CN101311339B - Process for discriminating high growth rate chemical vapour deposition diamond single crystal - Google Patents
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- CN101311339B CN101311339B CN2008100506516A CN200810050651A CN101311339B CN 101311339 B CN101311339 B CN 101311339B CN 2008100506516 A CN2008100506516 A CN 2008100506516A CN 200810050651 A CN200810050651 A CN 200810050651A CN 101311339 B CN101311339 B CN 101311339B
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Abstract
The invention discloses a method for identifying high-speed growing chemical vapor deposition diamond single crystal, belonging to the technology field of diamond material. By testing the photoluminescence fluorescence spectrum on the growing surface of the CVD diamond single crystal got by taking the methane, hydrogen and nitrogen as the reactive gas on different positions along the side of the growing direction, the diamond single crystal with regular change of spectra strength is nitrating high-speed chemical vapor deposition diamond single crystal. Therefore, the CVD diamond single crystal can be separated from other diamond single crystals according to the changes of the strength of the photoluminescence fluorescence peak related to the nitrogen content. The method of the invention is simple, suitable and rapid, which can not damage the growing CVD single crystal diamond.
Description
Technical field
The invention belongs to the characterization technique field of diamond single crystal material, relate to the method for the chemical vapor deposition (CVD) diamond single crystal of differentiating the two-forty growth.
Background technology
At the beginning of 21 century, Washington, DC Ka Neiji institute develops the high-speed rapid growth method of isoepitaxial growth single-crystal diamond, and growth velocity can obtain 10 carats and above diamond single crystal up to 50-150 μ m/h.The CVD method is produced diamond single crystal, and advantage such as have that equipment is simple, easy to operate, good reproducibility, crystalline growth size are unrestricted is just becoming the most promising method low-cost, large-particle monocrystal diamond of producing.Studies show that the CVD diamond single crystal that is obtained has the character identical or close with natural diamond.An important problem is, whether can distinguish CVD diamond single crystal and natural diamond, and diamond (gem grade diamond monocrystalline) industry is had tremendous influence.
With the present invention immediate be Carnegie Inst of Washington patent of invention (application number: 02826062.7), the patent of invention (application number: 200710055326.4) of patent of invention of Element Six Ltd. (ZL 01812728.2) and Jilin University.Above-mentioned patent provides the method for high speed isoepitaxial growth single-crystal diamond, but does not all mention the method for diamond single crystal how to distinguish CVD diamond single crystal and natural or additive method synthetic.
Summary of the invention
The technical problem to be solved in the present invention is, a kind of differentiation nitrating high speed chemical vapour deposition diamond single crystal (being called for short the N-CVD diamond single crystal) and other diamond single crystals are disclosed, comprise the natural diamond monocrystalline, the method of the diamond single crystal of High Temperature High Pressure synthetic etc., method of the present invention are to judge by the regular distribution of nitrogen content in the analysis N-CVD diamond single crystal.
The CVD diamond single crystal of the said high-speed rapid growth of the present invention is meant in common methane and hydrogen atmosphere and adds a certain amount of nitrogen, greater than 1 μ m/h (micron/hour), even can reach the diamond single crystal that obtains under the above situation of 100 μ m/h in growth velocity.Said other diamond single crystals can be the synthetic diamond single crystals who comprises that various natural diamond monocrystalline and High Temperature High Pressure synthetic method obtain.
In nitrogenous diamond multicrystal or monocrystalline, (photoluminescence PL) detects the existence of nitrogen and the content of being correlated with to available photic fluorescence spectrum.The general adamantine PL spectrum of nitrogenous CVD is referring to Fig. 1.At 575nm and 638nm place two sharp peaks appear, respectively the relevant nitrogen-room (N-V) of representative
oAnd (N-V)
-Glow peak; 700nm is that the broad peak at center is a corresponding phonon spectra copy (Phonon replicas).Along with the raising of nitrogen content, the intensity at the PL peak relevant with nitrogen increases.
Technical scheme of the present invention is: a kind of method of differentiating the chemical vapour deposition diamond single crystal of high-speed rapid growth, undertaken by the photoluminescence spectrum that detects diamond single crystal; Test points selected is on the surface of the diamond single crystal of being grown or/and 3～100 points are selected in the side, and the surface is or/and the diamond single crystal of the regular variation of intensity at the photoluminescence peak of each point of side is a nitrating high speed chemical vapour deposition diamond single crystal.
The surface of described diamond single crystal is an aufwuchsplate, i.e. (100) face, and the side of diamond single crystal is the side along the direction of growth; Described test points selected is that along straight-line segment select progressively check point, that is, series arrangement on the straight-line segment at center to limit or angle is selected check point on the surface of diamond single crystal; Or/and select check point along single crystal growing direction series arrangement in the side of diamond single crystal.
Concrete again test points selected can be that the test of surface growth face different positions comprises the center, edge, and angle; The side is near aufwuchsplate, and pointwise is down to the position near seed crystal.
The N-CVD diamond single crystal of indication of the present invention, under various growth conditionss, the corresponding PL spectrum of nitrogen content and nitrogen content is followed same rule.
N-CVD diamond single crystal PL results of spectral measurements is shown: nitrogen content is at the N-CVD diamond single crystal aufwuchsplate different positions of being grown and difference, and the nitrogen content in the growth surface center is higher than the nitrogen content near edge and drift angle; The intensity at the photoluminescence peak relevant with nitrogen increases.Nitrogen content at the N-CVD diamond single crystal of being grown along direction of growth difference, from the side along near aufwuchsplate to the seed crystal direction, nitrogen content increases gradually then that nitrogen content diminishes; The intensity increase at the photoluminescence peak relevant with the nitrogen then Strength Changes at photoluminescence peak diminishes.
The present invention is not subjected to the limitation of size of N-CVD diamond single crystal.The side of diamond single crystal can be handled by mechanical polishing.
The measurement of PL spectrum both can be that pointwise (3 test point and more than) is measured, and also can be to do face scanning (Mapping) to measure.
In the test of photoluminescence spectrographic, the excitation light source of employed instrument is the light source of laser or other continuous wavelengths, same group of excitation wavelength that detects, incident power, spot size, signal collection mode and time etc., and the factor that other possible influences are measured remains unchanged the minimizing experimental error as far as possible.
The excitation light source of employed instrument is LASER Light Source preferably.
The excitation wavelength of PL spectrum can be various wavelength, by comparing the PL spectrum relevant with nitrogen under the different wave length exciting light, judges the Changing Pattern of nitrogen content.
In general, because natural growth of diamond is chronic and the uncertainty of growing environment, the nitrogen regularity of distribution therein not necessarily obviously or do not have.A kind of method of artificially synthesizing diamond monocrystalline is a high temperature and high pressure method, has the method and the mechanism that are different from the CVD diamond film, and according to growth conditions, as temperature, pressure, cavity size, catalyst, nitrogenous source etc., its nitrogen distributes and has diversity.
And N-CVD diamond single crystal process of growth, all experiment conditions, as growth temperature, the speed of growth, plasma power and density, reactant gases pressure and proportioning etc., all be accurately control with recursive.Because have the diffusion of thermograde and nitrogen in the N-CVD diamond single crystal process of growth, nitrogen wherein will have certain distribution.The present invention obtains the regularity of distribution of nitrogen in the N-CVD diamond single crystal by the distinctive PL spectrometry relevant with nitrogen of N-CVD diamond single crystal, and distinguishes CVD diamond single crystal and other diamond single crystals according to this.
In fact, the variation of relatively more relevant PL spectrum infers that the rule of nitrogen content changes.The regular variation of nitrogen content be the N-CVD diamond single crystal, nitrogen content does not have that rule changes is natural diamond monocrystalline or High Temperature High Pressure synthetic diamond single crystal.
The present invention has found the rule of nitrogen content in the N-CVD diamond single crystal to change, and has solved problem how to differentiate the N-CVD diamond single crystal; Also find simultaneously the method for distinguishing the diamond single crystal of N-CVD diamond single crystal and natural or additive method synthetic, solved a difficult problem that the diamond industry is had very big influence.Method of the present invention is simple, suitable, quick, diamond single crystal is not damaged, and the shape quality to diamond single crystal does not produce any influence, therefore is the method that is fit to practical application.
Description of drawings
Fig. 1 is the adamantine PL spectrum of nitrogenous CVD.
Fig. 2 is the PL spectral detection point that the embodiment of the invention 1 is selected on N-CVD diamond single crystal surface.
Fig. 3 is the PL spectrum of each check point of Fig. 2.
Fig. 4 is the PL spectral detection point that the embodiment of the invention 2 is selected in N-CVD diamond single crystal side.
Fig. 5 is the PL spectrum of each check point of Fig. 4.
Fig. 6 is the PL spectrum of natural diamond (100) each check point of face.
Fig. 7 is the PL spectrogram of natural diamond side different positions.
Embodiment
The said N-CVD diamond single crystal of embodiments of the invention is ASTex 5250 type 5kw (2.45GHz) the microwave plasma CVD systems that adopt Seki company, iso-epitaxy high-speed rapid growth single-crystal diamond on monocrystalline (100) diamond.
The described PL spectroscopic analysis of each embodiment nitrogen content changes the laser excitation be to use the 514.5nm wavelength, excites but be not limited to this wavelength light, and as using 325nm, 488nm, 632.8nm equiwavelength excite same being suitable for.
The spectrometer of PL spectral measurement is Renishaw inVia micro Raman Spectroscope (RenishawinVis micro-Raman spectroscopy), uses the laser excitation light of 514.5nm wavelength, spot size 1-2 μ m, spectral resolution 1-2cm
-1
The following example is to further specify of the present invention, rather than limits to scope of the present invention.
Present embodiment is the growth surface at the N-CVD diamond single crystal, measures at the PL of different positions spectrum.Detected about 3 * 3 * 1cm of N-CVD diamond single crystal seed size
3, 10 hours growth 500 μ m, reaction gas flow is respectively H
2/ CH
4/ N
2Equal 500/60/2, the sccm of unit.
Fig. 2 has indicated the PL spectral detection point of selecting on N-CVD diamond single crystal surface.Wherein 1 is central point, and 3 is the proximal edge point, and 5 is nearly angle point, and 2 is the point on the straight-line segment at center to edge, and 4 is the point on the straight-line segment at center to angle.The measurement point on the straight-line segment can be selected, also measurement point can be arbitrarily selected.Reconnaissance can make the regularity of the intensity (corresponding N-CVD diamond single crystal nitrogen content) at PL peak represent more intuitively on straight-line segment.
Fig. 3 is one group of PL spectrogram of each check point of the growth surface different positions of N-CVD diamond single crystal.The characteristic peak relevant with nitrogen (peak at 575nm and 638nm place, and 700nm is the broad peak at center) approaching in the position, center 1,2 and the 4 characteristic peak intensity of sample, all be higher than the characteristic peak intensity that limit (position 3) and angle (position 5) are located.The characteristic peak Strength Changes that nitrogen is relevant is represented the variation of nitrogen content.So near the nitrogen content the aufwuchsplate center of N-CVD diamond single crystal is higher than the nitrogen content at limit, place, angle.This result can be used as a feature of N-CVD diamond single crystal.
Present embodiment is in the side of N-CVD diamond single crystal, along the PL spectrum of direction of growth different measuring position.Detected N-CVD diamond single crystal, about 3.1 * 3.1 * 1.1cm of seed size
3, 10 hours growth 600 μ m, reaction gas flow is respectively H
2/ CH
4/ N
2Equal 500/60/1.8, the sccm of unit.The sample side is through mechanical polishing.
1-6 represents lateral each measurement point of diamond among Fig. 4.
Fig. 5 is the PL spectrogram of the side different positions (corresponding to Fig. 4) of N-CVD diamond single crystal.As seen from Figure 5, the intensity at nitrogen correlated characteristic peak has certain Changing Pattern, the relation of considering nitrogen content and these characteristic peaks as can be known: along near aufwuchsplate to the seed crystal direction, it is to increase gradually that nitrogen content changes, reach after the certain distance, nitrogen content changes less.This result can be used as a feature of N-CVD diamond single crystal.
In order to prove actual effect of the present invention, measured Ib type (100) orientation natural diamond monocrystalline PL spectrum.Monocrystalline size 3.6 * 3.6 * 1cm
3
Fig. 6 is the PL spectrogram of surperficial different positions.Fig. 7 is the PL spectrogram of side different positions.The peak intensity relevant with nitrogen do not have clear regularity in its PL spectrum.
Same Ib type High Temperature High Pressure synthetic diamond single crystal's the PL spectrum peak relevant with nitrogen do not have clear regularity yet.
Claims (2)
1. a method of differentiating the chemical vapour deposition diamond single crystal of high-speed rapid growth is characterized in that, is undertaken by the photoluminescence spectra that detects diamond single crystal; Test points selected is at the aufwuchsplate of the diamond single crystal of being grown or/and 3～100 points are selected in the side; Aufwuchsplate is or/and the diamond single crystal of the regular variation of photoluminescence spectrographic intensity of each point of side is a nitrating high speed chemical vapour deposition diamond single crystal; Described photoluminescence spectral intensity rule changes, and the nitrogen content in the aufwuchsplate center is higher than the nitrogen content near edge and drift angle exactly, and the intensity at the photoluminescence peak relevant with nitrogen increases; From the side along aufwuchsplate to the seed crystal direction, nitrogen content increases gradually then that nitrogen content diminishes, the intensity increase at the photoluminescence peak relevant with the nitrogen then Strength Changes at photoluminescence peak diminishes; Described test points selected is along straight-line segment select progressively check point, that is, to select check point in aufwuchsplate series arrangement on the straight-line segment at center to limit or angle of diamond single crystal; Or/and select check point along single crystal growing direction series arrangement in the side of diamond single crystal.
2. according to the method for the chemical vapour deposition diamond single crystal of the described discriminating high-speed rapid growth of claim 1, it is characterized in that, the excitation light source of employed instrument is laser or other light sources, same group detect excite light wavelength, incident power, spot size, signal collection mode and detection time will remain unchanged.
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| GB201000768D0 (en) * | 2010-01-18 | 2010-03-03 | Element Six Ltd | CVD single crystal diamond material |
| CN107305185A (en) * | 2016-04-25 | 2017-10-31 | 潘栋雄 | Using Raman method naturally with synthesizing diamond is distinguished in the characteristic peak of three rank spectrum |
| CN110983437B (en) * | 2019-12-26 | 2021-06-22 | 长沙新材料产业研究院有限公司 | Method for producing single crystal diamond |
| CN111218664A (en) * | 2020-03-10 | 2020-06-02 | 上海三朗纳米技术有限公司 | Microwave-based artificial diamond preparation process |
| CN111584382B (en) * | 2020-04-27 | 2023-02-24 | 哈尔滨工业大学 | Method for in-situ characterization of heterogeneous interface state by using diamond NV color center |
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