CN105067570A - Dual-axis laser differential confocal LIBS (laser-induced breakdown spectroscopy), RS (Raman spectroscopy) and MS (mass spectrometry) imaging method and device - Google Patents
Dual-axis laser differential confocal LIBS (laser-induced breakdown spectroscopy), RS (Raman spectroscopy) and MS (mass spectrometry) imaging method and device Download PDFInfo
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Abstract
The invention relates to a dual-axis laser differential confocal LIBS (laser-induced breakdown spectroscopy), RS (Raman spectroscopy) and MS (mass spectrometry) imaging method and device and belongs to the technical field of confocal microscopy imaging, MS imaging and spectral measurement. A double-axis differential confocal microscopy imaging technology and spectrum and MS detection technologies are combined, a sample is subjected to high spatial resolution morphological imaging through micro focusing spots, processed with a super-resolution technology, of a dual-axis differential confocal microscope, an MS detection system is used for performing MS detection on electrically-charged molecules or atoms in a microcell of the sample, a spectrum detection system is used for performing microcell spectrum detection on focusing spot excitation spectra including Raman spectra and LIBS spectra, and high spatial resolution of the microcell of the sample and high-sensitivity imaging and detection of components and morphology are realized through advantage complementation of laser multi-spectrum detection and structural fusion. A brand new effective technological approach can be provided for imaging and detection of material components and morphology in the fields such as biology, materials and the like.
Description
Technical field
The invention belongs to confocal microscopic imaging technology, spectral imaging technology and mass spectrum imaging technical field, dual-axis differential confocal micro-imaging technique, Laser-induced Breakdown Spectroscopy imaging technique, Raman spectrum imaging technology are combined with mass spectrum imaging technology, relate to a kind of two-axis laser differential confocal LIBS, Raman spectrum-mass spectrum imaging method and device, have wide practical use in fields such as biology, material, mineral products, minute manufacturings.
Technical background
Mass spectrometer (MassSpectrometry) is ionized the component in sample, the charge atom of the different specific charges of generation, molecule or molecular fragment focused on respectively under the effect of Electric and magnetic fields and obtains the collection of illustrative plates instrument by the arrangement of mass-to-charge ratio size order.Mass spectrum imaging carries out mass spectrophotometry respectively to detect the distribution of specific mass-to-charge ratio (m/z) material to tiny area multiple in sample 2 dimensional region.
From the appearance of the substance assistant laser desorpted ionized this high sensitivity of the mid-80 in last century and high quality detection scope biological mass spectrometry imaging technique, open up field-biological mass spectrometry that mass-spectrometry one is brand-new, mass-spectrometric technique range of application is impelled to expand to the various fields of life science, the particularly application of mass spectrum in protein, nucleic acid, glycoprotein assay etc., not only for life science provides new tool, and also promote the development of mass-spectrometric technique self.
But there is following outstanding problem in existing substance assistant laser desorpted ionized mass spectrometer:
1) owing to utilizing simple Laser Focusing to carry out desorption ionization sample, thus still there is the problems such as Laser Focusing hot spot is large, mass spectrometry detection spatial resolution is not high in it;
2) cannot centering atom, molecule, intermediate ion and group etc. detect, its result constrains the accurate complete acquisition of sample component information;
3) mass spectrum imaging required time is long, and the relative sample of laser mass spectrometry instrument focal beam spot axial location often drifting problem occurs.
And " microcell " pattern of mineral products, space material and biological sample and the Obtaining Accurate of complete component information are all extremely important for scientific research and production testing.In fact, how detecting micro-area composition information is with sensitivity the important technological problems that the fields such as current mineral products analysis, biochemistry detection 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, can obtain the atom of sample and Small molecular element forms information by the fail spectrum that gives off of detection energy of plasma; 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, Laser-induced Breakdown Spectroscopy (LIBS) technology are combined and can to realize with mass spectrometry detection combine with technique having complementary advantages and structure function merges, utilize laser multispectral (mass spectrum, Raman spectrum and Laser-induced Breakdown Spectroscopy) integration technology to realize the complete component information detection of sample.
Laser dual-axis differential 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 two-axis laser differential confocal LIBS, Raman spectrum-mass spectrum imaging method and device, its innovation is: the dual-axis differential confocal microtechnic with high-space resolution ability merged mutually with laser Raman spectroscopy technology, Laser-induced Breakdown Spectroscopy (LIBS) technology and mass spectrometry detection technology first, can realize imaging and the detection of sample microcell high-space resolution and highly sensitive form and component.
The pattern component imaging detection that a kind of high-space resolution of the present invention confocal laser induced breakdown, Raman spectrum and mass spectrum micro imaging method and device can be the fields such as biology, material, physical chemistry, minute manufacturing provides a brand-new effective technical way.
Summary of the invention
The object of the invention is to improve the spatial resolving power of mass spectrum imaging, suppress the drift of focal beam spot relative sample in imaging process, a kind of two-axis laser differential confocal LIBS, Raman spectrum-mass spectrum imaging method and device are proposed, to obtaining sample micro-raman spectra information and component information simultaneously.The detecting function of laser dual-axis differential confocal microscope focal beam spot merges with Laser Focusing desorption ionization function by the present invention mutually, the microscopical small focal beam spot of dual-axis differential confocal through super resolution technology process is utilized to carry out the imaging of high-space resolution form to sample, Raman spectrum detection system is utilized to detect the Raman spectrum that dual-axis differential confocal microscopic system focal beam spot excited sample produces, utilize the charged molecule that mass spectrometry detection system produces dual-axis differential confocal microscopic system focal beam spot desorption ionization sample, atoms etc. carry out microcell mass spectrum imaging, the plasma emission spectroscopy information utilizing Laser-induced Breakdown Spectroscopy detection system to produce twin shaft confocal microscope system focal beam spot desorption ionization sample carries out Laser-induced Breakdown Spectroscopy imaging, and then by sample composition information that fusion and the comparison of detection data information have obtained, then imaging and the detection of sample microcell high-space resolution and highly sensitive form and component is realized.
The object of the invention is to be achieved through the following technical solutions.
A kind of two-axis laser differential confocal LIBS of the present invention, Raman spectrum-mass spectrum imaging method, the focal beam spot of high-space resolution dual-axis differential confocal microscopic system is utilized to focus and imaging sample, Raman spectrum detection system is utilized to detect the Raman spectrum that dual-axis differential confocal microscopic system focal beam spot excited sample produces, utilize the charged molecule that mass spectrometry detection system produces dual-axis differential confocal microscopic system focal beam spot desorption ionization sample, atoms etc. carry out microcell mass spectrum imaging, the plasma emission spectroscopy utilizing Laser-induced Breakdown Spectroscopy detection system to produce dual-axis differential confocal microscopic system focal beam spot desorption ionization sample detects, and then imaging and detection while then realizing sample microcell high-space resolution and highly sensitive form and component by the fusion of detection data information and compare of analysis, comprise the following steps:
Step one, make parallel beam by being shaped as annular beam after ring light generation systems, this annular beam focuses on sample through measuring object lens again;
Step 2, making computing machine control three-dimensional working platform drives sample to move up and down near measurement object focal point along measuring surface normal direction, utilize and gather object lens, optical splitter, dichro iotac beam, condenser lens, relaying amplifying lens detects with being positioned at relaying amplifying lens focal plane and carrying out segmentation about the first light intensity point probe and the second light intensity point probe that gather the placement of optical axis symmetry to amplification Airy disk, the strength characteristics obtaining Airy disk first microcell and Airy disk second microcell is respectively first from axle confocal axial strength curve and second from the confocal axial strength curve of axle,
Step 3, subtract each other process from axle confocal axial strength curve and second from the confocal axial strength curve of axle by first and obtain dual-axis differential confocal axial strength curve, utilize dual-axis differential confocal axial strength curve accurately can locate this axial height information of sample;
Step 4, computing machine drive sample to move along measuring surface normal direction according to the null position zA value control three-dimensional working platform of dual-axis differential confocal axial strength curve, make the focal beam spot of measurement object lens focus on sample;
Step 5, utilize Raman spectrum detection system to detect the Raman spectrum collected through spectrophotometric reflection, dichro iotac beam transmission and Raman spectral collection lens, record sample chemical key and the molecular structure information in corresponding focal beam spot region;
Step 6, change parallel beam light illumination mode, excite the microcell desorption ionization of sample to produce plasma plume;
Step 7, utilize ionized sample suction pipe to be produced by focal beam spot desorption ionization sample plasma plume in molecule, atom and ion suck in mass spectrometry detection system and carry out mass spectrum imaging, record the Information in Mass Spectra in corresponding focal beam spot region;
Step 8, utilize Laser-induced Breakdown Spectroscopy detection system to detect the Laser-induced Breakdown Spectroscopy of collecting through optical splitter transmission and Laser-induced Breakdown Spectroscopy collecting lens, record the sample element composition information in corresponding focal beam spot region;
The Information in Mass Spectra of the Laser Focusing microcell that the Raman spectrum of the Laser Focusing microcell of the Laser Focusing facula position height of specimen information that laser dual-axis differential confocal detection system records by step 9, computing machine, laser Raman spectroscopy detection system detection, the spectral information of the Laser Focusing microcell of Laser-induced Breakdown Spectroscopy detection system detection, mass spectrometry detection system record carries out fusion treatment, then obtains the height of focal beam spot microcell, spectrum and Information in Mass Spectra;
Step 10, computing machine control three-dimensional working platform makes measurement object focal point aim at the next one region to be measured of measurand, then operates by step 2 ~ step 9, obtains the height of next focal zone to be measured, spectrum and Information in Mass Spectra;
Step 11, repetition step 10, until all tested points on sample are all measured, then utilize computing machine to carry out process and can obtain sample shape information and complete component information.
The inventive method comprises step one and can be and make parallel beam by being shaped as annular beam after vector beam generation systems, iris filter, and this annular beam focuses on desorption ionization on sample produce plasma plume through measuring object lens again.
High-space resolution laser dual-axis differential confocal induced breakdown of the present invention, Raman spectrum-mass spectrum microscopic imaging device comprises pointolite, the collimation lens placed along incident light axis direction, produce the ring light generation systems of annular beam and the focal beam spot measurement object lens to sample, comprise the collection object lens for detecting measurement object lens focal beam spot intensity of reflected light signal along gathering optical axis direction placement, optical splitter and the dichroism optical splitter being positioned at spectrophotometric reflection direction, be positioned at the condenser lens of dichro iotac beam reflection direction, relaying amplifying lens and be positioned at relaying amplifying lens focal plane and about gather optical axis symmetry place the first light intensity point probe and the second light intensity point probe, also comprise and be positioned at dichro iotac beam transmission direction for detecting the Raman collection lens of Raman spectrum and being positioned at the Raman spectrum detection system of Raman collection lens focus, be positioned at optical splitter transmission direction for exploring laser light induced breakdown spectroscopy dichronic mirror, be positioned at the Laser-induced Breakdown Spectroscopy collecting lens of dichroic mirror light direction and be positioned at the Laser-induced Breakdown Spectroscopy detection system at Laser-induced Breakdown Spectroscopy collecting lens focus place, and along measuring surface normal direction, for detecting ionized sample suction pipe and the mass spectrometry detection system of the ion body feathers component measuring object lens focal beam spot desorption ionization, incident light axis and the angle gathered between optical axis are 2 θ, and symmetrical about measuring surface normal.
Apparatus of the present invention comprise ring light generation systems and can substitute with the vector beam generation systems of the generation vector beam placed along incident light axis direction and iris filter.
Beneficial effect
The present invention contrasts prior art, has the following advantages:
1) the dual-axis differential confocal microtechnic with high-space resolution ability is merged mutually with mass spectrometry detection technology, make the hot spot of dual-axis differential confocal micro imaging system realize focusing-detection and sample desorption ionization dual-use function, sample microcell mass spectrographic high spatial mass spectrum micro-imaging can be realized;
2) in conjunction with the detection of Raman spectrum and Laser-induced Breakdown Spectroscopy, overcome existing laser mass spectrometry instrument and centering atom, molecule, intermediate ion and group etc. cannot carry out the deficiency that detects, the mutual supplement with each other's advantages and the structure function that realize laser multispectral (mass spectrum, Raman spectrum and Laser-induced Breakdown Spectroscopy) component imaging detection merge, and can obtain microcell component information more comprehensively;
3) utilize the zero crossing of dual-axis differential confocal curve to carry out sample to focus in advance, minimum focal beam spot is made to focus on sample surfaces, sample microcell high-space resolution mass spectrometry detection and microcell micro-imaging can be realized, effectively play the potential differentiated between dual-axis differential confocal system altitude;
4) utilize dual-axis differential confocal curve zero crossing to carry out sample and focus process in advance, existing mass spectrometer can be suppressed because of the drifting problem of the relative sample of focal beam spot in long-time mass spectrum imaging;
5) utilize annular beam imaging both to have compressed the size of focal beam spot, again for mass spectrometry detection provides the best fusion of configuration aspects, the spatial resolving power of laser mass spectrometry instrument can be improved;
6) utilize the oblique incidence sounding of cross-compound arrangement light beam, overcome the defect that existing confocal microscopic imaging technology cannot suppress focal plane interference of stray light, anti-parasitic light ability is strong.
Accompanying drawing explanation
Fig. 1 is two-axis laser differential confocal LIBS of the present invention, Raman spectrum-mass spectrum imaging method;
Fig. 2 is two-axis laser differential confocal LIBS of the present invention, Raman spectrum-mass spectrum imaging method conversion schematic diagram;
Fig. 3 is the two-axis laser differential confocal LIBS of embodiments of the invention 1, Raman spectrum-mass spectrum imaging method and device schematic diagram.
Wherein: 1-pointolite, 2-collimation lens, 3-parallel beam, 4-ring light generation systems, 5-ring light, 6-measures object lens, 7-incident light axis, 8-sample, 9-plasma plume, 10-gathers optical axis, 11-gathers lens, 12-condenser lens, 13-relaying amplifying lens, 14-amplifies Airy disk, 15-first light intensity point probe, 16-second light intensity point probe, 17-Airy disk first microcell, 18-Airy disk second microcell, 19-first is from the confocal axial strength curve of axle, 20-second is from the confocal axial strength curve of axle, 21-differential confocal axial strength curve, 22-computing machine, 23-ionized sample suction pipe, 24-mass spectrometry detection system, 25-optical splitter, 26-Laser-induced Breakdown Spectroscopy collecting lens, 27-Laser-induced Breakdown Spectroscopy detection system, 28-three-dimensional working platform, 29-measuring surface normal, 30-CCD detector, 31-vector beam generation systems, 32-iris filter, 33-pulsed laser, 34-collector lens, 35-pin hole, 36-Optic transmission fiber, 37-outgoing beam attenuator, 38-detecting light beam attenuator.39-dichro iotac beam, 40-Raman spectrum, 41-Raman spectral collection lens, 42-Raman spectrum detection system, 43-Laser-induced Breakdown Spectroscopy.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
As shown in Figure 1, following examples all realize core methed of the present invention on Fig. 1 basis.
Embodiment 1
The embodiment of the present invention is based on high-space resolution laser dual-axis differential confocal induced breakdown, the Raman spectrum-mass spectrum microscopic imaging device shown in Fig. 3, this device adopts the pointolite 1 in Optic transmission fiber 36 alternate figures 1 at pulsed laser 33, collector lens 34 and collector lens 34 focus place, by the first light intensity point probe 15 and the second light intensity point probe 16 being positioned at relaying amplifying lens 13 focal plane in ccd detector 30 alternate figures 1.In the laser focusing system of Fig. 3, introduce outgoing beam attenuator 37, in laser dual-axis differential confocal detection system, introduce detecting light beam attenuator 38.
High-space resolution laser dual-axis differential confocal spectrum-mass spectrum microscopic imaging device as shown in Figure 3 comprises pulsed laser 33, the pointolite 1 of Optic transmission fiber 36 composition at collector lens 34 and collector lens 34 focus place, the collimation lens 2 placed along incident light axis 7 direction, outgoing beam attenuator 37, ring light generation systems 4, focal beam spot is to the measurement object lens 6 of sample 8, also comprise the collection lens 11 for detecting measurement object lens 6 focal beam spot intensity of reflected light signal along gathering the placement of optical axis 10 direction, optical splitter 25, Laser-induced Breakdown Spectroscopy collecting lens 26 and the Laser-induced Breakdown Spectroscopy detection system 27 being positioned at Laser-induced Breakdown Spectroscopy collecting lens 26 focus, be positioned at the dichro iotac beam 39 of optical splitter 25 reflection direction, Raman spectral collection lens 41 and the Raman spectrum detection system 42 being positioned at Raman spectral collection lens 41 focus, be positioned at the detecting light beam attenuator 38 of dichroic beamsplitter 39 reflection direction, condenser lens 12, relaying amplifying lens 13 and the ccd detector 30 being positioned at relaying amplifying lens 13 image planes, and be positioned at ionized sample suction pipe 23 and the mass spectrometry detection system 24 for detecting ion body feathers 9 component measuring object lens 6 focal beam spot desorption ionization in measuring surface normal 29 direction, incident light axis 7 and the angle gathered between optical axis 10 are 2 θ, and it is symmetrical about measuring surface normal 29.
The function of main composition is as follows:
The laser focusing system be made up of to the measurement object lens 6 of sample 8 pointolite 1, the collimation lens 2 placed along incident light axis 7 direction, ring light generation systems 4, focal beam spot is for generation of the small focal beam spot exceeding diffraction limit, and this super diffraction microsize hot spot has the dual-use function measuring sample surfaces and generation surface plasma.
By along gather the collection object lens 11 in optical axis 10 direction, optical splitter 25, be positioned at optical splitter 25 reflection direction dichro iotac beam 39 and be positioned at laser dual-axis differential confocal detection system that the condenser lens 12 of dichro iotac beam 35 reflection direction, condenser lens 12, relaying amplifying lens 13 and the ccd detector 30 that is positioned at relaying amplifying lens 13 image planes form and precision is carried out to sample 8 focus, and carry out axial location to measuring the facula position that object lens 6 focus on sample 8, record the height of specimen of corresponding focal beam spot position.
The mass spectrometry detection system be made up of ionized sample suction pipe 23 and mass spectrometry detection system 24 detects charge atom, molecule etc. in plasma plume 9 based on time-of-flight method (TOF), carry out flight time mass spectrum detection.
By the spectrum investigating system gathering object lens 11, optical splitter 25, the spectral collection lens 26 being positioned at optical splitter 25 reflected light direction and the spectrum investigating system 27 that is positioned at spectral collection lens 26 focus place and form, for detecting the Laser-induced Breakdown Spectroscopy 39 of sample 8, record the component information in corresponding focal beam spot region.
Light intensity regulating system is formed, for the spot intensity of decay focal beam spot and ccd detector 30 detection, with light intensity demand during location, accommodate sample surface by outgoing beam attenuator 37 and detecting light beam attenuator 38
The ring light transverse super-resolution system be made up of ring light generation systems 4 and measurement object lens 6, for compressing focal beam spot lateral dimension.
The tight focusing system of radial polarisation light longitudinal field be made up of vector beam generation systems 31, iris filter 32 and measurement object lens 6 is for compressing focal beam spot lateral dimension.
The three-dimensional motion system be made up of computing machine 22, three-dimensional working platform 28 can be carried out axis to sample 8 and be focused location and 3-D scanning.
The wavelength of pulsed laser 33, pulsewidth and repetition frequency can be selected as required.
The process of sample being carried out to high resolution mass spectrum imaging mainly comprises the following steps:
The light beam of step one, pulsed laser 33 outgoing collimates as parallel beam 3 after collector lens 34, Optic transmission fiber 36 and collimation lens 2, this parallel beam 3 generates annular beam 5 through outgoing beam attenuator 37, ring light generation systems 4, and annular beam 5 is focused to through measurement object lens 6 small spot exceeding diffraction limit again and is radiated on sample 8;
Step 2, utilize computing machine 22 to control three-dimensional working platform 28 to make to carry out axial scan by along gathering the laser dual-axis differential confocal detection system that the collection object lens 11 in optical axis 10 direction, condenser lens 12, relaying amplifying lens 13 and the ccd detector 30 that is positioned at relaying amplifying lens 13 focus place form to sample 8, carry out segmentation to amplification Airy disk 14 to detect, record first of corresponding Airy disk first microcell 17 and Airy disk second microcell 18 from axle confocal axial strength curve 19 and second from the confocal axial strength curve 20 of axle;
Step 3, subtract each other process from axle confocal axial strength curve 19 and second from the confocal axial strength curve 20 of axle by first and obtain dual-axis differential confocal axial strength curve 21, utilize dual-axis differential confocal axial strength curve 21 accurately can locate this axial height information of sample 8, detecting light beam attenuator 38 detects to avoid ccd detector 30 supersaturation for the light intensity that decays; ;
Step 4, computing machine drive sample 8 to move along measuring surface normal 29 direction according to the null position zA value control three-dimensional working platform 25 of dual-axis differential confocal axial strength curve 21, make the focal beam spot of measurement object lens 6 focus on sample, realize initially focusing sample 8;
Step 5, utilize Raman spectrum detection system 42 to reflecting through optical splitter 25, Raman spectrum 40 that dichro iotac beam 39 transmission and Raman spectral collection lens 41 are collected detects, and records sample chemical key and the molecular structure information in corresponding focal beam spot region;
Step 6, change pulsed laser 33 mode of operation, adjust irradiating light beam attenuator 37 and strengthen the focal beam spot intensity measuring object lens 6, excites the microcell desorption ionization of sample 8 to produce plasma plume 9;
Step 7, utilize ionized sample suction pipe 23 to be produced by focal beam spot desorption ionization sample 8 plasma plume 9 in molecule, atom and ion suck in mass spectrometry detection system 24 and carry out mass spectrum imaging, record the Information in Mass Spectra in corresponding focal beam spot region;
Step 8, utilize Laser-induced Breakdown Spectroscopy detection system 27 to carry out light spectrum image-forming detection to the Laser-induced Breakdown Spectroscopy 43 of collecting through optical splitter 25 transmission and Laser-induced Breakdown Spectroscopy collecting lens 26, record the sample element composition information in corresponding focal beam spot region;
The Information in Mass Spectra of the Laser Focusing microcell that the Laser-induced Breakdown Spectroscopy 43 of the Laser Focusing microcell that the Raman spectrum 40 of the Laser Focusing microcell that the Laser Focusing facula position height of specimen information that laser dual-axis differential confocal detection system records by step 9, computing machine 22, laser Raman spectroscopy detection system 42 detect, Laser-induced Breakdown Spectroscopy detection system 27 detect, mass spectrometry detection system 24 detect simultaneously carries out fusion treatment, then obtains the height of focal beam spot microcell, spectrum and Information in Mass Spectra;
Step 10, computing machine 22 control three-dimensional working platform 28 makes measurement object lens 6 aim at the next one region to be measured of sample, then operates by step 2 ~ step 9, obtains the height of next focal zone to be measured, spectrum and Information in Mass Spectra;
Step 11, repetition step 10, until all tested points on sample 8 are all measured, then utilize computing machine 18 to carry out data fusion and image reconstruction process, can obtain sample shape information and complete component information.
Embodiment 2
In high-space resolution laser dual-axis differential confocal spectrum-mass spectrum microscopic imaging device as shown in Figure 2, pointolite 1 can be substituted by the pin hole 35 along the pulsed laser 33 in incident light axis 7 direction, collector lens 34, collector lens 34 focus, ring light generation systems 4 can be substituted by vector beam generation systems 31, iris filter 32, and the first light intensity point probe 15 and the second light intensity point probe 16 that are positioned at relaying amplifying lens 13 focal plane are substituted by ccd detector 30.
The tight focusing system of radial polarisation light longitudinal field be made up of vector beam generation systems 31, iris filter 32 and measurement object lens 6 is for compressing focal beam spot lateral dimension.
All the other imaging measurement methods are identical with embodiment 1.
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 (4)
1. a two-axis laser differential confocal LIBS, Raman spectrum-mass spectrum imaging method, it is characterized in that: utilize the focal beam spot of high-space resolution dual-axis differential confocal microscopic system to focus and imaging sample, Raman spectrum detection system is utilized to detect the Raman spectrum that dual-axis differential confocal microscopic system focal beam spot excited sample produces, utilize the charged molecule that mass spectrometry detection system produces dual-axis differential confocal microscopic system focal beam spot desorption ionization sample, atoms etc. carry out microcell mass spectrum imaging, the plasma emission spectroscopy utilizing Laser-induced Breakdown Spectroscopy detection system to produce dual-axis differential confocal microscopic system focal beam spot desorption ionization sample detects, and then imaging and detection while then realizing sample microcell high-space resolution and highly sensitive form and component by the fusion of detection data information and compare of analysis, comprise the following steps:
Step one, make parallel beam (3) by being shaped as annular beam (5) after ring light generation systems (4), this annular beam (5) focuses on sample (8) through measuring object lens (6) again;
Step 2, making computing machine (22) control three-dimensional working platform (28) drives sample (8) to move up and down along measuring surface normal (29) direction at measurement object lens (6) near focal point, utilize and gather object lens (11), optical splitter (25), dichro iotac beam (39), condenser lens (12), relaying amplifying lens (13) and be positioned at relaying amplifying lens (13) focal plane and about gather optical axis (10) symmetry place the first light intensity point probe (15) and the second light intensity point probe (16) to amplification Airy disk (14) carry out segmentation detect, the strength characteristics obtaining Airy disk first microcell (17) and Airy disk second microcell (18) is respectively first from axle confocal axial strength curve (19) and second from the confocal axial strength curve (20) of axle,
Step 3, subtract each other process from axle confocal axial strength curve (19) and second from the confocal axial strength curve (20) of axle by first and obtain dual-axis differential confocal axial strength curve (21), utilize dual-axis differential confocal axial strength curve (21) accurately can locate this axial height information of sample (8);
Step 4, computing machine (22) are according to the null position z of dual-axis differential confocal axial strength curve (21)
avalue controls three-dimensional working platform (28) and drives sample (8) along the motion of measuring surface normal (29) direction, makes the focal beam spot of measurement object lens (6) focus on sample (8);
Step 5, utilize Raman spectrum detection system (42) to detect the Raman spectrum (40) collected through optical splitter (25) reflection, dichro iotac beam (39) transmission and Raman spectral collection lens (41), record sample chemical key and the molecular structure information in corresponding focal beam spot region;
Step 6, change parallel beam (3) light illumination mode, excite the microcell desorption ionization of sample (8) to produce plasma plume (9);
Step 7, utilize ionized sample suction pipe (23) to be produced by focal beam spot desorption ionization sample (8) plasma plume (9) in molecule, atom and ion suck in mass spectrometry detection system (24) and carry out mass spectrum imaging, record the Information in Mass Spectra in corresponding focal beam spot region;
Step 8, utilize Laser-induced Breakdown Spectroscopy detection system (27) to detect the Laser-induced Breakdown Spectroscopy (43) of collecting through optical splitter (25) transmission and Laser-induced Breakdown Spectroscopy collecting lens (26), record the sample element composition information in corresponding focal beam spot region;
The Information in Mass Spectra of the Laser Focusing microcell that the spectral information of the Laser Focusing microcell that the Raman spectrum (36) of the Laser Focusing microcell that the Laser Focusing facula position height of specimen information that laser dual-axis differential confocal detection system records by step 9, computing machine (22), laser Raman spectroscopy detection system (38) detect, Laser-induced Breakdown Spectroscopy detection system (27) detect, mass spectrometry detection system (24) record carries out fusion treatment, then obtains the height of focal beam spot microcell, spectrum and Information in Mass Spectra;
Step 10, computing machine (22) control three-dimensional working platform (28) makes measurement object lens (6) focus aim at the next one region to be measured of measurand (8), then operate by step 2 ~ step 9, obtain the height of next focal zone to be measured, spectrum and Information in Mass Spectra;
Step 11, repetition step 10, until all tested points on sample (8) are all measured, then utilize computing machine (22) to carry out process and can obtain sample shape information and complete component information.
2. a kind of two-axis laser differential confocal LIBS according to claim 1, Raman spectrum-mass spectrum imaging, it is characterized in that: comprise step one and can be and make parallel beam (3) by being shaped as annular beam (5) after vector beam generation systems (31), iris filter (32), this annular beam (5) focuses on the upper desorption ionization of sample (8) produce plasma plume (9) through measuring object lens (6) again.
3. a two-axis laser differential confocal LIBS, Raman spectrum-mass spectrum imaging device, it is characterized in that: comprise pointolite (1), the collimation lens (2) placed along incident light axis (7) direction, produce the ring light generation systems (4) of annular beam and the focal beam spot measurement object lens (6) to sample (8), comprise the collection object lens (11) for detecting measurement object lens (6) focal beam spot intensity of reflected light signal along gathering the placement of optical axis (10) direction, optical splitter (25) and be positioned at the dichro iotac beam (39) of optical splitter (25) reflection direction, be positioned at the condenser lens (12) of dichroism optical splitter (39) reflection direction, relaying amplifying lens (13) and be positioned at relaying amplifying lens (13) focal plane and about gather optical axis (10) symmetry place the first light intensity point probe (15) and the second light intensity point probe (16), also comprise and be positioned at dichro iotac beam (39) transmission direction for detecting the Raman collection lens (41) of Raman spectrum (40) and being positioned at the Raman spectrum detection system (42) of Raman collection lens (41) focus, be positioned at optical splitter (25) transmission direction be used for the Laser-induced Breakdown Spectroscopy collecting lens (26) of exploring laser light induced breakdown spectroscopy (43) and be positioned at the Laser-induced Breakdown Spectroscopy detection system (27) at Laser-induced Breakdown Spectroscopy collecting lens (26) focus place, and along measuring surface normal (29) direction, for detecting ionized sample suction pipe (23) and the mass spectrometry detection system (24) of ion body feathers (9) component measuring object lens (6) focal beam spot desorption ionization, incident light axis (7) and the angle gathered between optical axis (10) are 2 θ, and it is symmetrical about measuring surface normal (29).
4. a kind of two-axis laser differential confocal LIBS according to claim 3, Raman spectrum-mass spectrum imaging device, is characterized in that: comprising ring light generation systems (4) can substitute with the vector beam generation systems (31) of the generation vector beam placed along incident light axis (7) direction and iris filter (32).
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| CN106238928A (en) * | 2016-07-28 | 2016-12-21 | 孝感市森茂激光数控设备有限公司 | The upper and lower laser probe of laser cutting machine is coaxial, elevating adjusting device and method |
| CN107727635A (en) * | 2017-10-13 | 2018-02-23 | 中国科学院上海技术物理研究所 | A kind of adaptive laser spectrum of deep space microcell and imaging detection system |
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| CN106238928A (en) * | 2016-07-28 | 2016-12-21 | 孝感市森茂激光数控设备有限公司 | The upper and lower laser probe of laser cutting machine is coaxial, elevating adjusting device and method |
| CN107727635A (en) * | 2017-10-13 | 2018-02-23 | 中国科学院上海技术物理研究所 | A kind of adaptive laser spectrum of deep space microcell and imaging detection system |
| CN107727725A (en) * | 2017-10-13 | 2018-02-23 | 中国科学院上海技术物理研究所 | Detection system in a kind of planet cabin for microcell material explication de texte |
| CN107727725B (en) * | 2017-10-13 | 2023-07-04 | 中国科学院上海技术物理研究所 | Planetary vehicle cabin inner detection system for micro-area substance fine analysis |
| CN107727635B (en) * | 2017-10-13 | 2023-09-12 | 中国科学院上海技术物理研究所 | Deep space micro-area self-adaptive laser spectrum and imaging detection system |
| CN109164084A (en) * | 2018-08-13 | 2019-01-08 | 中国科学院上海高等研究院 | Super-resolution Raman spectrum imaging system and method |
| CN109164084B (en) * | 2018-08-13 | 2020-09-08 | 中国科学院上海高等研究院 | Super-resolution Raman spectrum imaging system and method |
| CN114660047A (en) * | 2022-03-15 | 2022-06-24 | 中国工程物理研究院材料研究所 | Full-spectrum coaxial optical lens barrel |
| CN114660047B (en) * | 2022-03-15 | 2023-10-27 | 中国工程物理研究院材料研究所 | Full spectrum coaxial optical lens cone |
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