CN105136750A - Laser differential confocal LIBS, Raman spectrum-mass spectrum imaging method and Raman spectrum-mass spectrum imaging device - Google Patents
Laser differential confocal LIBS, Raman spectrum-mass spectrum imaging method and Raman spectrum-mass spectrum imaging device Download PDFInfo
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Abstract
The invention relates to a laser differential confocal LIBS, a Raman spectrum-mass spectrum imaging method and a Raman spectrum-mass spectrum imaging device and belongs to the technical fields of confocal microscopy imaging, mass spectrum imaging and spectral measurement. In the invention, the differential confocal microscopy imaging technology is combined with a spectrum and mass spectrum detection technology; a high-spatial-discrimination differential confocal system is used for axially focusing and imaging a sample; a mass spectrum detection system is used for performing mass spectrum detection to charged molecules and atoms in a sample microcell; and a spectral detection system is used for performing microcell spectrum detection to focal spot excitation spectrums (Raman spectrum and induced breakdown spectrum) of a differential confocal microscopy system, thereby achieving high-spatial discrimination and high-sensitivity imaging and detection of complete component information and configuration parameters of the sample microcell. The invention achieves advantage complement and structure and function fusion of laser poly-spectrum component imaging detection (mass spectrum, Raman spectrum and laser-induced breakdown spectrum). The method and the device have wide application prospect in the fields of biology, physical chemistry, micro-fabrication and nano-fabrication and the like.
Description
Technical field
The invention belongs to differential confocal microscopic imaging technology, spectral imaging technology and mass spectrum imaging technical field, laser 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 high-space resolution laser differential confocal induced breakdown, Raman spectrum-mass spectrum micro 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.
The imaging detection mechanism of laser scanning confocal microscopy " some illumination " and " some detection ", its transverse resolution is not only made to improve 1.4 times compared with the optical microscope of equivalent parameters, but also make confocal microscope pole be convenient to combine to compress focal beam spot with super-resolution pupil filtering technique, the tight focusing technology of radial polarisation light etc., realize high-space resolution micro-imaging further.
Based on this, the present invention proposes a kind of high-space resolution laser differential confocal induced breakdown, Raman spectrum and mass spectrum micro imaging method and device, its innovation is: the 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 the spatial resolution in order to improve mass spectrum micro-imaging technique, suppressing the drift of focal beam spot relative sample in imaging process, a kind of laser differential confocal LIBS, Raman spectrum-mass spectrum imaging are proposed, to obtaining sample component space information and function information simultaneously.
The object of the invention is to be achieved through the following technical solutions.
High-space resolution laser differential confocal induced breakdown of the present invention, Raman spectrum-mass spectrum micro imaging method, it is characterized in that: utilize the focal beam spot of high-space resolution laser differential confocal microscopic system to carry out axis to sample and focus and imaging, Raman spectrum detection system is utilized to detect the Raman spectrum that confocal microscope system focal beam spot excited sample produces, utilize the charged molecule that mass spectrometry detection system produces laser 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 differential confocal microscopic system focal beam spot desorption ionization sample detects, and then imaging and the detection of sample microcell high-space resolution and highly sensitive form and component is then realized 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 again along light output direction through spectroscope, to enter through mesopore splitter reflects and be arranged in the optical axis reciprocal hole measurement object lens of folding and focus on sample;
Step 2, computing machine control by the spectroscope in middle hole measurement object lens, the axial objective scanner of coaxially placing with middle hole measurement object lens, mesopore optical splitter, mesopore spectrophotometric reflection direction and the dichro iotac beam being positioned at dichroic mirror light direction, and the laser differential confocal detection system that the differential confocal light intensity detector of dichro iotac beam reflection direction is formed is carried out axial scan by axial objective scanner to sample and recorded the first confocal axial strength curve and the second confocal axial strength curve;
Step 3, the second confocal axial strength curve and differential the subtracting each other of the first confocal axial strength curve are obtained differential confocal axial strength curve, utilize differential confocal axial strength curve accurately can locate this axial height information of sample (8);
Step 4, computing machine are according to the null position z of differential confocal axial strength curve
avalue controls axial objective scanner makes the focal beam spot of middle hole measurement object lens focus on sample;
Step 5, utilize by the spectroscope in middle hole measurement object lens, the axial objective scanner of coaxially placing with middle hole measurement object lens, mesopore optical splitter, mesopore spectrophotometric reflection direction, be positioned at dichroic mirror light direction dichro iotac beam, the microcell that the Raman spectrum detection system centring hole measurement object lens that the Raman spectral collection lens of dichro iotac beam transmission direction and the Raman spectrum detection system at Raman spectral collection lens focus place are formed focus on sample carries out Raman spectrum detection, records 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 measure to the Laser-induced Breakdown Spectroscopy centring hole of collecting through the transmission of mesopore colour annalyzer, the reflection of mesopore catoptron and Laser-induced Breakdown Spectroscopy collecting lens the microcell that object lens focus on sample to carry out Laser-induced Breakdown Spectroscopy detection, record the sample element composition information in corresponding focal beam spot region;
The Raman spectrum of the Laser Focusing microcell of the Laser Focusing facula position height of specimen information that laser differential confocal detection system records by step 9, computing machine, laser Raman spectroscopy detection system detection, the Laser-induced Breakdown Spectroscopy of Laser Focusing microcell of Laser-induced Breakdown Spectroscopy detection system detection, the Information in Mass Spectra of the Laser Focusing microcell of mass spectrometry detection system looks carry out fusion treatment, then obtain the height of focal beam spot microcell, spectrum and Information in Mass Spectra;
Step 10, computing machine control two-dimentional work bench makes middle hole measurement object lens 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 are all measured, then utilize computing machine to carry out process and can obtain sample shape information and complete component information.
The inventive method comprise step one can be make parallel beam pass through to place along optical axis direction vector beam generation systems, be shaped as annular beam after spectroscope and iris filter, this annular beam enters middle hole measurement object lens through mesopore splitter reflects again and focuses on sample.
The inventive method comprises step 9 and can be the next one region to be measured that computing machine control two-dimensional scanning mirrors system makes middle hole measurement object lens aligning sample, then operate by step 2 ~ step 9, obtain the height of next focal beam spot to be measured, spectrum and Information in Mass Spectra.
Apparatus of the present invention comprise laser point light source system, along the collimation lens that optical axis direction is placed, produce the annular beam light generation systems of annular beam, spectroscope, mesopore optical splitter and along turn back optical axis direction place focal beam spot to hole measurement object lens in sample, comprise the differential confocal light intensity detector for hole measurement object lens focal beam spot intensity of reflected light signal in detecting, for the dichro iotac beam of harmless separation Raman spectrum, the Raman spectral collection lens of the Raman spectrum excited for hole measurement object lens focal beam spot in detecting and be arranged in Raman spectral collection lens focus Raman spectrum detection system and for the ionized sample suction pipe of the ion body feathers component that detects hole measurement object lens focal beam spot desorption ionization and mass spectrometry detection system, also comprise the mesopore colour annalyzer of exploring laser light induced breakdown spectroscopy, be positioned at the mesopore catoptron in mesopore colour annalyzer transmitted light direction, be positioned at the Laser-induced Breakdown Spectroscopy collecting lens in mesopore catoptron reflected light direction and the Laser-induced Breakdown Spectroscopy detection system at Laser-induced Breakdown Spectroscopy collecting lens focus place.
In apparatus of the present invention, differential confocal intensity detector comprises detection spectroscope, be placed on first light collecting lens in detection spectroscope transmitted light direction successively, first detecting pinhole, first light intensity detector, also comprise the second light collecting lens being placed on detection dichroic mirror light direction successively, second detecting pinhole and the second light intensity detector, before first detecting pinhole is placed in first light collecting lens Jiao, it is defocused that second detecting pinhole is placed in the second light collecting lens, first light collecting lens is equal with the second light collecting lens focal length, first detecting pinhole is contrary with the second detecting pinhole defocusing amount size equidirectional.
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 optical axis direction and iris filter.
Apparatus of the present invention comprise laser point light source system and can be made up of pulsed laser, the condenser lens being positioned at laser emitting direction and the pin hole being positioned at condenser lens focus.
Beneficial effect
The present invention contrasts prior art, has the following advantages:
1) the laser differential confocal microtechnic with high-space resolution ability is merged mutually with mass spectrometry detection technology, make the hot spot of laser 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 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 differential confocal system altitude;
4) utilize the zero crossing of differential confocal curve to carry out sample to focus 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.
Accompanying drawing explanation
Fig. 1 is high-space resolution laser differential confocal induced breakdown, Raman spectrum-mass spectrum micro imaging method schematic diagram;
Fig. 2 is high-space resolution laser differential confocal induced breakdown, Raman spectrum-mass spectrum micro imaging method conversion schematic diagram;
Fig. 3 is high-space resolution laser differential confocal induced breakdown, Raman spectrum-mass spectrum microscopic imaging device schematic diagram;
Fig. 4 is the schematic diagram of embodiment 1 high-space resolution laser differential confocal spectrum-mass spectrum micro imaging method and device embodiment;
Fig. 5 is embodiment 2 and 3 high-space resolution laser differential confocal induced breakdown, Raman spectrum-mass spectrum microscopic imaging device schematic diagram.
Wherein, 1-parallel beam, 2-differential confocal light intensity detector, 3-ring light generation systems, 4-annular beam, 5-spectroscope, 6-mesopore optical splitter, hole measurement object lens in 7-, 8-sample, 9-plasma plume, 10-computing machine, the axial objective scanner of 11-, 12-first light collecting lens, 13-first detecting pinhole, 14-first light intensity detector, the confocal axial strength curve of 15-first, the confocal axial strength curve of 16-second, 17-differential confocal axial strength curve, 18-ionized sample suction pipe, 19-mass spectrometry detection system, 20-two-dimentional work bench, 21-vector beam generation systems, 22-iris filter, 23-annular beam, 24-laser point light source system, 25-collimation lens, 26-pulsed laser, 27-condenser lens, 28-pin hole, 29-mesopore catoptron, 30-Laser-induced Breakdown Spectroscopy collecting lens, 31-Laser-induced Breakdown Spectroscopy detection system, 32-Laser-induced Breakdown Spectroscopy, 33-detects spectroscope, 34-second light collecting lens, 35-second detecting pinhole, 36-second light intensity detector, 37-two-dimensional scanning mirrors system, 38-outgoing beam attenuator, 39-detecting light beam attenuator, 40-dichro iotac beam, 41-Raman spectral collection lens, 42-Raman spectrum detection system, 43-Raman spectrum.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
The detecting function of laser differential confocal microscope focal beam spot and Laser Focusing desorption ionization function merge by the present invention mutually, the small focal beam spot through the differential 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 differential confocal microscopic system focal beam spot desorption ionization sample, atoms etc. carry out microcell mass spectrum imaging, Raman spectrum detection system is utilized to carry out Raman spectrum imaging to the sample Raman spectrum that confocal microscope system focal beam spot excites, the plasma emission spectroscopy information utilizing Laser-induced Breakdown Spectroscopy detection system to produce differential confocal microscopic 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.
As shown in figs. 1 and 3, wherein, the ring light transverse super-resolution system be made up of ring light generation systems 3 and middle hole measurement object lens 7, for compressing focal beam spot lateral dimension for core methed of the present invention and device.
As shown in Figure 3, the parallel beam 1 shown in Fig. 1 can be generated by the laser of point light source system 24 outgoing after collimator objective 25 collimates.
As shown in Figure 2, can by the ring light generation systems 3 in vector beam generation systems 21, iris filter 22 alternate figures 1, the tight focusing system of radial polarisation light longitudinal field be made up of vector beam generation systems 21, iris filter 22 and middle hole measurement object lens 7 is for compressing focal beam spot lateral dimension.
Following examples all realize on Fig. 1 and 3 bases.
Embodiment 1
The embodiment of the present invention is based on the high-space resolution laser differential confocal spectrum-mass spectrum microscopic imaging device shown in Fig. 4, comprise laser point light source system 24, along the collimation lens 25 that optical axis direction is placed, outgoing beam attenuator 38, ring light generation systems 3, spectroscope 5, mesopore optical splitter 6 and be arranged in the catadioptric direction of optical axis and focus on the hole measurement object lens 7 of mesopore colour annalyzer 6 folded light beam to sample 8, comprise for hole measurement object lens 7 focal beam spot intensity of reflected light signal in detecting by dichro iotac beam 40, detecting light beam attenuator 39, the differential confocal light intensity detection system that differential confocal light intensity detector 2 is formed, the Raman spectral collection lens 41 of the Raman spectrum 43 excited for hole measurement object lens 7 focal beam spot in detecting and be positioned at the Raman spectrum detection system 42 of Raman spectral collection lens 41 focus, and for the ionized sample suction pipe 18 of plasma plume 9 component of hole measurement object lens 7 focal beam spot desorption ionization in detecting and mass spectrometry detection system 19, also comprise the mesopore colour annalyzer 6 for exploring laser light induced breakdown spectroscopy 32, mesopore catoptron 29, be positioned at Laser-induced Breakdown Spectroscopy collecting lens 30 and the Laser-induced Breakdown Spectroscopy detection system 31 in mesopore catoptron 29 reflected light direction.Wherein laser point light source system 24 can be made up of pulsed laser 26, condenser lens 27 and the pin hole 28 being positioned at condenser lens 27 focus, differential confocal light intensity detector 2 can comprise detection spectroscope 33, be placed on first light collecting lens 12 in detection spectroscope 33 transmitted light direction successively, first detecting pinhole 13, first light intensity detector 14, also comprise the second light collecting lens 34 being placed on detection spectroscope 33 reflected light direction successively, second detecting pinhole 35 and the second light intensity detector 36, before first detecting pinhole 13 is placed in first light collecting lens 12 Jiao, it is defocused that second detecting pinhole 35 is placed in the second light collecting lens 34, first light collecting lens 12 is equal with the second light collecting lens 34 focal length, first detecting pinhole 13 is contrary with the second detecting pinhole 35 defocusing amount size equidirectional.
The laser focusing system be made up of laser point light source system 24, collimation lens 25, ring light generation systems 3, spectroscope 5, mesopore colour annalyzer 6, axial objective scanner 11 and middle hole measurement object lens 7 is for generation of the small focal beam spot exceeding diffraction limit, and this super diffraction microsize hot spot has the dual-use function measured sample surfaces and produce surface plasma.
The laser differential confocal detection system be made up of middle hole measurement object lens 7, mesopore colour annalyzer 6, spectroscope 5, differential confocal light intensity detector 2, for carrying out to sample 8 height of specimen that precision focused and measured small focal beam spot position.
The mass spectrometry detection system be made up of ionized sample suction pipe 18 and mass spectrometry detection system 19 detects charge atom, molecule etc. in plasma plume 9 based on time-of-flight method (TOF), carry out flight time mass spectrum detection.
The Laser-induced Breakdown Spectroscopy detection system be made up of mesopore optical splitter 6, mesopore catoptron 29, the Laser-induced Breakdown Spectroscopy collecting lens 30 being positioned at mesopore catoptron 29 reflected light direction and Laser-induced Breakdown Spectroscopy detection system 31, for detecting the Laser-induced Breakdown Spectroscopy 32 of sample 8, record the element composition information in corresponding focal beam spot region;
The ring light transverse super-resolution system be made up of ring light generation systems 3 and middle hole measurement object lens 7, 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 21, iris filter 22 and middle hole measurement object lens 7 is for compressing focal beam spot lateral dimension.
The three-dimensional motion system be made up of computing machine 10, two-dimentional work bench 20 and axial objective scanner 11 can be carried out axis to sample 8 and be focused location and 3-D scanning.
Form Light intensity regulating system by outgoing beam attenuator 38 and detecting light beam attenuator 39, detect the intensity of hot spot for decay focal beam spot and differential light intensity detector 2, with light intensity demand during location, accommodate sample surface.
The wavelength of pulsed laser 26, pulsewidth and repetition frequency can be selected as required.
The process of sample being carried out to high-resolution spectra-mass spectrum imaging mainly comprises the following steps:
After the light beam line focus lens 27 of step one, pulsed laser 26 outgoing, pin hole 28 and collimation lens 25, collimation is parallel beam 1, and this parallel beam 1 reflects through outgoing beam attenuator 38, ring light generation systems 3, spectroscope 5, mesopore optical splitter 6, be focused to the small spot exceeding diffraction limit after middle hole measurement object lens 7 is radiated on sample 8;
Step 2, computing machine 10 is utilized to control axial objective scanner 11, make by middle hole measurement object lens 7, axial objective scanner 11 of placing coaxial with middle hole measurement object lens 7, mesopore optical splitter 6, the spectroscope 5 of mesopore optical splitter 6 reflection direction, be positioned at the dichro iotac beam 40 in spectroscope 5 reflected light direction, the detecting light beam attenuator 39 of dichro iotac beam 40 reflection direction, the laser differential confocal detection system that differential confocal light intensity detector 2 is formed carries out axial scan to sample 8, record the first confocal axial strength curve 15 and the second confocal axial strength curve, detecting light beam attenuator 39 detects to avoid light intensity point probe 2 supersaturation for the light intensity that decays,
Step 3, the second confocal axial strength curve 15 and differential the subtracting each other of the first confocal axial strength curve 16 are obtained differential confocal axial strength curve 17, utilize differential confocal axial strength curve 17 accurately can locate this axial height information of sample 8;
Step 4, computing machine are according to the null position z of differential confocal axial strength curve 17
avalue controls axial objective scanner makes the focal beam spot of middle hole measurement object lens 7 focus on sample 8, realizes focusing the axis of sample 8;
Step 5, utilize by middle hole measurement object lens 7, axial objective scanner 11 of placing coaxial with middle hole measurement object lens 7, mesopore optical splitter 6, the spectroscope 5 of mesopore optical splitter 6 reflection direction, be positioned at spectroscope 5 reflected light direction dichro iotac beam 40, the microcell that the Raman spectrum detection system centring hole measurement object lens 7 that the Raman spectral collection lens 41 of dichro iotac beam 40 transmission direction and the Raman spectrum detection system 42 at Raman spectral collection lens 41 focus place are formed focus on sample 8 carries out Raman spectrum detection, record sample chemical key and the molecular structure information in corresponding focal beam spot region,
Step 6, change the output mode of pulsed laser 26, adjust irradiating light beam attenuator 38 strengthen in the focal beam spot intensity of hole measurement object lens 7, excite the microcell desorption ionization of sample 8 to produce plasma plume 9;
Step 7, utilize ionized sample suction pipe 18 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 19 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 31 to measure to Laser-induced Breakdown Spectroscopy 32 centring hole reflected through mesopore optical splitter 6 transmission, mesopore catoptron 29 and Laser-induced Breakdown Spectroscopy collecting lens 30 is collected the microcell that object lens 7 focus on sample 8 to carry out Laser-induced Breakdown Spectroscopy detection, 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 32 of the Laser Focusing microcell that the Raman spectrum 43 of the Laser Focusing microcell that the Laser Focusing facula position height of specimen information that confocal laser detection system records by step 9, computing machine 10, Raman spectrum detection system 42 detect, Laser-induced Breakdown Spectroscopy detection system 31 detect simultaneously, mass spectrometry detection system 19 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 10 control the next one region to be measured that two-dimentional work bench 20 makes middle hole measurement object lens 7 optical axis alignment sample 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 9, until all tested points on sample 8 are all measured, then utilize computing machine 10 to carry out process and can obtain sample 8 shape information and complete component information.
Embodiment 2
As shown in Figure 5, in the high-space resolution laser differential confocal induced breakdown, Raman spectrum-mass spectrum microscopic imaging device of embodiment 1, ring light generation systems 3 can substitute with the vector beam generation systems 21 of the generation vector beam placed along optical axis direction and iris filter 22, initial ring shaped light beam 23, this annular beam reflects through mesopore colour annalyzer 6, middle hole measurement object lens 7 are focused to the small spot exceeding diffraction limit and are radiated on sample 8.
All the other imaging measurement methods are identical with embodiment 1.
Embodiment 3
As shown in Figure 5, in the high-space resolution laser differential confocal induced breakdown, Raman spectrum-mass spectrum microscopic imaging device of embodiment 1, computing machine 10 can control the next one region to be measured that two-dimensional scanning mirrors system 37 makes middle hole measurement object lens 7 aim at sample 8.
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 (7)
1. laser differential confocal LIBS, Raman spectrum-mass spectrum imaging method, it is characterized in that: utilize the focal beam spot of high-space resolution laser differential confocal microscopic system to carry out axis to sample and focus and imaging, Raman spectrum detection system is utilized to detect the Raman spectrum that confocal microscope system focal beam spot excited sample produces, utilize the charged molecule that mass spectrometry detection system produces laser 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 differential confocal microscopic system focal beam spot desorption ionization sample detects, and then imaging and the detection of sample microcell high-space resolution and highly sensitive form and component is then realized by the fusion of detection data information and compare of analysis, comprise the following steps:
Step one, make parallel beam (1) by being shaped as annular beam (4) after ring light generation systems (3), this annular beam (4) again along light output direction through spectroscope (5), to enter through mesopore colour annalyzer (6) reflection and be arranged in the optical axis reciprocal hole measurement object lens (7) of folding and focus on sample (8);
Step 2, computing machine (10) controls by middle hole measurement object lens (7), axial objective scanner (11) of placing coaxial with middle hole measurement object lens (7), mesopore optical splitter (6), the spectroscope (5) of mesopore optical splitter (6) reflection direction and be positioned at the dichro iotac beam (36) in spectroscope (5) reflected light direction, the laser differential confocal detection system that the differential confocal light intensity detector (2) of dichro iotac beam (36) reflection direction is formed is carried out axial scan by axial objective scanner (11) to sample (8) and is recorded the first confocal axial strength curve (15) and the second confocal axial strength curve (16),
Step 3, the second confocal axial strength curve (16) and differential the subtracting each other of the first confocal axial strength curve (15) are obtained differential confocal axial strength curve (17), utilize differential confocal axial strength curve (17) accurately can locate this axial height information of sample (8);
Step 4, computing machine (10) are according to the null position z of differential confocal axial strength curve (17)
avalue controls axial objective scanner (11) makes the focal beam spot of middle hole measurement object lens (7) focus on sample (8);
Step 5, utilize by middle hole measurement object lens (7), axial objective scanner (11) of placing coaxial with middle hole measurement object lens (7), mesopore optical splitter (6), the spectroscope (5) of mesopore optical splitter (6) reflection direction, be positioned at spectroscope (5) reflected light direction dichro iotac beam (40), the microcell that Raman spectrum detection system centring hole measurement object lens (7) that the Raman spectral collection lens (41) of dichro iotac beam (40) transmission direction and the Raman spectrum detection system (42) at Raman spectral collection lens (41) focus place are formed focuses on sample (8) carries out Raman spectrum detection, record sample chemical key and the molecular structure information in corresponding focal beam spot region,
Step 6, change parallel beam (1) light illumination mode, excite the microcell desorption ionization of sample (8) to produce plasma plume (9);
Step 7, utilize ionized sample suction pipe (18) 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 (19) 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 (31) to carry out Laser-induced Breakdown Spectroscopy detection to the microcell measuring object lens (7) through mesopore colour annalyzer (6) transmission, mesopore catoptron (29) reflection and Laser-induced Breakdown Spectroscopy collecting lens (30) Laser-induced Breakdown Spectroscopy (32) centring hole of collecting and focus on sample (8), the sample element recording corresponding focal beam spot region forms information;
The Information in Mass Spectra of the Laser Focusing microcell that the Laser-induced Breakdown Spectroscopy (32) of the Laser Focusing microcell that the Raman spectrum (43) of the Laser Focusing microcell that the Laser Focusing facula position height of specimen information that laser differential confocal detection system records by step 9, computing machine (10), laser Raman spectroscopy detection system (42) detect, Laser-induced Breakdown Spectroscopy detection system (31) detect, mass spectrometry detection system (19) detect carries out fusion treatment, then obtains the height of focal beam spot microcell, spectrum and Information in Mass Spectra;
Step 10, computing machine (10) control two-dimentional work bench (20) makes middle hole measurement object lens (7) aim at the next one region to be measured of sample (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 (10) to carry out process and can obtain sample (8) shape information and complete component information.
2. a kind of laser differential confocal LIBS according to claim 1, Raman spectrum-mass spectrum imaging method, it is characterized in that: comprise after step one can be vector beam generation systems (21), spectroscope (5) and the iris filter (22) making parallel beam (1) pass through to place along optical axis direction and be shaped as annular beam (23), this annular beam (23) enters mesopore through mesopore colour annalyzer (6) reflection again and measures object lens (7) and focus on sample (8).
3. a kind of laser differential confocal LIBS according to claim 1, Raman spectrum-mass spectrum imaging method, it is characterized in that: comprise step 9 and can be the next one region to be measured that computing machine (10) control two-dimensional scanning mirrors system (37) makes middle hole measurement object lens (7) aligning sample (8), then operate by step 2 ~ step 9, obtain the height of next focal beam spot to be measured, spectrum and Information in Mass Spectra.
4. a laser differential confocal LIBS, Raman spectrum-mass spectrum imaging device, it is characterized in that: comprise laser point light source system (24), along the collimation lens (25) that optical axis direction is placed, produce the annular beam light generation systems (3) of annular beam, spectroscope (5), mesopore optical splitter (6) and the focal beam spot placed along optical axis direction of turning back are to the middle hole measurement object lens (7) of sample (8), comprise the differential confocal light intensity detector (2) for hole measurement object lens (7) focal beam spot intensity of reflected light signal in detection, for the dichro iotac beam (40) of harmless separation Raman spectrum, the Raman spectral collection lens (41) of Raman spectrum (43) excited for hole measurement object lens (7) focal beam spot in detection and be arranged in Raman spectral collection lens (41) focus Raman spectrum detection system (42) and for the ionized sample suction pipe (18) of ion body feathers (9) component that detects hole measurement object lens (7) focal beam spot desorption ionization and mass spectrometry detection system (19), also comprise the mesopore colour annalyzer (6) of exploring laser light induced breakdown spectroscopy (32), be positioned at the mesopore catoptron (29) in mesopore colour annalyzer (6) transmitted light direction, be positioned at the Laser-induced Breakdown Spectroscopy collecting lens (30) in mesopore catoptron (29) reflected light direction and the Laser-induced Breakdown Spectroscopy detection system (31) at Laser-induced Breakdown Spectroscopy collecting lens (30) focus place.
5. a kind of laser differential confocal LIBS according to claim 4, Raman spectrum-mass spectrum imaging device, it is characterized in that: differential confocal intensity detector (2) comprises detection spectroscope (33), be placed on first light collecting lens (12) in detection spectroscope (33) transmitted light direction successively, first detecting pinhole (13), first light intensity detector (14), also comprise the second light collecting lens (34) being placed on detection spectroscope (33) reflected light direction successively, second detecting pinhole (35) and the second light intensity detector (36), before first detecting pinhole (13) is placed in the first light collecting lens (12) Jiao, it is defocused that second detecting pinhole (35) is placed in the second light collecting lens (34), first light collecting lens (12) is equal with the second light collecting lens (34) focal length, first detecting pinhole (13) is contrary with the second detecting pinhole (35) defocusing amount size equidirectional.
6. a kind of laser differential confocal LIBS according to claim 4, Raman spectrum-mass spectrum imaging device, is characterized in that: comprising ring light generation systems (3) can substitute with the vector beam generation systems (21) of the generation vector beam placed along optical axis direction and iris filter (22).
7. a kind of laser differential confocal LIBS according to claim 4, Raman spectrum-mass spectrum imaging device, is characterized in that: comprising laser point light source system (24) can be made up of pulsed laser (26), the condenser lens (27) being positioned at laser emitting direction and the pin hole (28) being positioned at condenser lens (27) focus.
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