CN107305186A - Utilize the method for Raman spectrum differentiation naturally with artificial synthesized CVD diamonds - Google Patents
Utilize the method for Raman spectrum differentiation naturally with artificial synthesized CVD diamonds Download PDFInfo
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- CN107305186A CN107305186A CN201610261540.4A CN201610261540A CN107305186A CN 107305186 A CN107305186 A CN 107305186A CN 201610261540 A CN201610261540 A CN 201610261540A CN 107305186 A CN107305186 A CN 107305186A
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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 method of utilization Raman spectrum differentiation naturally with artificial synthesized CVD diamonds, comprise the following steps：A Raman analyser is provided, its laser power is 450 mw, and the spectral collection time is 1~5 second, average 12 times, and utilizes its S/N>10,000 highly sensitive characteristics, then with detecting head sweep test sample；There is provided one and correct unit, it is obtained with the flat Raman setting collection of illustrative plates scope of correct intensity and baseline to perform automatic wave number with intensity correction with removing background fluorescence with profit；And natural artificial synthetic diamond is identified by the raman characteristic peak after calibration standard.
Description
Technical field
The method divided naturally with artificial synthetic diamond is distinguished the invention relates to a kind of, one kind is particularly related to and utilizes Raman
The method of spectral discrimination naturally with artificial synthesized CVD diamonds.
Background technology
The artificial synthetic diamond occurred on the market at present is segmented into two kinds according to synthetic method, and one kind is chemical vapor deposition
Area method (CVD) diamond, another is high temperature and high pressure method (HPHT) diamond, and due to technique improvement and cost reduction, in the market is
Through there are many high-quality artificial synthetic diamonds, and rough diamond can be distinguished and artificial still without a kind of effective ways so far
How synthesizing diamond, distinguish effectively and correctly naturally and artificial synthetic diamond, be need most at present the technical problem of solution with
Blind spot.
The content of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is providing a kind of innovative technology differentiation of utilization Raman spectrum
Naturally with the method for artificial synthesized CVD diamonds.
To reach object defined above, the present invention using the innovative technology of Raman spectrum distinguish naturally with artificial synthesized CVD diamonds
Method, comprise the following steps：A Raman analyser is provided, its laser power is 450 mw, the spectral collection time is 1~5 second,
It is average 12 times, and utilize its S/N>10,000 highly sensitive characteristics, then with detecting head sweep test sample；One is provided to correct
Unit, it obtains flat with correct intensity and baseline to perform automatic wave number with intensity correction with removing background fluorescence with profit
Raman setting collection of illustrative plates scope；And natural artificial synthetic diamond is identified by the raman characteristic peak after calibration standard.
According to the specific implementation of the present invention, it should be defined with the flat Raman setting collection of illustrative plates scope of correct intensity and baseline
For 100 ~ 3300 cm-1。
According to another specific implementation of the present invention, rough diamond is in 2030 cm of Raman spectrum-1 With a Raman signatures
Peak, its intensity is higher than CVD diamonds.
According to another specific implementation of the present invention, CVD diamonds are in 982 cm of Raman spectrum-1With a Raman fluorescence peak,
And in 2030 cm-1Do not occur or intensity is only presented close to zero raman characteristic peak.
According to the present invention another specific implementation, the CVD diamonds handled via microwave method, its in Raman spectrum 200
cm-1、440 cm-1There is significant lattice defect peak respectively.
Brief description of the drawings
Fig. 1 a are for diamond in Raman spectrum scope in 100 cm-1And 3300 cm-1Between spectrogram.
Fig. 1 b are natural DGA 01 ~ 50 2030 cm-1The folded figure of Raman spectrum.
Fig. 1 c are natural DGA 51 ~ 100 2030 cm-1The folded figure of Raman spectrum.
Fig. 1 d are naturally with artificial synthesized CVD diamonds in 2030 cm-1C-N keys Raman spectrum fold figure discrimination analysis.
Fig. 2 a are sample CVD-01 Raman spectrogram.
Fig. 2 b are the enlarged drawing (A) of sample CVD-01 Raman spectrum, wherein in 982 cm-1With small fluorescence peak.
Fig. 2 c are the enlarged drawing (B) of sample CVD-01 Raman spectrum, wherein in 2030 cm-1Peak value does not have intensity.
Fig. 3 a are sample CVD-02 Raman spectrograms.
Fig. 3 b are sample CVD-02 Raman spectrums enlarged drawing (A), wherein in 982 cm-1With small fluorescence peak.
Fig. 3 c are sample CVD-02 Raman spectrums enlarged drawing (B), wherein in 2030 cm-1Peak value does not have intensity.
Fig. 3 d are microwave method CVD diamond lattice defect characteristics peak.
Embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings, so that those skilled in the art can be with
It is better understood from the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Area of the method for the present invention using high performance portable Raman analyser come good authentication naturally with synthesizing diamond
Not.General natural Ia diamonds all can be in 2030 cm when being detected with Raman analyser-1One and nitrogen carbon (N- is presented in beam location
C) related vibration performance peak, however, raman characteristic peak of the artificial synthesized CVD diamonds but without this vibration；In addition, being closed with CVD
Into diamond also can be in 982 cm-1A silicon residual from substrate is presented in beam location（Si-derived) characteristic peak, and CVD
Microwave method synthesizing diamond then in addition can be in 200 cm-1、440 cm-1There are two Raman lattice defect peaks left and right（lattice
Defects), these raman characteristic peaks may serve to the very efficiently area of Rapid identification naturally with artificial synthetic diamond
Not.
The method of the present invention comprises the following steps：Using the Raman analyser of Toptek-Enwave (TSI) A6 types,
Laser power is 450 mw, and the spectral collection time is 1~5 second, average 12 times.Utilize its S/N>10,000 highly sensitive spies
Property, then scanned with large spot large area detecting head（>100 um）Test sample, automatic wave number and intensity are done via special-purpose software again
Correction（Auto - XY Calibration）With removing background fluorescence（Autobaseline）, with profit obtain have correct intensity with
Flat Raman setting collection of illustrative plates scope (100 ~ 3300 cm of baseline-1), then again with the drawing after calibration standard (Normalised)
Graceful characteristic peak identifies natural artificial synthetic diamond.Herein analyzed it is all more than 100 naturally with CVD synthesizing diamonds, entirely
Portion is all provided in DGA certified program.
Rough diamond（Ia,Ib,lla）In color-causing element be micro nitrogen, due to being denier, in IIa types
20 ppm can be even less than in diamond, if so being intended to detect the micro nitrogen content in diamond with Raman analyser, instrument is clever
The requirement standard of sensitivity needs very high（S/N>10000) these trace elements can not, otherwise be measured.In general air
Nitrogen, if can be in 2330 cm with the spectrum main peak of Raman detection-1If the carbon-to-nitrogen bond in diamond then can be in Raman spectrum
In in 2030 cm-1Nearby (ginseng Fig. 1 a), these micro nitrogens are the color-causing elements of diamond, and the more, diamond is just for nitrogen content
It is more yellow, conversely, fewer just more colourless.If so with Raman detection nitrogen content therein the more, its 2030 cm-1Peak strength
Just higher, vice versa！
The raman characteristic peak of general diamond is in 1332 cm-1, this characteristic peak is the tension vibration mould of carbon-carbon bond (C-C), and day
Right diamond is in 2030 cm-1There is an extra raman characteristic peak（Nitrogen impurity）, 2030 cm of method discovery of the present invention-1Raman
Characteristic peak is only present in rough diamond (ginseng Fig. 1 b, 1c), in addition, the present invention also collects artificial synthesized CVD diamonds in same range
Raman collection of illustrative plates, artificial synthesized CVD diamonds are in 2030 cm-1Do not occur or raman characteristic peak of the intensity close to zero is (referring to figure
1d), thus utilize 2030 cm-1The presence or absence of Raman peaks, you can with as natural first judgement with artificial synthesized CVD diamonds
Foundation.
In general, CVD synthesizing diamond is not because almost nitrogenous, we in Fig. 2 c, Fig. 3 c enlarged drawing,
It is hardly visible the cm of raman characteristic peak 2030 of nitrogen-1In the presence of, and in Fig. 2 b, Fig. 3 b) enlarged drawing in, we can observe
To 982 cm-1(Huong 1991;Weringhaus 1996) there are an obvious characteristic peak, this 982 cm-1Feature
Peak is the carbon silicon of CVD diamonds denier in the fabrication process（Si-C）Remain (Alexander M.Zaitsev 2000), because
It is a residue of denier, so the analyzer for also there was only hypersensitivity can detect this micro Raman fluorescence
The presence at peak, such 982 cm-1Fluorescence spectrum can similarly be present in other CVD samples (Pic.2) detections, such as Fig. 3
Among CVD-02, in addition, we also observe the amplification in Fig. 2 c, Fig. 3 c（zoom in）In spectrum, wherein 2187 cm-1、
2260 cm-1、2336 cm-1、2470 cm-1、2667 cm-1These peaks spectrum is the second order spectrum of diamond, if so we are with drawing
Graceful spectral detection CVD diamond, there is the peak value of two observation index spectrum：First: 2030 cm-1, second: 982 cm-1, its
In 2030 cm-1Intensity is there's almost no in CVD diamond, because the nitrogen impurity contained by such synthesizing diamond is
Denier or do not have, so much nitrogen impurity contained by general diamond is not as, so the CVD diamonds that someone mediates are almost
IIa type diamonds.
The CVD diamonds of microwave current method are except 982 cm-1Silicon residual value characteristic peak outside, generally also can be in 200 cm-1、440
cm-1Have very strong lattice defect peak, this two lattice defect peaks can as one of identification mark of microwave method CVD synthesizing diamonds,
It is also very fast and accurately decision method (ginseng Fig. 3 d).
The method of the present invention utilizes the advantage of Raman spectrometer：Non-destructive, pin fast without pre-treatment and analyze speed
A kind of differentiating method is provided to rough diamond and artificial synthesized CVD diamonds, its characteristic is as follows：(a) using diamond in 2030 cm-1
Raman characteristic peak whether there is as the method natural with artificial synthesized CVD diamonds of differentiation, set up science and just objective identification
Mode.(b) diamond of CVD synthesis can be in 982 cm-1A silicon residual from substrate is presented in beam location（Si-derived)
Characteristic peak, if but substrate when being diamond or polishing, polishing, then the silicon persistence characteristic peak from substrate may not then be present.(c)
200 cm can be then presented in microwave method CVD diamonds-1、440 cm-1Lattice defect peak.(d) this method can be naked to various diamonds
Stone is identified with the diamond inlayed, and can also be made a distinction for the diamond of various sizes.(e) this method utilizes soft
Part is with standard sample progress intensity correction and Baseline Survey, diamond Raman peaks strength difference when reduction is analyzed every time, allows and divides every time
Data during analysis can be consistent.(f) hundreds of CVD diamonds have been validated successfully and true school.
Embodiment described above is only the preferred embodiment to absolutely prove the present invention and being lifted, protection model of the invention
Enclose not limited to this.Equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, in the present invention
Protection domain within.Protection scope of the present invention is defined by claims.
Claims (5)
1. a kind of utilization Raman spectrum distinguishes method naturally with artificial synthesized CVD diamonds, it is characterised in that including following step
Suddenly：
A Raman analyser is provided, its laser power is 450 mw, and the spectral collection time is 1~5 second, average 12 times, and is utilized
Its S/N>10,000 highly sensitive characteristics, then with detecting head sweep test sample；
There is provided one and correct unit, it is to perform automatic wave number and intensity correction and remove background fluorescence, and being obtained with profit has correctly
The intensity Raman setting collection of illustrative plates scope flat with baseline；And
Natural artificial synthetic diamond is identified by the raman characteristic peak after calibration standard.
2. the method as described in claim 1, it is characterised in that should be with the flat Raman setting collection of illustrative plates of correct intensity and baseline
Scope is defined as 100 ~ 3300 cm-1。
3. the method as described in claim 1, it is characterised in that rough diamond is in 2030 cm of Raman spectrum-1 Drawn with one
Graceful characteristic peak, its intensity is higher than CVD diamonds.
4. the method as described in claim 1, it is characterised in that CVD diamonds are in 982 cm of Raman spectrum-1It is glimmering with a Raman
Photopeak, and in 2030 cm-1Do not occur or intensity is only presented close to zero raman characteristic peak.
5. method as claimed in claim 4, it is characterised in that the CVD diamonds handled via microwave method, it is in Raman spectrum
200 cm-1、440 cm-1There is lattice defect peak respectively.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585895A (en) * | 2001-09-12 | 2005-02-23 | 杰桑企业 | Examining a diamond |
| US20160109374A1 (en) * | 2014-10-18 | 2016-04-21 | Dong-Shyogn Pan | Examination method for distinguishing between natural diamond and synthetic cvd/hpht diamonds |
| US20160109373A1 (en) * | 2014-10-18 | 2016-04-21 | Dong-Shyogn Pan | Examination method to apprais corundum that has undergone beryllium diffusion treatment |
-
2016
- 2016-04-25 CN CN201610261540.4A patent/CN107305186A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585895A (en) * | 2001-09-12 | 2005-02-23 | 杰桑企业 | Examining a diamond |
| US20160109374A1 (en) * | 2014-10-18 | 2016-04-21 | Dong-Shyogn Pan | Examination method for distinguishing between natural diamond and synthetic cvd/hpht diamonds |
| US20160109373A1 (en) * | 2014-10-18 | 2016-04-21 | Dong-Shyogn Pan | Examination method to apprais corundum that has undergone beryllium diffusion treatment |
Non-Patent Citations (1)
| Title |
|---|
| 康亚楠 等: ""天然蓝宝石与合成蓝宝石的拉曼光谱研究"", 《昆明理工大学学报》 * |
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Application publication date: 20171031 |