresponding focusing is measured
The Information in Mass Spectra of spot area；
Step 7: plasma plume, which is buried in oblivion, issues LIBS spectrum, LIBS spectrum passes through dichroscope A (6) and dichroscope B (24)
It after transmission, is detected by LIBS spectrum investigating system (28), measures the sample element group in sample (8) corresponding focal beam spot region
At information；
Step 8: the laser focal beam spot position that computer (33) measures postposition light splitting pupil laser differential confocal detection system (13)
Set height of specimen information, the laser of Raman spectroscopic detection system (25) detection focuses the Raman spectral information of microcell, LIBS spectrum
The laser that LIBS spectral information, the mass spectrograph (32) that the laser of detection system (28) detection focuses microcell measure focuses the matter of microcell
Spectrum information carries out fusion treatment, then obtains height, spectrum and the Information in Mass Spectra of focal beam spot microcell；
Step 9: computer (33) control precision three-dimensional workbench (10) makes to measure the next of object lens (7) focus alignment sample (8)
A region to be measured, is then operated by step 1~step 8, and height, spectrum and the matter of next focal zone to be measured are obtained
Spectrum information；
Step 10: repetition step 9 is measured until all tested points on sample (8), then computer (34) is utilized to carry out
Sample morphology information and complete component information can be obtained in processing.
2. a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method according to claim 1, special
Sign is: the compression focal beam spot system (4) can be substituted by vector optical generator (34) and iris filter (35)；It is described
Vector optical generator (34) is placed between collimation lens (2) and Amici prism (5)；The iris filter (35) is placed in light splitting rib
Between mirror (5) and dichroscope A (6).
3. a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method according to claim 1, special
Sign is: the light source is point light source (1) or pulse laser (38), collector lens (39) and Optic transmission fiber (40)；The biography
Light optical fiber (40) is located at the focal point of collector lens (39), is used for light conduction.
4. a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method according to claim 1, special
Sign is: the shape that the D type collects pupil (12) can be by circular collection pupil (36) or the pupil of other shapes Lai complete
At.
5. realizing a kind of laser differential confocal Raman-LIBS- mass spectrometry micro imaging method as described in claim 1
Device: it is characterized by comprising generate the point light source (1) of excitation beam, measurement object lens (7), precision three-dimensional workbench (10), divide
Light prism (5), dichroscope A (6), dichroscope B (24), postposition are divided pupil laser differential confocal detection system (13), Raman
Spectrum investigating system (25), LIBS spectrum investigating system (28), mass spectrograph (32) and computer (33).
Postposition light splitting pupil laser differential confocal detection system (13) include collect object lens (11), D type collect pupil (12), in
Wherein after amplifying lens (14) and dual-quadrant detector (15), D collects pupil (12) and is placed on the pupil plane for collecting object lens (11)
On；
The Raman spectroscopic detection system (25) includes Raman-Coupled lens (26) and Raman spectroscopy detector (27)；
The LIBS spectrum investigating system (28) includes LIBS coupled lens (29) and LIBS spectral detector (30)；
Sample (8) is placed on precision three-dimensional workbench (10)；The excitation beam of point light source (1) outgoing, by collimation lens (2) standard
Directly be collimated light beam (3), collimated light beam (3) by compression focal beam spot system (4), successively through Amici prism (5) transmission, two to
After Look mirror A (6) reflection, is focused on sample (8) by measurement object lens (7), inspire and be loaded with sample microcell characterisitic parameter information
Raman diffused light, while reflecting Rayleigh scattering light；Raman diffused light and Rayleigh scattering light are collected by measurement object lens (7), warp
It crosses dichroscope A (6) to be divided into two bundles, wherein the Rayleigh scattering light reflected by dichroscope A (6) is anti-by Amici prism (5)
After penetrating, by postposition light splitting pupil laser differential confocal detection system (13) acquisition；The Raman scattering transmitted by dichroscope A (6)
Light enters in Raman spectroscopic detection system (25) after dichroscope B (24) are reflected；Change the Working mould of point light source (1)
Formula improves illumination intensity, and the microcell desorption ionization of excitation sample (8) generates plasma plume (9), part plasma plume (9)
It is detected by ion suction pipe (31) by mass spectrograph (32)；Plasma plume (9), which is buried in oblivion, issues LIBS spectrum, and LIBS spectrum passes through two
To Look mirror A (6) transmission, dichroscope B (24) transmission, detected by LIBS spectrum investigating system (28).
6. a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging device according to claim 5, special
Sign is: postposition be divided pupil laser differential confocal detecting module (13) can by collection object lens (11), D type collect pupil (12), in
Constituted after amplifying lens (14) and dual-quadrant detector (15), wherein the first detection on dual-quadrant detector (15) test surface as
It limits (16) and the second detection quadrant (17) is symmetrical about optical axis.
7. a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging device according to claim 5, special
Sign is: dual-quadrant detector (15) can be substituted by ccd detector (37), wherein the Airy of ccd detector (37) detection
First microcell (19) and the second microcell of Airy (20), it is symmetrical about optical axis.
8. a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging device according to claim 5, special
Sign is: point light source (1) can be substituted by pulse laser (39), collector lens (40) and Optic transmission fiber (41)；Optic transmission fiber
(41) it is located at the focal point of collector lens (40), is used for light conduction.
9. a kind of laser differential confocal Raman-LIBS- mass spectrometry microscopic imaging device according to claim 5, special
Sign is: further including the Light intensity regulating system being made of outgoing beam attenuator (41) and detection beam attenuator (42), with suitable
Light intensity demand when sample surfaces being answered to position；The outgoing beam attenuator (41) is placed in collimation lens (2) and light splitting rib
Any position between mirror (5)；The detection beam attenuator (42) is placed in Amici prism (5) and collects between object lens (11).
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