CN105241850A - Biaxial laser differential confocal LIBS, Raman spectrum-mass spectrum microscopic imaging method and Raman spectrum-mass spectrum microscopic imaging device - Google Patents
Biaxial laser differential confocal LIBS, Raman spectrum-mass spectrum microscopic imaging method and Raman spectrum-mass spectrum microscopic imaging device Download PDFInfo
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Abstract
The invention relates to a biaxial laser differential confocal LIBS, a Raman spectrum-mass spectrum microscopic imaging method and a Raman spectrum-mass spectrum microscopic imaging device and belongs to the technical fields of confocal microscopic imaging, optical-spectrum imaging and mass spectrum imaging. In the invention, biaxial laser differential confocal imaging is combined with optical-spectrum and mass spectrum detection technologies, so that high-spatial-discrimination form imaging to a sample is carried out by means of a micro focus light spot of a biaxial laser differential confocal microscope which is subjected to ultra-discrimination technology treatment; mass spectrum detection to charged molecules and atoms in a micro zone of a sample is carried out by means of the mass spectrum detection system; micro zone optical spectrum detection is carried out to a focused light spot excitation spectrum (Raman spectrum, induced breakdown spectrum) through the optical-spectrum detection system; and high-spatial discrimination, high-sensitive imaging and high-sensitive detection to complete component information and form parameters of the sample micro zone through advantage complement and structural fusion of laser multi-spectrum detection. The invention provides a novel effective technical approach for imaging detection of substance components and formations in the field of biology, material and the like.
Description
Technical field
The invention belongs to confocal microscopic imaging technology, spectral imaging technology and mass spectrum imaging technical field, twin shaft confocal microscopic imaging technology, Laser-induced Breakdown Spectroscopy imaging technique, Raman spectrum imaging technology are combined with mass spectrum imaging technology, relate to the confocal LIBS of a kind of two-axis laser, 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 the confocal LIBS of a kind of two-axis laser, Raman spectrum-mass spectrum imaging method and device, its innovation is: merged mutually with laser Raman spectroscopy technology, Laser-induced Breakdown Spectroscopy (LIBS) technology and mass spectrometry detection technology by the twin shaft confocal microscopy with high-space resolution ability 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 the spatial resolution improving mass spectrum imaging, propose the confocal LIBS of a kind of two-axis laser, Raman spectrum-mass spectrum imaging method and device, to obtaining sample micro-raman spectra information and component information simultaneously.The detecting function of laser twin shaft confocal microscope focal beam spot merges with Laser Focusing desorption ionization function by the present invention mutually, the small focal beam spot through the twin shaft confocal microscope of super resolution technology process is utilized to carry out the imaging of high-space resolution form to sample, utilize the charged molecule that mass spectrometry detection system produces twin shaft confocal microscope 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 obtain complete sample composition information by the fusion of detection data information and comparison, 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.
The confocal LIBS of a kind of two-axis laser of the present invention, Raman spectrum-mass spectrum imaging method, utilize the focal beam spot of high-space resolution twin shaft confocal microscope system to carry out axis to sample to focus and imaging, Raman spectrum detection system is utilized to detect the Raman spectrum that twin shaft confocal microscope system focal beam spot excited sample produces, utilize the charged molecule that mass spectrometry detection system produces twin shaft confocal microscope 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 twin shaft confocal microscope 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, make computing machine control three-dimensional working platform drive sample along measuring surface normal direction measurement object focal point near move up and down, utilize collection object lens, optical splitter, dichro iotac beam, condenser lens and hot spot detector to carry out focus point detection to the measuring beam reflected through sample reflection and spectroscope, dichro iotac beam, obtain the confocal axial strength curve of twin shaft;
Step 3, confocal for twin shaft axial strength curve is obtained displacement twin shaft confocal axial strength curve along z after translation s, then confocal for displacement twin shaft axial strength curve and twin shaft confocal axial strength curve are subtracted each other process and obtain the confocal axial strength curve of twin shaft that misplaces, utilize dislocation to subtract each other confocal curves and accurately can locate this axial height information of sample;
Step 4, by the null position z of dislocation twin shaft confocal axial strength curve
adeduct shift value s/2 and obtain (z
a-s/2), computing machine is according to (z
a-s/2) value control three-dimensional working platform drive sample move along measuring surface normal direction, 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, the transmission of dichroism optical splitter 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 twin shaft confocal detection system records by step 9, computing machine, laser Raman spectroscopy detection system detection, the Laser-induced Breakdown Spectroscopy 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 lens 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.
Method of the present invention 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.
Method of the present invention comprises step 4 and can be position z corresponding to computing machine foundation twin shaft confocal axial strength curve maximum M
bvalue controls three-dimensional working platform and drives sample to move along measuring surface normal direction, makes the focal beam spot of measurement object lens focus on sample;
The confocal LIBS of two-axis laser of the present invention, Raman spectrum-mass spectrum imaging device, comprise 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 lens for detecting measurement object lens focal beam spot intensity of reflected light signal along gathering optical axis direction placement, optical splitter and the dichro iotac beam being positioned at spectrophotometric reflection direction, be positioned at the condenser lens of dichro iotac beam reflection direction and be positioned at the light intensity point probe of condenser lens focus, 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 the Laser-induced Breakdown Spectroscopy collecting lens of optical splitter transmission direction for exploring laser light induced breakdown spectroscopy and the Laser-induced Breakdown Spectroscopy detection system at Laser-induced Breakdown Spectroscopy collecting lens focus place, and for the ionized sample suction pipe that detects the ion body feathers component measuring object lens focal beam spots desorption ionization and mass spectrometry detection system, 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 twin shaft confocal microscopy with high-space resolution ability is merged mutually with mass spectrometry detection technology, make the hot spot of twin shaft 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) zero crossing utilizing dislocation to subtract each other the confocal axial strength curve of twin shaft carries out sample and focuses 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 of twin shaft confocal system high-space resolution;
4) utilize dislocation to subtract each other twin shaft confocal axial strength 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 the confocal LIBS of two-axis laser, Raman spectrum-mass spectrum imaging method schematic diagram;
Fig. 2 is the confocal LIBS of two-axis laser, Raman spectrum-mass spectrum imaging method conversion schematic diagram;
Fig. 3 is the confocal LIBS of two-axis laser of embodiment 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-optical splitter, 13-condenser lens, 14-hot spot detector, the confocal axial strength curve of 15-twin shaft, the confocal axial strength curve of 16-displacement twin shaft, the confocal axial strength curve of twin shaft is subtracted each other in 17-dislocation, 18-computing machine, 19-Laser-induced Breakdown Spectroscopy, 20-ionized sample suction pipe, 21-mass spectrometry detection system, 22-three-dimensional working platform, 23-measuring surface normal, 24-pin hole, 25-light intensity detector, 26-Laser-induced Breakdown Spectroscopy collecting lens, 27-Laser-induced Breakdown Spectroscopy detection system, 28-vector beam generation systems, 29-iris filter, 30-pulsed laser, 31-collector lens, 32-Optic transmission fiber, 33-outgoing beam attenuator, 34-detecting light beam attenuator, 35-dichroic filter, 36-Raman spectrum, 37-Raman spectral collection lens, 38-Raman spectrum detection system.
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 the confocal LIBS of the two-axis laser shown in Fig. 3, Raman spectrum-mass spectrum imaging device, and this device adopts the pointolite 1 in Optic transmission fiber 32 alternate figures 1 at pulsed laser 30, collector lens 31 and collector lens 31 focus place.In the laser focusing system of Fig. 3, introduce outgoing beam attenuator 33, in laser twin shaft confocal detection system, introduce detecting light beam attenuator 34.
As shown in Figure 3, the confocal LIBS of two-axis laser, Raman spectrum-mass spectrum imaging device comprises pulsed laser 30, the pointolite 1 of Optic transmission fiber 32 formation at collector lens 31 and collector lens 31 focus place, the collimation lens 2 placed along incident light axis 7 direction, outgoing beam attenuator 33, 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 12, 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 dichroic beamsplitter 35 of optical splitter 12 reflection direction, Raman spectral collection lens 37 and the Raman spectrum detection system 38 being positioned at Raman spectral collection lens 37 focus, be positioned at the detecting light beam attenuator 34 of dichroic beamsplitter 35 reflection direction, condenser lens 13 and the hot spot detector 14 being positioned at condenser lens 13 focus, also comprise the ionized sample suction pipe 20 for detecting ion body feathers 9 component measuring object lens 6 focal beam spot desorption ionization and mass spectrometry detection system 21, incident light axis 7 and the angle gathered between optical axis 10 are 2 θ, and it is symmetrical about measuring surface normal 23.Wherein, hot spot detector 14 can be made up of pin hole 24 and light intensity detector 25.
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 12, be positioned at optical splitter 12 reflection direction dichro iotac beam 35 and be positioned at the condenser lens 13 of dichro iotac beam 35 reflection direction, laser twin shaft confocal detection system that the hot spot detector 14 at condenser lens 13 focus place is formed carries out precision to sample 8 and focuses, 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.
By the Raman spectrum detection system gathering object lens 11, optical splitter 12, the dichro iotac beam 35 being positioned at optical splitter 12 reflected light direction and Raman collection lens 37 and the Raman spectrum detection system 38 that is positioned at Raman spectral collection lens 37 focus place and form, for detecting the Raman spectrum 36 of sample 8, record sample molecule structure and the chemical bond information in corresponding focal beam spot region.
The mass spectrometry detection system be made up of ionized sample suction pipe 20 and mass spectrometry detection system 21 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 Laser-induced Breakdown Spectroscopy detection system gathering object lens 11, optical splitter 12, the Laser-induced Breakdown Spectroscopy collecting lens 26 being positioned at optical splitter 12 transmission direction and the Laser-induced Breakdown Spectroscopy detection system 27 that is positioned at Laser-induced Breakdown Spectroscopy collecting lens 26 focus place and form, for detecting the Laser-induced Breakdown Spectroscopy 19 of sample 8, record the sample element composition information in corresponding focal beam spot region.
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 three-dimensional motion system be made up of computing machine 18, three-dimensional working platform 22 can be carried out axis to sample 8 and be focused location and 3-D scanning.
Light intensity regulating system is formed, for the spot intensity of decay focal beam spot and hot spot detector 14 detection, with light intensity demand during location, accommodate sample surface by outgoing beam attenuator 33 and detecting light beam attenuator 34.
The wavelength of pulsed laser 30, 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 30 outgoing collimates as parallel beam 3 after collector lens 31, Optic transmission fiber 32 and collimation lens 2, this parallel beam 3 generates annular beam 5 through outgoing beam attenuator 33, 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 18 control three-dimensional working platform 22 make by along gather the collection object lens 11 in optical axis 10 direction, optical splitter 12, be positioned at optical splitter 12 reflection direction and the condenser lens 13 being positioned at dichro iotac beam 35 reflection direction, laser twin shaft confocal detection system that the hot spot detector 14 at condenser lens 13 focus place is formed axial scan is carried out to sample 8, record the confocal axial strength curve 15 of twin shaft;
Step 3, confocal for twin shaft axial strength curve 15 is obtained displacement twin shaft confocal axial strength curve 16 along z after translation s, then confocal for displacement twin shaft axial strength curve 16 and twin shaft confocal axial strength curve 15 are subtracted each other process to obtain dislocation and subtract each other the confocal axial strength curve 17 of twin shaft, utilize dislocation to subtract each other the confocal axial strength curve 17 of twin shaft and accurately can locate this axial height information of sample 8, detecting light beam attenuator 33 detects to avoid hot spot detector 14 supersaturation for the light intensity that decays;
Step 4, computing machine 18 subtract each other the null position z of the confocal axial strength curve 17 of twin shaft according to dislocation
adeduct (the z of translation s/2
a-s/2) value controls three-dimensional working platform 22, and the focal beam spot of measurement object lens 6 is focused on sample 8, realizes initially focusing sample 8;
Step 5, utilize Raman spectrum detection system 38 to reflecting through optical splitter 12, Raman spectrum 36 that dichro iotac beam 35 transmission and Raman spectral collection lens 37 are collected detects, and records sample chemical key and the molecular structure information in corresponding focal beam spot region;
Step 6, change pulsed laser 30 mode of operation, adjust irradiating light beam attenuator 30 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 20 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 21 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 Laser-induced Breakdown Spectroscopy imaging detection to the Laser-induced Breakdown Spectroscopy 19 of collecting through optical splitter 12 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 19 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 twin shaft confocal detection system records by step 9, computing machine 18, Raman spectrum detection system 38 detect, Laser-induced Breakdown Spectroscopy detection system 27 detect, mass spectrometry detection system 21 detect carries out fusion treatment, then obtains the height of focal beam spot microcell, spectrum and Information in Mass Spectra;
Step 10, computing machine 18 control three-dimensional working platform 22 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 the confocal LIBS of two-axis laser as shown in Figure 2, Raman spectrum-mass spectrum imaging device, ring light generation systems 4 can be substituted by vector beam generation systems 28, iris filter 29.
The tight focusing system of radial polarisation light longitudinal field be made up of vector beam generation systems 28, iris filter 29 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 (5)
1. the confocal LIBS of two-axis laser, Raman spectrum-mass spectrum imaging method, it is characterized in that: utilize the focal beam spot of high-space resolution twin shaft confocal microscope system to carry out axis to sample and focus and imaging, Raman spectrum detection system is utilized to detect the Raman spectrum that twin shaft confocal microscope system focal beam spot excited sample produces, utilize the charged molecule that mass spectrometry detection system produces twin shaft confocal microscope 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 twin shaft confocal microscope 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, make computing machine (18) control three-dimensional working platform (22) drive sample (8) along measuring surface normal (23) direction measurement object lens (6) near focal point move up and down, utilize collection object lens (11), optical splitter (12), dichro iotac beam (35), condenser lens (13) and hot spot detector (14) to carry out focus point detection to the measuring beam reflected through sample (8) reflection and optical splitter (12), dichro iotac beam (35), obtain the confocal axial strength curve (15) of twin shaft;
Step 3, confocal for twin shaft axial strength curve (15) is obtained displacement twin shaft confocal axial strength curve (16) along z after translation s, then twin shaft confocal axial strength curve (16) that will be shifted and twin shaft confocal axial strength curve (15) are subtracted each other process and are obtained the confocal axial strength curve (17) of twin shaft that misplaces, and utilize dislocation to subtract each other confocal curves (17) and accurately can locate this axial height information of sample (8);
The null position z of the confocal axial strength curve (17) of step 4, the twin shaft that will misplace
adeduct shift value s/2 and obtain (z
a-s/2), computing machine (18) is according to (z
a-s/2) value control three-dimensional working platform (22) drive sample (8) along measuring surface normal (23) direction motion, make the focal beam spot of measurement object lens (6) focus on sample (8);
Step 5, utilize Raman spectrum detection system (38) to detect the Raman spectrum (36) collected through optical splitter (12) reflection, dichro iotac beam (35) transmission and Raman spectral collection lens (37), 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 (20) 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 (21) 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 (19) of collecting through optical splitter (12) 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 (19) 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 twin shaft confocal detection system records by step 9, computing machine (18), laser Raman spectroscopy detection system (38) detect, Laser-induced Breakdown Spectroscopy detection system (27) detect, mass spectrometry detection system (21) record carries out fusion treatment, then obtains the height of focal beam spot microcell, spectrum and Information in Mass Spectra;
Step 10, computing machine (18) control three-dimensional working platform (22) makes measurement object lens (6) 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 (18) to carry out process and can obtain sample shape information and complete component information.
2. the confocal LIBS of a kind of two-axis laser according to claim 1, Raman spectrum-mass spectrum imaging method, 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 (28), iris filter (29), this annular beam (5) focuses on the upper desorption ionization of sample (8) produce plasma plume (9) through measuring object lens (6) again.
3. the confocal LIBS of a kind of two-axis laser according to claim 1, Raman spectrum-mass spectrum imaging method, is characterized in that: comprise step 4 and can be position z corresponding to computing machine (18) foundation twin shaft confocal axial strength curve (15) maximal value M
bvalue controls three-dimensional working platform (22) and drives sample (8) along the motion of measuring surface normal (23) direction, and the focal beam spot of measurement object lens (6) is focused on sample (8).
4. the confocal LIBS of two-axis laser, 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 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 (12) and be positioned at the dichro iotac beam (35) of optical splitter (12) reflection direction, be positioned at the condenser lens (13) of dichro iotac beam (35) reflection direction and be positioned at the light intensity point probe (14) of condenser lens (13) focus, also comprise and be positioned at dichro iotac beam (35) transmission direction for detecting the Raman collection lens (37) of Raman spectrum (36) and being positioned at the Raman spectrum detection system (38) of Raman collection lens (37) focus, be positioned at optical splitter (12) transmission direction and be used for the Laser-induced Breakdown Spectroscopy collecting lens (26) of exploring laser light induced breakdown spectroscopy (19) and the Laser-induced Breakdown Spectroscopy detection system (27) at Laser-induced Breakdown Spectroscopy collecting lens (26) focus place, and for detecting the ionized sample suction pipe (20) of ion body feathers (9) component and mass spectrometry detection system (21) of 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 (23).
5. the confocal LIBS of a kind of two-axis laser according to claim 4, Raman spectrum-mass spectrum imaging device, is characterized in that: comprising ring light generation systems (4) can substitute with the vector beam generation systems (28) of the generation vector beam placed along incident light axis (7) direction and iris filter (29).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106198490A (en) * | 2016-08-17 | 2016-12-07 | 中国原子能科学研究院 | A kind of spatial deviation Raman spectroscopic detection system |
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| CN106198490A (en) * | 2016-08-17 | 2016-12-07 | 中国原子能科学研究院 | A kind of spatial deviation Raman spectroscopic detection system |
| CN107219214A (en) * | 2017-07-26 | 2017-09-29 | 大连理工大学 | A kind of spectrum combines the quantitative analysis device of element in mass spectrographic unknown sample |
| CN107219214B (en) * | 2017-07-26 | 2023-10-27 | 大连理工大学 | Quantitative analysis device for elements in unknown sample by spectrum combination with mass spectrum |
| CN108020163A (en) * | 2017-12-26 | 2018-05-11 | 中国科学技术大学 | A kind of device of micro- tracking particulate three-D displacement |
| CN108020163B (en) * | 2017-12-26 | 2020-01-31 | 中国科学技术大学 | device for microscopically tracking three-dimensional displacement of particles |
| CN109297940A (en) * | 2018-09-06 | 2019-02-01 | 中国科学院沈阳自动化研究所 | One kind laser defocusing amount self-checking device and its adjusting method under micro-meter scale |
| CN109187727A (en) * | 2018-11-13 | 2019-01-11 | 北京理工大学 | The femtosecond laser for being divided pupil differential confocal Raman-LIBS- mass spectrometry detection processes monitoring method |
| CN109254071A (en) * | 2018-11-13 | 2019-01-22 | 北京理工大学 | A kind of confocal laser Raman-LIBS- mass spectrometry micro imaging method and device |
| CN111879239A (en) * | 2020-06-11 | 2020-11-03 | 东莞市神州视觉科技有限公司 | Spectrum confocal measuring device and measuring method |
| CN111879239B (en) * | 2020-06-11 | 2022-09-02 | 东莞市神州视觉科技有限公司 | Spectrum confocal measuring device and measuring method |
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