CN109254071A - A kind of confocal laser Raman-LIBS- mass spectrometry micro imaging method and device - Google Patents
A kind of confocal laser Raman-LIBS- mass spectrometry micro imaging method and device Download PDFInfo
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Abstract
The present invention relates to a kind of confocal laser 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 confocal laser 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 confocal microscope handled through super resolution technology, using spectrum investigating system to focal beam spot excitation spectrum (Raman spectrum, induced breakdown spectroscopy) carry out microscopic spectrum detection, using mass spectrograph 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 provide a completely new effective technical way for the fields material composition such as biomedicine, material science and form imaging detection.
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 confocal laser micro-imaging technique, laser induced breakdown spectroscopy imaging technique, Raman spectrum imaging technology and mass spectrum imaging skill
Art combines, and is related to a kind of confocal laser Raman-LIBS- mass spectrometry micro imaging method and device, in biomedical, material
The fields such as 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 a kind of micro- laser for focusing excitation and detection of postposition light splitting pupil confocal laser
Confocal Raman-LIBS- mass spectrometry micro imaging method and device, innovation are: will have high-space resolution ability for the first time
Postposition light splitting pupil confocal laser microtechnic and laser Raman spectroscopy technology, laser induced breakdown spectroscopy (LIBS) technology and matter
Spectrum Detection Techniques blend imaging and detection, it can be achieved that sample microcell high-space resolution and highly sensitive pattern and component.
A kind of confocal laser Raman-LIBS- mass spectrometry micro imaging method of the present invention and device can for it is biomedical,
The pattern component imaging detection in the fields such as material science, physical chemistry, mineral products, minute manufacturing provides a completely new effective technology
Approach.
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 confocal laser Raman-LIBS- mass spectrometry micro imaging method and device, to obtain simultaneously
Obtain measurand micro-raman spectra information and component information.Postposition is divided the spy of pupil laser scanning confocal microscopy focal beam spot by the present invention
Brake focuses desorption ionization function with laser and blends, aobvious using the postposition light splitting pupil confocal laser handled through super resolution technology
The small focal beam spot of micro mirror carries out the imaging of high-space resolution pattern to sample, is divided using Raman spectroscopic detection system to postposition
The Raman spectrum that pupil confocal laser microscopic system focal beam spot excitation sample generates is detected, and laser induced breakdown spectroscopy is utilized
The plasma emission that detection system generates postposition light splitting pupil confocal laser microscopic system focal beam spot desorption ionization sample
Spectral information carries out laser induced breakdown spectroscopy imaging, is divided pupil confocal laser microscopic system to postposition using mass spectrometry detection system
Focal beam spot desorption ionization sample and charged molecule, atom for generating etc. carry out microcell mass spectrum imaging, then pass through detection number again
It is believed that the fusion of breath and the sample composition information for comparing acquisition completion, then realize sample microcell high-space resolution and Gao Ling
The imaging and detection of quick pattern, component.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of confocal laser Raman-LIBS- mass spectrometry micro imaging method of the invention, after high-space resolution
The focal beam spot for setting light splitting pupil confocal laser microscopic system carries out axial fixed-focus and imaging to sample, utilizes Raman spectroscopic detection system
The Raman spectrum generated to postposition light splitting pupil confocal laser microscopic system focal beam spot excitation sample of uniting detects, and utilizes laser
Induced breakdown spectroscopy detection system is divided pupil confocal laser microscopic system focal beam spot desorption ionization sample to postposition and generates
Plasma emission spectroscopy is detected, and is divided pupil confocal laser microscopic system focal beam spot to postposition using mass spectrometry detection system
Desorption ionization sample and charged molecule, atom for generating etc. carry out microcell mass spectrum imaging, then pass through detection data information again
Merge and compare imaging and detection that sample microcell high-space resolution and highly sensitive pattern and component are then realized in analysis, packet
Include 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: computer control precise three-dimensional working platform drives sample measuring near object focal point up and down along measuring surface
It is mobile；The Raman diffused light and Rayleigh scattering light for being loaded with sample message are collected by measurement object lens, and being divided to by dichroscope A is two
Beam, wherein the Rayleigh scattering light reflected by dichroscope A after Amici prism reflects, is visited by postposition light splitting pupil confocal laser
Examining system acquisition, after collecting object lens and collecting pupil focusing, hot spot is amplified by relaying amplifying lens, and amplification Airy is saturating
The light intensity signal of needle passing hole, search coverage is acquired by light intensity detector, obtains postposition light splitting pupil confocal laser axial strength curve；
Step 3: axial high using the microcell that postposition light splitting pupil confocal laser axial strength curve can be accurately positioned sample
Spend information；
Step 4: " extreme point " the accurately corresponding measurement of computer according to postposition light splitting pupil confocal laser axial strength curve
This characteristic of object lens focal beam spot focus, control precision three-dimensional workbench drive sample to move along measuring surface normal direction, make to survey
The focal beam spot of amount object lens focuses 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 transmitted by dichroscope A and dichroscope
It after B transmission, is detected by LIBS spectrum investigating system, measures the sample element composition letter that sample corresponds to focal beam spot region
Breath；
Step 8: the laser focal beam spot position sample that computer measures postposition light splitting pupil confocal laser detection system is high
Spend information, the laser of Raman spectroscopic detection system detection focuses the Raman spectral information of microcell, the detection of LIBS spectrum investigating system
Laser focus the laser that measures of LIBS spectral information, mass spectrograph of microcell and focus the Information in Mass Spectra of microcell and carry out fusion treatment,
Then height, spectrum and the Information in Mass Spectra of focal beam spot microcell are obtained；
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 measure object lens again and focus on desorption ionization generation plasma plume on sample.
In method of the invention, D type, which collects pupil, can pass through circular collection pupil or the collection pupil of other shapes
To complete.
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 confocal laser Raman-LIBS- mass spectrometry microscopic imaging devices, including light source, measurement
Object lens, three-dimensional precision worktable, Amici prism, dichroscope A, dichroscope B, postposition light splitting pupil confocal laser detection system,
Raman spectroscopic detection system, LIBS spectrum investigating system, mass spectrograph, computer.
In apparatus of the present invention, postposition, which is divided pupil confocal laser detection system, to be amplified by collection object lens, collection pupil, relaying
Lens, pin hole and light intensity detector are constituted, and wherein pin hole is located in the image planes of relaying amplifying lens.
In apparatus of the present invention, postposition light splitting pupil confocal laser detection system can also be put by collection object lens, collection pupil, relaying
Big lens and ccd detector are constituted, and wherein search coverage is located at the image plane center of ccd detector.
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, collector lens focal point
Generation；Meanwhile outgoing beam attenuator is introduced in laser focusing system, it is introduced in postposition light splitting pupil confocal laser detection system
Detect beam attenuator；Light intensity regulating system is constituted by outgoing beam attenuator and detection beam attenuator, to adapt to sample table
Light intensity demand when face positions.
Beneficial effect
1) pass through high axial " extreme point " and high-acruracy survey differentiated postposition and be divided pupil confocal laser axial strength curve
The focus of object lens accurately corresponds to this characteristic, realizes accurate fixed-focus to sample, can inhibit existing mass spectrograph because long-time mass spectrum at
Drifting problem of the focal beam spot with respect to sample as in；
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) preparatory using high axial " extreme point " progress sample for differentiating postposition light splitting pupil confocal laser axial strength curve
Fixed-focus makes minimum focal beam spot focus on sample surfaces, it can be achieved that sample microcell high-space resolution mass spectrometry detection and microcell are micro-
Imaging effectively plays the potential differentiated between postposition light splitting pupil confocal laser 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, can be detected on focal plane by changing in image detection system
The parameter of set tiny area is to match the reflectivity of different samples, so as to extend its application field；It can be with
Only by computer system software handle can be realized to different NA values measurement object lens matching, without again to system into
Any hardware adjustment of row, is advantageously implemented the versatility of instrument.
Detailed description of the invention
Fig. 1 is a kind of confocal laser Raman-LIBS- mass spectrometry micro imaging method schematic diagram of the present invention；
Fig. 2 is a kind of confocal laser Raman-LIBS- mass spectrometry microscopic imaging device schematic diagram of the present invention；
Fig. 3 is a kind of confocal laser Raman-LIBS- mass spectrometry microscopic imaging device schematic diagram of the present invention；
Fig. 4 is that postposition is divided pupil confocal laser axial strength simulation curve；
Fig. 5 is that postposition is divided pupil confocal laser 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 confocal laser detection system, 14- relaying amplifying lens, 15- pin hole, 16- light intensity detector,
17- amplifies Airy, 18- search coverage, 19- postposition and is divided pupil confocal laser axial strength curve, 20- dichroscope B, 21-
Raman spectroscopic detection system, 22- Raman-Coupled lens, 23- Raman spectroscopy detector, 24-LIBS spectrum investigating system, 25-
LIBS coupled lens, 26-LIBS spectral detector, 27- ion suction pipe, 28- mass spectrograph, 29- computer, 30- vector light occur
Device, 31- iris filter, 32- circular collection pupil, 33-CCD detector, 34- pulse laser, 35- collector lens, 36- are passed
Light optical fiber, 37- outgoing beam attenuator, 38- detection beam attenuator, the light splitting pupil confocal laser axial strength actual measurement of 39- postposition
Curve.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and examples.
Embodiment 1
The excitation beam that point light source 1 is emitted as shown in Figure 1: 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 29 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
Light confocal detection system 13 acquires, and after collecting object lens 11 and the collection focusing of pupil 12 of D type, hot spot is by relaying amplifying lens
14 amplifications, amplification Airy 17 penetrate pin hole 15, and the light intensity signal of search coverage 18 is acquired by light intensity detector 16, obtains postposition
It is divided pupil confocal laser axial strength curve 19；
Believed using the microcell axial height that postposition light splitting pupil confocal laser axial strength curve 19 can be accurately positioned sample 8
Breath.Fig. 5 is that postposition is divided pupil confocal laser axial strength measured curve, wherein 39 are divided pupil confocal laser axial strength for postposition
Measured curve；
Computer 29 accurately corresponds to measurement object according to " extreme point " of postposition light splitting pupil confocal laser axial strength curve 19
7 focal beam spot focus this characteristic of mirror, control precision three-dimensional workbench 10 drive sample 8 to move along measuring surface normal direction, make
The focal beam spot of measurement object lens 7 focuses on sample 8；
At the same time, drawing is entered after dichroscope B20 reflection by the Raman diffused light of dichroscope A6 transmission
In graceful spectrum investigating system 21, 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 27 by mass spectrograph 28, 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 saturating by dichroscope A6 transmission, dichroscope B20
It penetrates, is detected by LIBS spectrum investigating system 24, measure the sample element composition information in the corresponding focal beam spot region of sample 8；
The laser focal beam spot position height of specimen that computer 29 measures postposition light splitting pupil confocal laser detection system 13
The laser that information, Raman spectroscopic detection system 21 detect focuses the Raman spectral information of microcell, LIBS spectrum investigating system 24 is visited
The Information in Mass Spectra that the laser that LIBS spectral information, the mass spectrograph 28 that the laser of survey 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；
Embodiment 2
It is as shown in Figure 2: in a kind of confocal laser Raman-LIBS- mass spectrometry microscopic imaging device, to compress focal beam spot
System 4 is substituted by vector beam generating system 30 and iris filter 31, and D type is collected pupil 12 and can be replaced by circular collection pupil 32
Generation, the pin hole 15 and light intensity detector 16 that postposition is divided in pupil confocal laser detection system can be replaced by ccd detector 33, wherein
Search coverage 18 is located at the image plane center of ccd detector 33.
Remaining imaging method and process are identical as Fig. 1.
Embodiment 3
As shown in Figure 3: in a kind of confocal laser Raman-LIBS- mass spectrometry microscopic imaging device, point light source 1 is by pulse
Laser 34, collector lens 35 and Optic transmission fiber 36 substitute；Optic transmission fiber 36 is located at the focal point of collector lens 35, is used for light
Conduction.Meanwhile outgoing beam attenuator 37 is introduced in laser focusing system, in postposition light splitting pupil confocal laser detection system
Introduce detection beam attenuator 38.Light intensity regulating system is constituted by outgoing beam attenuator 37 and detection beam attenuator 38, is used
In the spot intensity that decaying focal beam spot and light intensity detector 16 detect, needed with light intensity when adapting to sample surfaces positioning
It asks.
Remaining imaging method and process and identical as Fig. 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)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811343645.XA CN109254071A (en) | 2018-11-13 | 2018-11-13 | A kind of confocal laser Raman-LIBS- mass spectrometry micro imaging method and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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