CN1763267A - Preparation method for large-particle monocrystal diamond by DC plasma sedimentation - Google Patents
Preparation method for large-particle monocrystal diamond by DC plasma sedimentation Download PDFInfo
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- CN1763267A CN1763267A CN 200510086580 CN200510086580A CN1763267A CN 1763267 A CN1763267 A CN 1763267A CN 200510086580 CN200510086580 CN 200510086580 CN 200510086580 A CN200510086580 A CN 200510086580A CN 1763267 A CN1763267 A CN 1763267A
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Abstract
The present invention is DC plasma deposition process of preparing large grain monocrystal diamond, and belongs to the field of DC plasma technology. Large grain monocrystal diamond is prepared in 5-100 KW DC plasma spraying apparatus with initial deposition cavity vacuum degree of 0.01-0.1 Pa, deposition cavity pressure of 1-10000 Pa after filling reaction gas Ar, H2 and CH3; gas flow rate of Ar 1-3 slm, H2 4-8 slm and CH3 100-300 sccm; plasma comprising H, CH and C2 excimer; base material of monocrystal diamond of orientation of <111>+/-30 deg; and base material temperature of 950-1100 deg.c. The present invention is superior in that the fast monocrystal diamond way has monocrystal diamond preparing speed as high as 30-40 mg/hr.
Description
Technical field
The invention belongs to the direct-current plasma technical field, a kind of DC plasma sedimentation preparation method of large-particle monocrystal diamond particularly is provided, in the dc plasma jet environment, the preparation large-particle monocrystal diamond.
Technical background
Current, the adamantine dominant technology of synthetic single crystal is High Temperature High Pressure (HTHP) technology, and still, the speed of growth of this technology is very low, adopt thermograde control method, the fastest 6-7mg/h (H.Sumiya, et al, the J.CrystalGrowth of reaching, 237-239, (2002), 1281).Since 1999, the method that non-HTHP method prepares large-particle monocrystal diamond fast began to occur, and comprising flame CVD and micropore plasma jet CVD, obtained 3.9 * 10
6μ m
3The speed of growth of/s is equivalent to 49mg/h (A.V.Palnichenko, et al, Nature, 402, (1999), 162; B.Atakan, et al, New Diamond Front.Carbon Technol., 11, (2001), 159; R.M.Sankaran, et al, J.Appl.Phys., 92 (5), (2002), 2406).Report is arranged recently, and the free-standing diamond film of isoepitaxial growth has reached 3 * 3 * 0.5mm
3, be equivalent to 16mg.(G.J.Schmid, et al, Nuclear Instruments and Methodsin Physics Research, A527 (2004): 554) domestic, the preparation of large size single crystal diamond CVD is also at the early-stage, can reach 100 * 100 * 4 μ m at present
3, be equivalent to 2 * 10
-4Mg.(make widely known, Chen Guanghua, Zhu Hesun, Yang Xin's force, etc., artificial lens journal, 29 (3) (2000): 250).
The research of Zong Guan home and abroad large size single crystal diamond CVD preparation, following problem is more outstanding: the i. speed of growth is slow, and some technology is in the speed of short transverse even be lower than 0.5 μ m/h; (M.Kasu, et al, Diamond andRelated Materials, 13 (2004): 226) ii. iso-epitaxy substrate is with the bulky diamond processing of natural diamond or high temperature and high pressure method preparation, all at the square millimeter order of magnitude, is no more than 5 * 5mm
2, be difficult to accomplish big area, so large-area iso-epitaxy substrate is difficult to obtain; Iii. heteroepitaxial growth is prone to polycrystalline.Though foreign substrate can be accomplished big area, the epitaxy diamond is very difficult on foreign substrate, because lattice mismatch, its extension nucleus ratio is very little, is unfavorable for oriented growth, so be difficult to transform to monocrystalline.The preparation transition layer can improve lattice mismatch on foreign substrate, improves extension nucleus ratio, but people also not quite understand the proterties and the preparation of transition layer.(make widely known, Chen Guanghua, Zhu Hesun, Yang Xin's force, etc., the artificial lens journal, 29 (3) (2000): 250) in these three problems, the speed of growth is maximum bottleneck slowly.At present, in the epitaxy technology, what often adopt both at home and abroad is that microwave plasma strengthens the CVD technology, and reason is its sedimentary environment cleaning, preparation film body quality height.But the speed of growth of this technology is unhappy, the short transverse maximum deposition speed is no more than 100 μ m/h, generally all at 1 μ m/h, (0.A.Williams, R.B.Jackman, Diamond and Related Materials, 13 (2004): 557) thus epitaxial deposition speed low be to be subjected to microwave plasma to strengthen the CVD technology limitation in a sense.In addition, the homogeneity range of microwave excited plasma is little, (Wang Chuanxin, Wang Jianhua, Ma Zhibin, Man Weidong, etc., the material Leader, 16 (10) (2002): 52) though can by the design special shape reaction chamber and add the high-power homogeneity range that increases, this equipment cost costliness, and since the reduction microwave frequency, the reactant gases ionization level is reduced, cause sedimentation velocity lower.Therefore, the microwave plasma of taking a long view strengthens the CVD technology and prepares single-crystal diamond and can be very restricted.
Summary of the invention
Goal of the invention is to provide a kind of DC plasma sedimentation preparation method of large-particle monocrystal diamond, solved the problem of the low and equipment cost costliness of preparation speed.
Large-particle monocrystal diamond of the present invention prepares on 5-100kW dc plasma jet equipment, and the initial vacuum of deposit cavity is 10
-2-10
-1Pa, charge into reactant gases after, the pressure of deposit cavity is 10
0-10
4Between the Pa, the reactant gases that charges into is Ar, H
2And CH
3, flow is respectively: Ar is 1-3slm; H
2Be 4-8slm; CH
3Be 100-300sccm.The main component of plasma body is H, CH, C
2Excimer.Base material is＜111〉± single-crystal diamond of 30 ° of crystalline orientations.Base material in preparation in the process temperature remain between 950-1100 ℃.In preparation process, base material divides the direction sedimentation 150-300 μ m of clockwise away from plasma body every 15-25.Whole preparation time 6～16 hours.
The invention has the advantages that: an approach of preparation single-crystal diamond fast is provided, has made single crystal preparation speed reach 30-40mg/h.
Description of drawings
Fig. 1 is reactant gases Ar of the present invention, H
2And CH
4Light emission (OES) typical diagnostic result at the following plasma body that produces of preparation condition.Spectral results shows and is mainly H, CH and C in the plasma composition
2Excimer, the excimer relevant with the required carbon atom of diamond film is CH and C
2Excimer, wherein C
2Excimer plays a major role.What etching was played a major role is α and the β excimer of H, in whole plasma body, has only small amount of H γ excimer.Therefore, the preparation process of single-crystal diamond also is the homeostasis process of cohesion and etching.
Fig. 2 is the prepared single-crystal diamond photo of the present invention.Photo shows that prepared crystal volume is similar, but different in the quality of crystallographic features, purity and optical transmittance.
Fig. 3 is the Raman spectrum detected result of the prepared single-crystal diamond of the present invention.Diamond in the detection of Raman spectrum, wave number 1332.2cm
-1Peak position be unstressed adamantine characteristic peak.The Raman spectrum result of the prepared single-crystal diamond of the present invention shows at 1332.2cm
-1Sharp-pointed spectrum peak has appearred near prepared crystal, and spectrum peak position is at 1333.2cm
-1, at 1556cm
-1The peak is dispersed near one of existence, illustrates to have the graphite composition in the detected crystal.
Fig. 4 is the Raman spectrum detected result of the prepared single-crystal diamond of the present invention.Diamond in the detection of Raman spectrum, wave number 1332.2cm
-1Peak position be unstressed adamantine characteristic peak.The Raman spectrum result of the prepared single-crystal diamond of the present invention shows at 1332.2cm
-1Sharp-pointed spectrum peak has appearred near prepared crystal, and spectrum peak position is at 1332.4cm
-1, near adamantine unstressed characteristic peak, and the halfwidth of spectral line (FWHM) is little, and does not have other spectrum peaks.
Fig. 5 is the Raman spectrum detected result of the prepared single-crystal diamond of the present invention.Diamond in the detection of Raman spectrum, wave number 1332.2cm
-1Peak position be unstressed adamantine characteristic peak.The Raman spectrum result of the prepared single-crystal diamond of the present invention shows at 1332.2cm
-1Sharp-pointed spectrum peak has appearred near prepared crystal, and spectrum peak position is at 1332.8cm
-1, near adamantine unstressed characteristic peak, and the halfwidth of spectral line (FWHM) is little, and does not have other spectrum peaks.
Fig. 6 is the XRD detected result of the prepared single-crystal diamond of the present invention.The XRD result of the prepared single-crystal diamond of the present invention shows the feature of monocrystalline X-ray diffraction, promptly has only a diffracted ray in the diffraction spectra.Position of spectral line is 73 °.This is because the crystal face of participation X-ray diffraction is that single crystal (220) crystal face causes.
Fig. 7 is the XRD detected result of the prepared single-crystal diamond of the present invention.The XRD result of the prepared single-crystal diamond of the present invention shows the feature of monocrystalline X-ray diffraction, promptly has only a diffracted ray in the diffraction spectra.Position of spectral line is 43 °.This is because the crystal face of participation X-ray diffraction is that single crystal (111) crystal face causes.
Fig. 8 is the XRD detected result of the prepared single-crystal diamond of the present invention.The XRD result of the prepared single-crystal diamond of the present invention shows the feature of monocrystalline X-ray diffraction, promptly has only a diffracted ray in the diffraction spectra.Position of spectral line is 43 °.This is because the crystal face of participation X-ray diffraction is that single crystal (111) crystal face causes.
Embodiment
Example 1: with＜111 〉+30 ° of single-crystal diamonds are base material, and preparation temperature is 950 ℃, and the initial vacuum of deposit cavity is 8.6 * 10
-2Pa, reactant gases are Ar, H
2And CH
3, flow is respectively: Ar is 1slm; H
2Be 4slm; CH
3Be 150sccm.After charging into reactant gases, the pressure of deposit cavity is 4000Pa.Preparation time is 8 hours.In preparation process, base material is downward sedimentation 250 μ m every 20 minutes.
Prepared crystalline plasma environment is seen the OES diagnostic result of accompanying drawing 1; Prepared single-crystal diamond is seen the scale 26 pairing crystal in the accompanying drawing 2; The Raman spectrum detected result of prepared single-crystal diamond is seen accompanying drawing 3; The XRD detected result of prepared single-crystal diamond is seen accompanying drawing 6.
Example 2:; With＜111 〉+30 ° of single-crystal diamonds are base material, and preparation temperature is 990 ℃, and the initial vacuum of deposit cavity is 8.6 * 10
-2Pa, reactant gases are Ar, H
2And CH
3, flow is respectively: Ar is 2slm; H
2Be 5slm; CH
3Be 150sccm.After charging into reactant gases, the pressure of deposit cavity is 6000Pa.Preparation time is 8 hours.In preparation process, base material is downward sedimentation 250 μ m every 20 minutes.
Prepared crystalline plasma environment is seen the OES diagnostic result of accompanying drawing 1; Prepared single-crystal diamond is seen the scale 28 pairing crystal in the accompanying drawing 2; The Raman spectrum detected result of prepared single-crystal diamond is seen accompanying drawing 4; The XRD detected result of prepared single-crystal diamond is seen accompanying drawing 7.
Example 3: with＜111 〉+30 ° of single-crystal diamonds are base material, and preparation temperature is 1050 ℃, and the initial vacuum of deposit cavity is 8.6 * 10
-2Pa, reactant gases are Ar, H
2And CH
3, flow is respectively: Ar is 2slm; H
2Be 4slm; CH
3Be 100sccm.After charging into reactant gases, the pressure of deposit cavity is 5000Pa.Preparation time is 8 hours.In preparation process, base material is downward sedimentation 250 μ m every 20 minutes.
Prepared crystalline plasma environment is seen the OES diagnostic result of accompanying drawing 1; Prepared single-crystal diamond is seen the scale 29 pairing crystal in the accompanying drawing 2; The Raman spectrum detected result of prepared single-crystal diamond is seen accompanying drawing 5; The XRD detected result of prepared single-crystal diamond is seen accompanying drawing 8.
Claims (2)
1, a kind of DC plasma sedimentation preparation method of large-particle monocrystal diamond is characterized in that: large-particle monocrystal diamond prepares on 5-100kW dc plasma jet equipment, and the initial vacuum of deposit cavity is 10
-2-10
-1Pa, charge into reactant gases after, the pressure of deposit cavity is 10
0-10
4Between the Pa, the reactant gases that charges into is Ar, H
2And CH
3, flow is respectively: Ar is 1-3slm; H
2Be 4-8slm; CH
3Be 100-300sccm.
2, in accordance with the method for claim 1, it is characterized in that: the composition of plasma body is H, CH, C
2Excimer; Base material is＜111〉± single-crystal diamond of 30 ° of crystalline orientations; Base material in preparation in the process temperature remain between 950-1100 ℃, in preparation process, base material divides the direction sedimentation 150-300 μ m of clockwise away from plasma body, whole preparation time 6～16 hours every 15-25.
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| CNB2005100865801A CN100395378C (en) | 2005-10-10 | 2005-10-10 | Preparation method for large-particle monocrystal diamond by DC plasma sedimentation |
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| CN1763267A true CN1763267A (en) | 2006-04-26 |
| CN100395378C CN100395378C (en) | 2008-06-18 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457983C (en) * | 2007-03-23 | 2009-02-04 | 北京科技大学 | Method for preparing single-crystal diamond by immersion type solid carbon resource |
| US9962669B2 (en) | 2011-09-16 | 2018-05-08 | Baker Hughes Incorporated | Cutting elements and earth-boring tools including a polycrystalline diamond material |
| US10005672B2 (en) | 2010-04-14 | 2018-06-26 | Baker Hughes, A Ge Company, Llc | Method of forming particles comprising carbon and articles therefrom |
| US10066441B2 (en) | 2010-04-14 | 2018-09-04 | Baker Hughes Incorporated | Methods of fabricating polycrystalline diamond, and cutting elements and earth-boring tools comprising polycrystalline diamond |
| CN109234806A (en) * | 2018-11-21 | 2019-01-18 | 中国科学院大学 | A kind of method of the plasma-deposited single-crystal diamond of dual band radio frequency |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029135C (en) * | 1987-04-03 | 1995-06-28 | 富士通株式会社 | Method and apparatus for vapor deposition of diamond |
| CN1016364B (en) * | 1989-09-19 | 1992-04-22 | 北京市科学技术研究院 | Chemical gaseous deposition process of thin diamond film by means of arc discharge |
| JPH0417655A (en) * | 1990-05-11 | 1992-01-22 | Sumitomo Electric Ind Ltd | Composite material and its production |
| JP3227544B2 (en) * | 1992-07-28 | 2001-11-12 | 三和シヤッター工業株式会社 | balcony |
| CN100335677C (en) * | 2004-12-28 | 2007-09-05 | 北京科技大学 | DC electric arc plasma chemical vapor deposition apparatus and diamond coating method |
-
2005
- 2005-10-10 CN CNB2005100865801A patent/CN100395378C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457983C (en) * | 2007-03-23 | 2009-02-04 | 北京科技大学 | Method for preparing single-crystal diamond by immersion type solid carbon resource |
| US10005672B2 (en) | 2010-04-14 | 2018-06-26 | Baker Hughes, A Ge Company, Llc | Method of forming particles comprising carbon and articles therefrom |
| US10066441B2 (en) | 2010-04-14 | 2018-09-04 | Baker Hughes Incorporated | Methods of fabricating polycrystalline diamond, and cutting elements and earth-boring tools comprising polycrystalline diamond |
| US9962669B2 (en) | 2011-09-16 | 2018-05-08 | Baker Hughes Incorporated | Cutting elements and earth-boring tools including a polycrystalline diamond material |
| CN109234806A (en) * | 2018-11-21 | 2019-01-18 | 中国科学院大学 | A kind of method of the plasma-deposited single-crystal diamond of dual band radio frequency |
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|---|---|
| CN100395378C (en) | 2008-06-18 |
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