CN109839369A - A method of the graphite degree of order is measured based on LR laser raman Mapping - Google Patents
A method of the graphite degree of order is measured based on LR laser raman Mapping Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 85
- 239000010439 graphite Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000001530 Raman microscopy Methods 0.000 title claims abstract description 18
- 238000013507 mapping Methods 0.000 claims abstract description 36
- 238000004458 analytical method Methods 0.000 claims abstract description 25
- 238000005259 measurement Methods 0.000 claims abstract description 19
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 13
- 238000012937 correction Methods 0.000 claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 238000003384 imaging method Methods 0.000 claims abstract description 8
- 239000003086 colorant Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 239000003550 marker Substances 0.000 claims abstract description 4
- 238000001228 spectrum Methods 0.000 claims description 35
- 238000001069 Raman spectroscopy Methods 0.000 claims description 33
- 230000003287 optical effect Effects 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 230000003595 spectral effect Effects 0.000 claims description 7
- 230000013011 mating Effects 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000004164 analytical calibration Methods 0.000 claims description 3
- 238000012790 confirmation Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims description 3
- 238000004611 spectroscopical analysis Methods 0.000 claims description 3
- 238000011017 operating method Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003841 Raman measurement Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002493 microarray Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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Abstract
The invention discloses a kind of methods based on the LR laser raman Mapping measurement graphite degree of order, comprising the following steps: S1, sample preparation；S2, graphite observation analysis；S3, device parameter setting；S4, instrumental calibration correction；S5, data processing and imaging: the step S1 sample prepared is placed in corresponding detection zone, system according to setting condition acquisition step S2 marker site Raman spectrum and save measured graphite Mapping initial data, and initial data is carried out to be fitted the data at the peak D and G analysis, select the area ratio at the peak D and G, different color, which is arranged, indicates range, it is reflected to the degree of order of graphite with different colours.This method sample preparation is simple, and sample requirement is low, and ordinary sheet can be tested directly, while this method uses high-precision coatings by situ, and precision can actually solve the problems, such as to be difficult to the coatings by situ measurement graphite degree of order with traditional means of experiment up to 2 μm.
Description
Technical field
The invention belongs to mineral detection technique fields, and in particular to one kind is had based on LR laser raman Mapping measurement graphite
The method of sequence degree.
Background technique
Graphite (graphite) is a kind of crystalline carbon, hexagonal crystal system, for iron mass colour to Dark grey, 2.25 gram/li of density
Rice 3, hardness 1.5,3652 DEG C of molten point, 4827 DEG C of boiling point.Graphite crystal is characterized in typical layer structure, carbon atom stratification row
Column, are equidistantly connected between each carbon and adjacent carbon, and the carbon in each layer is arranged by hexagonal ring shape, six side of carbon of neighbouring layer
Ring is stacked again after being mutually displaced by parallel wire side direction and forms layer structure, and the azimuth-range difference of displacement results in difference
Multi-structure.Loosely accumulation is exactly that the degree of disorder is poor to same carbon atom in a jumble, can only form the graphite of pitch-black weakness, and is had
Good then being combined with cuboctahedron structure of sequence to form hard unmatched diamond.
Laser Raman spectroscopy is a kind of microarrays techniques of nondestructively measuring material molecule ingredient, is based on laser light
After with material molecule inelastic collision occurs for son, change a kind of molecular scattering spectrum of original incident frequencies.In recent years, with drawing
The development of graceful spectral technique, not only directly reflects molecular structure information, and form, half width values, area ratio also reflect ground
The variation of crystallinity and the degree of order in quality sample and by extensive concern.
Raman spectroscopy utilizes 3D fast imaging Raman spectroscopy in the fast development of mineralogy field in recent years
(Mapping technology) etc. also will appreciate that the information such as mineral composition, stress distribution.The technology be by equipped with StreamLineHR at
As attachment novel inVia series Raman spectrum system realize, can unrestricted choice imaging area, thus on a large scale, three-dimensionally
The Raman data for collecting and showing sample interior, such as the intensity or other more complicated parameters of Raman spectrum band, make test pattern from
Conventional " spot scan " has risen to " Surface scan ".
The conventional method for obtaining the graphite degree of order at present is to utilize XDR method, but XDR test method can only symbolize magnetic material
The presence of matter is but carbon without any corresponding peak, to further determine that carbon is with existing for what state, Raman spectrum is
Preferable selection, but have a disadvantage in that measuring point quantity is excessive, efficiency is lower.
Summary of the invention
Present invention aim to address the above problems, provide a kind of based on the LR laser raman Mapping measurement graphite degree of order
Method.
In order to solve the above technical problems, the technical scheme is that a kind of measure graphite based on LR laser raman Mapping
The method of the degree of order, comprising the following steps:
S1, sample preparation: film-making is carried out to rock sample, grinds polishing both surfaces thin slice, obtains ordinary graphite thin slice；
S2, graphite observation analysis: confirmation graphite position and form, and be marked；
S3, parameter setting: carrying out conventional parameter setting to Raman instrument, and wherein the time for exposure is 1S~1.5S, microscope
Object lens 100X or 50X are selected, is adopted between time spectrum as 1S~1.5S, 1~3 μm of step-length；
S4, instrumental calibration correction: instrument optical path and peak position are calibrated；
S5, data processing and imaging: the step S1 sample prepared is placed in corresponding detection zone, system is according to setting item
The Raman spectrum of part acquisition step S2 marker site simultaneously saves measured graphite Mapping initial data, and to initial data
It carries out being fitted the data at the peak D and G analysis, selects the area ratio at the peak D and G, setting different color indicates range, used
Different colours reflect the degree of order of graphite.
In above-mentioned technical proposal, in the step S1, the blocked up test and identification for influencing sample of thin slice is excessively thin to certain mines
Object is improper.The thickness of thin slice is preferably 0.1~0.3mm.The preferred 50mm*25mm of lamina dimensions, for Raman, shape and
Length and width have no specifically limited.Further, sample preparation is carried out preferably under room temperature, thin slice clears up surface impurity after completing
Re-polishing.If surface is already oxidised too long or there are other impurity for sample placement before testing, cleaning again need to be carried out to thin slice and is polished.
Further, slide no longer preferably is covered on sample in the present invention.Laser can wear slide, and sample is put into
It is not influenced generally below bright glass cover-slip.But coverslip is not added, it is possible to reduce the possibility of glue stain, and have coverslip
When, it is possible to misoperation Raman focal position is not right, gathers on slide, measure come the result is that the spectrum of glass.And glue produces
Raw the reason of influencing: fluorescence is produced.Raman measurement is reflected light after molecule is stimulated, thus for some substances for example without
Substance glass of sizing etc. can generate strong fluorescence interference in the assay, and Raman signal is covered.Now for disappearing for fluorescence
Except replacement light source is usually used, avoids fluorescence from occurring in the wave-number range of measurement by changing excitation wavelength, sometimes do
Fluorescence background is stronger when Raman, it is necessary to change excitation wavelength to eliminate fluorescence and influence, will increase the complexity of test in this way
Property.
In above-mentioned technical proposal, in the step S2, the purpose of the position and form that confirm graphite is to do standard in next step
It is standby, find test target because in sample may include multiple graphite, be mapping test first select a range come into
Row.Range size does not have special limitation, is drawn a circle to approve according to the actual situation, but range should not be too big, because size is determined
Determined a little number, influence test total time efficiency.Concrete operation step is to find graphite under an optical microscope first,
Drawn a circle to it label using marking pen, everybody point be marked using Arabic numerals in sequence, then scribing line by everybody
Point is linked in sequence, and photographs to record the object of reference near its form and graphite.Form includes the shape, big of graphite mineral
Small, gloss, external crack, surface pattern.
In above-mentioned technical proposal, in the step S3, time for exposure, microscope selection object lens multiple, adopt between time spectrum and
Step-length will affect the precision of test.The present invention preferred time for exposure is 1S, and microscope selects object lens 100X, is adopted between time spectrum as 1S,
1 μm of step-length.For other conventional parameters of Raman instrument, the setting including laser, grating, confocal pinhole and slit can root
It is configured according to this field conventional arrangement parameter, in the present invention preferred 514nm/30-50mW laser, 1800 line of grating, altogether
200~400 μm of burnt aperture size, slit are 100 μm.514 nanometers of (green light) lasers, performance is sufficiently stable, and in addition 532 nanometers
Solid state diode pump laser, 632.8 nanometers (feux rouges), the visible lasers such as 780 nanometers and 785 nanotube diodes,
830 nm near-infrared lasers are used equally for the present invention.
Theoretically, Raman spectrum is unrelated with the wavelength of exciting light.But some samples are under a kind of laser excitation of wavelength
Intense fluorescence can be generated, interference is generated to Raman spectrum.At this moment a kind of exciting light is changed, to avoid the interference of fluorescence.If sample
It does not fluoresce under different laser excitations, then with using any laser to be ok.
In above-mentioned technical proposal, in the step S4, and also specifically includes the following steps:
S41, the correction of laser optical path hot spot: facula position has uniformity and eupnea in cross searching, hot spot；
The calibration of S42, signal optical path: signal optical path includes mating plate, focus lamp, slit, prism, grating W and detection
Device ccd signal detection system adjusts slit size and location and the signal receiving area of detector C CD；
S43, XY automatic platform with manually control it is mating and calibration state of white light it is consistent with the focussing plane of laser state；
The wave number calibration correction of S44, Raman instrument: 520.7cm is used first-1Silicon wafer makees the wave number calibration of Raman instrument, mark
Sample timing selects the laser of 514nm, adopts spectrum in real time to silicon wafer progress, by going back end, mark peak position to obtain the peak position of spectrum,
Then silicon wafer peak position is transferred to the 520.7cm of standard by the Instrument calibration in setup menu-1。
It is worth noting that being this field routine operation means to instrument peak position and light path calibration.For laser optical path light
Spot, distinct device Raman spot size should be also different under the same equipment difference of difference focuses, it is necessary to be configured
And correction, guarantee the reproducibility and accuracy of Raman.It for signal optical path, if not changing light source, does not need generally to calibrate, only need
Optical path and intensity are corrected, carrys out sample when needing replacing laser, just needs to correct again.XY automatic platform is according to journey
The point of sequence is tested, and is tested interested point manually, acts on identical, manual dexterity height.State of white light
Calibration with laser state is complemented each other to make result relatively reliable, and the information of the two detection is relatively reliable.
In above-mentioned technical proposal, in the step S5, and also specifically includes the following steps:
S51, sample is moved to and does the region Mapping, confirmed laser facula heart position in the sample, be then turned off laser；
S52, four points are successively selected along upper left, bottom right, upper right and lower-left using the point mapping mode of system,
Then X, Y are chosen in mapping prosities, selects single window mode, adopted and be set as 1-10 between time spectrum
Second, parameter, which clicks Mapping acquisition after all setting, allows automatic platform successively along upper left, bottom right, upper right and lower-left
Four spot scans one are enclosed, and do Mapping range with box is selected, the step-length of X-axis and Y direction, step-length in the present embodiment is arranged
It is set as 1um, adopts spectral limit and be changed to multiwindow mode, Mapping acquisition is clicked after parameter setting is good and is adopted
Test analysis is composed, tetra- windows of Spim, Point, Map and Video are obtained after test, while saving Spim and Video window
Mouthful, the peak spectrum of the graphite Mapping raw process parameter data that Lai Baocun is measured, the graphite Mapping initial data measured is reflected in
On three-dimensional space；
S53, Mapping spectroscopic data obtain on the basis of, handled using data of the Wire software to the peak D and G,
Concrete operation method are as follows: all spectrum be fitted except baseline and peak position in Spim window, when sample is by fluorescence or heat
The influence of back end, making Raman spectrum, there are angle tilts, and contain signal source in inclined substrate, it is necessary to by removing baseline
Method obtain the flat spectrum of baseline, can be direct by the Processing subtract baseline function of software window
Operation；Peak position includes that peak intensity, half-peak breadth, peak area are fitted analysis, it is generally the case that required peak position can have offset
Or two and the superposition of more than two peak positions, peak position fitting not only available simple unimodal accurate parameter can be with
The accurate parameter of the overlapping complex spectrum band in multiple peaks is obtained, method particularly includes: selection Analysis curve fit function is beaten
Open curve is fitted window, and the peak G and D being fitted to needs amplifies, and mobile mouse to the position for the bands of a spectrum for needing to be fitted is clicked
Peak position is added, can be added with adopting consecutive click chemical reaction, Add curves in context menu can be clicked when not having peak position to continue to occur i.e.
Can, both component spectras of D and G are then defined by Model function, to obtain exhibition of two components on the two-dimensional surface
Cloth constructs graphite three-dimensional space D and the peak G spread on above-mentioned analysis foundation, by Raman spectrometer read the peak graphite D and
The distribution situation of the peak G relevant parameter acquires the D/G area ratio of graphite, finally selects the area ratio at the peak D and G, and different color is arranged
It indicates range, it is reflected to the degree of order of graphite with different colours.
The basic principle that step S53 is related to: after deducting substrate, according to the position at the peak D, G of standard, the peak D corresponds to
1360cm-1Left and right, the peak G is 1580cm-1Left and right, might have positive and negative 10 or so deviation, to determine the correspondence position of sample spectral line
The peak area set is parsed using symmetrical peak principle.(there is superposition at two peaks) carries out swarming fitting, graphite sample when necessary
It does not need generally.The peak D is disordering peak (disorder), and the peak D and G is all caused by having sp2.1585cm-1The Raman peaks of left and right
It is the typical Raman peaks of body phase crystalline graphite, claims G band.This peak is the basic vibration mode of graphite crystal, intensity and crystal
Size is related.1360cm-1The Raman peaks at place are originated from the vibration at graphitic carbon crystalline state edge, referred to as D band.This at two Raman peaks be class stone
The typical Raman peaks of black carbon (such as graphite, carbon black, activated carbon etc.).
Additionally can with other methods, such as the operation to be carried out curve fitting using mathematical software MAPLE.
Method provided by the invention based on the LR laser raman Mapping measurement graphite degree of order has the advantages that
(1) the XDR method that tradition obtains the graphite degree of order is based on putting and test, but in fact, graphite mineral in thin slice,
It may be affected by various factors and uneven, and especially manual pointwise test, analysis may go to miss part important
Point, especially time of measuring is longer, needs the human-computer interaction time long；And this method sample preparation is simple, sample requirement is low, ordinary sheet
It can directly test, while this method uses high-precision coatings by situ, precision can be up to 2 μm；
(2) based on the LR laser raman analytical technology of layer mineral structure measurement, there is stronger visualization and summary
Operation, non-destructive and quickly provide a kind of new technological means for acquisitions of the graphite degree of order, actually solve use it is traditional
Experimental method is difficult to the problem of the coatings by situ measurement graphite degree of order, mentions for researchs such as graphite genesis mechanism and structural analyses
Reliable technical guarantee is supplied.
Detailed description of the invention
Fig. 1 is that the present invention is based on the flow charts of the LR laser raman mapping measurement graphite degree of order.
Fig. 2 is Mapping measuring point and Raman peaks spectrogram of the present invention.
Specific embodiment
The present invention is described further in the following with reference to the drawings and specific embodiments:
As shown in Figure 1, the method for the invention based on the LR laser raman Mapping measurement graphite degree of order, including following step
It is rapid:
S1, sample preparation: carrying out film-making to rock sample, grind polishing both surfaces thin slice, thin slice with a thickness of 0.1~0.3
㎜ obtains ordinary graphite thin slice, coverslip is not added；
S2, graphite observation analysis: confirmation graphite position and form, and be marked, specifically,
It finds graphite under an optical microscope first, is drawn a circle to it label using marking pen, in sequence using Arab
Everybody point is marked in number, and then crossing to put everybody is linked in sequence, and it is attached with graphite to photograph to record its form
Close object of reference；
S3, parameter setting: selection 514nm/30-50mW laser, 1800 line of grating, 200~400 μ of confocal pinhole size
M, slit are 100 μm, time for exposure 1S, and microscope selects object lens 100X, are adopted between time spectrum as 1S, step-length 1um；
S4, instrumental calibration correction: peak position is calibrated using standard specimen, specific step is as follows
S41, the correction of laser optical path hot spot: facula position has uniformity and eupnea in cross searching, hot spot；
The calibration of S42, signal optical path: signal optical path includes mating plate, focus lamp, slit, prism, grating W and detection
Device ccd signal detection system adjusts slit size and location and the signal receiving area of detector C CD；
S43, XY automatic platform with manually control it is mating and calibration state of white light it is consistent with the focussing plane of laser state；
The wave number calibration correction of S44, Raman instrument: 520.7cm is used first-1Silicon wafer makees the wave number calibration of Raman instrument, mark
Sample timing selects the laser of 514nm, adopts spectrum in real time to silicon wafer progress, by going back end, mark peak position to obtain the peak position of spectrum,
Then silicon wafer peak position is transferred to the 520.7cm of standard by the Instrument calibration in setup menu-1；
S5, data processing and imaging: the step S1 sample prepared is placed in corresponding detection zone, system is according to setting item
The Raman spectrum of part acquisition step S2 marker site simultaneously saves measured graphite Mapping initial data, and to initial data
It carries out being fitted the data at the peak D and G analysis, selects the area ratio at the peak D and G, setting different color indicates range, used
Different colours reflect the degree of order of graphite, specifically,
S51, sample is moved to and does the region Mapping, confirmed laser facula heart position in the sample, be then turned off laser；
S52, four points are successively selected along upper left, bottom right, upper right and lower-left using the point mapping mode of system,
Then X, Y are chosen in mapping prosities, selects single window mode, adopted and be set as 1-10 between time spectrum
Second, parameter, which clicks Mapping acquisition after all setting, allows automatic platform successively along upper left, bottom right, upper right and lower-left
Four spot scans one are enclosed, and do Mapping range with box is selected, the step-length of X-axis and Y direction, step-length in the present embodiment is arranged
It is set as 1um, adopts spectral limit and be changed to multiwindow mode, Mapping acquisition is clicked after parameter setting is good and is adopted
Test analysis is composed, tetra- windows of Spim, Point, Map and Video are obtained after test, while saving Spim and Video window
Mouthful, the peak spectrum of the graphite Mapping raw process parameter data that Lai Baocun is measured, the graphite Mapping initial data measured is reflected in
On three-dimensional space；
S53, Mapping spectroscopic data obtain on the basis of, handled using data of the Wire software to the peak D and G,
Concrete operation method are as follows: all spectrum be fitted except baseline and peak position in Spim window, when sample is by fluorescence or heat
The influence of back end, making Raman spectrum, there are angle tilts, and contain signal source in inclined substrate, it is necessary to by removing baseline
Method obtain the flat spectrum of baseline, can be direct by the Processing subtract baseline function of software window
Operation；Peak position includes that peak intensity, half-peak breadth, peak area are fitted analysis, it is generally the case that required peak position can have offset
Or two and the superposition of more than two peak positions, peak position fitting not only available simple unimodal accurate parameter can be with
The accurate parameter of the overlapping complex spectrum band in multiple peaks is obtained, method particularly includes: selection Analysis curve fit function is beaten
Open curve is fitted window, and the peak G and D being fitted to needs amplifies, and mobile mouse to the position for the bands of a spectrum for needing to be fitted is clicked
Peak position is added, can be added with adopting consecutive click chemical reaction, Add curves in context menu can be clicked when not having peak position to continue to occur i.e.
Can, both component spectras of D and G are then defined by Model function, to obtain exhibition of two components on the two-dimensional surface
Cloth constructs graphite three-dimensional space D and the peak G spread on above-mentioned analysis foundation, by Raman spectrometer read the peak graphite D and
The distribution situation of the peak G relevant parameter acquires the D/G area ratio of graphite, finally selects the area ratio at the peak D and G, and different color is arranged
It indicates range, it is reflected to the degree of order of graphite with different colours.
In the present embodiment the graphite sample of geological sample by mapping analyze to obtain the peak G, D parameter value and last point
The situation of change for analysing the graphite degree of order, selects different color end member range and color range, shows two-dimensional surface with different colours
On.
As shown in Fig. 2, Raman shift is in 1370cm-1(peak D) and 1583cm-1Two spectral peaks of (peak G) nearby are more apparent,
Its area ratio is to characterize one of the method for the graphite degree of order, therefore select the spectral peak of two above Raman shift as Main Analysis
Object.According to a large amount of samples Raman spectrum analysis as a result, become larger with D peak area, cause D/G area ratio to increase, virtue
Fragrant number of rings increases, and the defect of carbon atom skeleton is caused to increase, and the graphite degree of order is deteriorated.Therefore, it as the graphite degree of order is got higher, draws
Graceful peak Raman shift is in 1370cm-1Left and right area reduces, and D/G peak area ratio reduces, can also in the geological sample analyzed
See the phenomenon that D peak area becomes smaller.
In conclusion the method for the LR laser raman Mapping measurement graphite degree of order shows as gridding operation, Mapping
It is a kind of new imaging technique of LR laser raman instrument, sample mobile using software control automatic sample platform (X, Y both direction)
It is recorded by point, each point can be imaged on the detector, so as to realize spatially finer imaging test analysis.And
The Parameters variation of each point can be intuitively shown in two dimension or three-dimensional space, therefore this method is compared with the prior art, it is more smart
Really and efficiently.
Those of ordinary skill in the art will understand that the embodiments described herein, which is to help reader, understands this hair
Bright principle, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.This field
Those of ordinary skill disclosed the technical disclosures can make according to the present invention and various not depart from the other each of essence of the invention
The specific variations and combinations of kind, these variations and combinations are still within the scope of the present invention.
Claims (8)
1. a kind of method based on the LR laser raman Mapping measurement graphite degree of order, it is characterised in that: the following steps are included:
S1, sample preparation: film-making is carried out to rock sample, grinds polishing both surfaces thin slice, obtains ordinary graphite thin slice；
S2, graphite observation analysis: confirmation graphite position and form, and be marked；
S3, parameter setting: carrying out conventional parameter setting to Raman instrument, and wherein the time for exposure is 1S~1.5S, microscope selection
Object lens 100X or 50X are adopted between time spectrum as 1S~1.5S, 1~3 μm of step-length；
S4, instrumental calibration correction: instrument optical path and peak position are calibrated；
S5, data processing and imaging: the step S1 sample prepared is placed in corresponding detection zone, system is adopted according to setting condition
Collect the Raman spectrum of step S2 marker site and save measured graphite Mapping initial data, and initial data is carried out
Analysis is fitted to the data at the peak D and G, selects the area ratio at the peak D and G, setting different color indicates range, it is used different
Color reflects the degree of order of graphite.
2. the method according to claim 1 based on the LR laser raman Mapping measurement graphite degree of order, it is characterised in that:
In the step S1, thin slice with a thickness of 0.1~0.3mm.
3. the method according to claim 1 based on the LR laser raman Mapping measurement graphite degree of order, it is characterised in that:
In the step S1, after obtaining ordinary graphite thin slice, slide is not covered on graphite flake.
4. the method according to claim 1 based on the LR laser raman Mapping measurement graphite degree of order, it is characterised in that:
In the step S2, concrete operation step is to find graphite under an optical microscope first, is drawn a circle to it mark using marking pen
Note is in sequence marked everybody point using Arabic numerals, then crosses and everybody point is linked in sequence, and clap
According to the object of reference recorded near its form and graphite.
5. the method according to claim 1 based on the LR laser raman Mapping measurement graphite degree of order, it is characterised in that:
In the step S3, time for exposure 1S, microscope selects object lens 100X, adopts between time spectrum as 1S, 1 μm of step-length.
6. the method according to claim 1 based on the LR laser raman Mapping measurement graphite degree of order, it is characterised in that:
It further include selection 514nm/30-50mW laser, 1800 line of grating, 200~400 μ of confocal pinhole size in the step S3
M, slit are 100 μm.
7. the method according to claim 1 based on the LR laser raman Mapping measurement graphite degree of order, it is characterised in that:
In the step S4, and also specifically includes the following steps:
S41, the correction of laser optical path hot spot: facula position has uniformity and eupnea in cross searching, hot spot
The calibration of S42, signal optical path: signal optical path includes mating plate, focus lamp, slit, prism, grating W and detector C CD
Signal detection system adjusts slit size and location and the signal receiving area of detector C CD；
S43, XY automatic platform with manually control it is mating and calibration state of white light it is consistent with the focussing plane of laser state；
The wave number calibration correction of S44, Raman instrument: 520.7cm is used first-1Silicon wafer makees the wave number calibration of Raman instrument, standard specimen school
Timing selects the laser of 514nm, adopts spectrum in real time to silicon wafer progress, by going back end, mark peak position to obtain the peak position of spectrum, then
Silicon wafer peak position is transferred to the 520.7cm of standard by the Instrument calibration in setup menu-1。
8. the method according to claim 1 based on the LR laser raman Mapping measurement graphite degree of order, it is characterised in that:
In the step S5, and also specifically includes the following steps:
S51, sample is moved to and does the region Mapping, confirmed laser facula heart position in the sample, be then turned off laser；
S52, four points are successively selected along upper left, bottom right, upper right and lower-left using the point mapping mode of system, then
X, Y are chosen in mapping prosities, select single window mode, adopts and is set as 1-10 seconds between time spectrum,
Parameter, which clicks Mapping acquisition after all setting, allows automatic platform successively along upper left, bottom right, upper right and lower-left four
Spot scan one is enclosed, and is done Mapping range with box is selected, the step-length of X-axis and Y direction is arranged, step-length is all provided in the present embodiment
It is set to 1um, adopts spectral limit and be changed to multiwindow mode, Mapping acquisition is clicked after parameter setting is good and carries out adopting spectrum survey
Examination analysis, obtains tetra- windows of Spim, Point, Map and Video, while saving Spim and Video window after test, come
The graphite Mapping raw process parameter data measured is saved, the peak spectrum of the graphite Mapping initial data measured is reflected in three-dimensional space
Between on；
S53, Mapping spectroscopic data obtain on the basis of, handled using data of the Wire software to the peak D and G, specifically
Operating method are as follows: all spectrum be fitted except baseline and peak position in Spim window, when sample is by fluorescence or hot back end
Influence, making Raman spectrum, there are angle tilts, and contain signal source in inclined substrate, need to be by obtain except the method for baseline
The spectrum flat to baseline is directly operated by the Processing subtract baseline function of software window；
Peak position includes that peak intensity, half-peak breadth, peak area are fitted analysis, concrete operations are as follows: selection Analysis curve fit
Function opening curves are fitted window, and the peak G and D being fitted to needs amplifies, mobile mouse to the position for the bands of a spectrum for needing to be fitted
It sets, clicks and peak position is added, the Add curves in context menu is clicked when not having peak position to continue to occur, is then passed through
Model function defines both component spectras of D and G, so that spread of two components on the two-dimensional surface is obtained, in above-mentioned analysis
On the basis of construct graphite three-dimensional space D and the peak G spread, the peak graphite D and the peak G relevant parameter are read by Raman spectrometer
Distribution situation acquires the D/G area ratio of graphite, finally selects the area ratio at the peak D and G, setting different color indicates range, by it
Reflect the degree of order of graphite with different colours.
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| CN115452796A (en) * | 2022-08-19 | 2022-12-09 | 中国科学院上海硅酸盐研究所 | High-sensitivity identification method of immunochromatography test strip T line based on surface-enhanced Raman scattering imaging |
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