CN106744931A - A kind of method that plasma etching graphite prepares diamond particles - Google Patents
A kind of method that plasma etching graphite prepares diamond particles Download PDFInfo
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- CN106744931A CN106744931A CN201611130191.9A CN201611130191A CN106744931A CN 106744931 A CN106744931 A CN 106744931A CN 201611130191 A CN201611130191 A CN 201611130191A CN 106744931 A CN106744931 A CN 106744931A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000010432 diamond Substances 0.000 title claims abstract description 146
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 145
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 139
- 239000010439 graphite Substances 0.000 title claims abstract description 139
- 239000002245 particle Substances 0.000 title claims abstract description 70
- 238000001020 plasma etching Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004381 surface treatment Methods 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 20
- 239000012808 vapor phase Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000002390 adhesive tape Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000013078 crystal Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000001069 Raman spectroscopy Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000003321 amplification Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of method that plasma etching graphite prepares diamond particles, the present invention relates to diadust growing technology field.The invention solves the problems that it is existing prepare that diamond is relatively costly, quality is relatively low, be difficult dispersion, the problem that technique is uncontrollable, substrate selection is limited.Method：First, the surface treatment of graphite flake；2nd, diamond is prepared on graphite using plasma etching method；3rd, disperse diamond particles, that is, complete the method that plasma etching graphite prepares diamond particles.A kind of method that the present invention prepares diamond particles for plasma etching graphite.
Description
Technical field
The present invention relates to diadust growing technology field.
Background technology
Diamond possesses excellent physics, chemical property, such as hardness highest, chemical stability, thermal conductivity and heat endurance
It is good etc. so that it is widely paid close attention to and applied in many fields.However, the natural diamond reserves in nature are limited,
And difficulty is exploited, causes natural diamond expensive, it is difficult to for industrialized production.
Manually prepare at present more than diamond using HTHP (HPHT) method, with graphite as raw material, catalyst is made with catalyst
Prepare diamond.Diamond prepared by the method contains more impurity (such as catalyst) and fault of construction, of low quality, it is difficult to
Satisfaction is widely applied, especially in high-end fields such as semiconductors.And high temperature and high pressure method equipment is complicated, expensive, danger coefficient
Greatly.
Using Microwave Irradiation Assisted Chemical vapour deposition (MPCVD) method, with microwave-excitation reacting gas, there is no electrode fouling, work
Make stabilization, be easy to precise control, high quality diamond can be prepared under compared with low pressure.CVD prepares carbon used by diamond
Mainly there is CH in source4、C2H2、CH3OH、C2H5OH、CH3COCH3、CH3COOH, graphite.Conventional carbon source is mainly gaseous carbon source at present
CH4, its mix with hydrogen after under microwave action, in matrix surface depositing diamond.The diamond particles of the method generation hold
Easy film forming, and should not separate.And need to increase hydrocarbon gas gas circuit, prepare diamond compared with by carbon source of graphite in experimental implementation
Method it is cumbersome.And, it is necessary to control hydrocarbon gas proportion well during using hydrocarbon gas diamond synthesis.If hydrocarbon
Gas concentration is higher, and the diamond quality of synthesis can be caused to decline, and graphite increases with the content of amorphous carbon；If hydrocarbon gas concentration
It is relatively low, generation diamond speed can be caused to reduce, the diamond content reduction of synthesis.And graphite does carbon source diamond synthesis purity
Higher, reaction speed is very fast, it is only necessary to single hydrogen source gas, simple to operate, cost reduction.
CVD prepares temperature needed for diamond for 200 DEG C~1200 DEG C, it is necessary to select substrate, Ying Xuan according to temperature requirement
The small material of high temperature resistant, thermal coefficient of expansion is selected, matrix melts or bursts apart in preventing reaction and cooling procedure, and this causes that substrate is selected
Receive many limitations.
The content of the invention
The invention solves the problems that it is existing prepare that diamond is relatively costly, quality is relatively low, be difficult dispersion, technique is uncontrollable,
The limited problem of substrate selection, and a kind of method that plasma etching graphite prepares diamond particles is provided.
A kind of method that plasma etching graphite prepares diamond particles, specifically follows the steps below：
First, the surface treatment of graphite flake：
Graphite flake adhesive tape is glued and goes to top layer, then surpassed respectively using absolute ethyl alcohol, acetone and deionized water successively
Sound cleans 10min~20min, and be placed in the graphite flake after cleaning in vacuum drying chamber and dry, do by the graphite flake after being cleaned
Dry temperature is 60 DEG C~80 DEG C, and the time is 15min~30min, and dried graphite flake is cooled into room temperature, is surface-treated
Graphite flake afterwards；
2nd, diamond is prepared on graphite using plasma etching method：
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, is in hydrogen flow rate
50sccm~1000sccm, temperature are 200 DEG C~1200 DEG C, pressure is 100mbar~500mbar and microwave power is 1800W
Under conditions of~5000W, 30min~24h is deposited, obtain the diamond of plasma etching graphite preparation；
3rd, diamond particles are disperseed：
Diamond prepared by plasma etching graphite is scraped from graphite flake surface, the diamond particles reunited,
With stainless steel mortar grinder and beat the diamond particles 25min~35min of reunion, the diamond particles after being ground,
Water bath heating temperature is under conditions of 50 DEG C~80 DEG C, by the diamond particles after grinding be placed in mass percent for 20%~
30min~1h in 70% sulfuric acid, then diamond particles are cleaned with deionized water, until the pH of cleaning solution is 7, it is then sharp successively
It is cleaned by ultrasonic 25min~35min respectively with acetone and alcohol, the diamond particles after being cleaned, finally by the gold after cleaning
Hard rock particle is placed in vacuum drying chamber and is dried, that is, complete the method that plasma etching graphite prepares diamond particles.
The beneficial effects of the invention are as follows：Using solid graphite as carbon source and substrate, etched in the bombardment of hydrogen plasma
Under, diamond particles directly can be grown on graphite.Diamond is grown compared to using gaseous carbon source, graphite had not only made carbon source but also can
Make matrix, save the trouble of selection backing material, simple to operate, raising prepares the quality and quantity of diamond, with natural Buddha's warrior attendant
Stone composition is almost identical, and size can reach micron order.And the reunion diamond for preparing only need to be dispersibled by simple treatment.
Compared with other processing methods for preparing diamond, with diamond prepared by hydrogen plasma etching solid graphite method, treatment side
Method is simpler, quick, economical, environment-friendly.
A kind of method that the present invention prepares diamond particles for plasma etching graphite.
Brief description of the drawings
Fig. 1 is that the amplification 10000 of diamond prepared by plasma etching graphite prepared by the step 2 of embodiment one is swept again
Retouch electron microscope picture；
Fig. 2 is 1300 times of scannings of amplification of diamond prepared by plasma etching graphite prepared by the step 2 of embodiment one
Electron microscope picture；
Fig. 3 is the X-ray diffractogram of diamond prepared by plasma etching graphite prepared by the step 2 of embodiment one；1
It is (111) crystal face of diamond, 2 is (220) crystal face of diamond, and 3 is (311) crystal face of diamond, and 4 is diamond
(400) crystal face, 5 is (331) crystal face of diamond；
Fig. 4 is laser Raman spectroscopy figure, and 1 is natural diamond, and 2 is plasma etching prepared by the step 2 of embodiment one
Diamond prepared by graphite, 3 is the polycrystalline graphite piece described in the step one of embodiment one；
Fig. 5 is the scanning electron microscope diagram of 1500 times of the diamond particles amplification of high degree of dispersion prepared by embodiment one；
Fig. 6 is the scanning electron microscope diagram of 10000 times of the diamond particles amplification of high degree of dispersion prepared by embodiment one.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, also including each specific embodiment it
Between any combination.
Specific embodiment one：A kind of plasma etching graphite described in present embodiment prepares the side of diamond particles
Method, specifically follows the steps below：
First, the surface treatment of graphite flake：
Graphite flake adhesive tape is glued and goes to top layer, then surpassed respectively using absolute ethyl alcohol, acetone and deionized water successively
Sound cleans 10min~20min, and be placed in the graphite flake after cleaning in vacuum drying chamber and dry, do by the graphite flake after being cleaned
Dry temperature is 60 DEG C~80 DEG C, and the time is 15min~30min, and dried graphite flake is cooled into room temperature, is surface-treated
Graphite flake afterwards；
2nd, diamond is prepared on graphite using plasma etching method：
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, is in hydrogen flow rate
50sccm~1000sccm, temperature are 200 DEG C~1200 DEG C, pressure is 100mbar~500mbar and microwave power is 1800W
Under conditions of~5000W, 30min~24h is deposited, obtain the diamond of plasma etching graphite preparation；
3rd, diamond particles are disperseed：
Diamond prepared by plasma etching graphite is scraped from graphite flake surface, the diamond particles reunited,
With stainless steel mortar grinder and beat the diamond particles 25min~35min of reunion, the diamond particles after being ground,
Water bath heating temperature is under conditions of 50 DEG C~80 DEG C, by the diamond particles after grinding be placed in mass percent for 20%~
30min~1h in 70% sulfuric acid, then diamond particles are cleaned with deionized water, until the pH of cleaning solution is 7, it is then sharp successively
It is cleaned by ultrasonic 25min~35min respectively with acetone and alcohol, the diamond particles after being cleaned, finally by the gold after cleaning
Hard rock particle is placed in vacuum drying chamber and is dried, that is, complete the method that plasma etching graphite prepares diamond particles.
Graphite flake adhesive tape is glued in this specific embodiment step one goes to top layer, it is found that left on adhesive tape
The graphite marking, and the new surface that graphite flake is obtained.
It is to utilize microwave excitation in this specific embodiment step 2, glow discharge is produced in reative cell, makes hydrogen point
Sub- ionization, forms hydrogen plasma, and diamond is prepared for etching graphite flake.Using Non-contact Infrared Temperature Measurement meter measurement etc. from
The temperature on the graphite flake surface under daughter effect；The parameter such as temperature and pressure is realized by certain physics law in reaction cavity
Coupling regulation and control, it is to avoid the independent regulation and control difficulty such as cause the workload big, inaccurate.Therefore can be by the single pressure of precise control
The isoparametric adjustment of temperature, plasma density is realized in the change of value in linkage.The carbon source and substrate of this specific embodiment
Graphite is, graphite surface that can be after being bombarded by hydrogen plasma after above-mentioned steps obtains the diamond with aggregate structure
Particle.Gas needed for this specific embodiment is mainly single hydrogen, for the diamond quality for changing synthesis also may be used with size
Add the inert gas of proper content, such as helium, argon gas.
To improve the growth rate of diamond, increase the particle size of diamond synthesis, can be ground with diadust
Be put into for graphite flake ultrasonic wave decentralized processing carried out in the suspension containing diadust by graphite flake；Then this is being carried out
Specific embodiment step 2, diamond is prepared using the method for plasma etching on graphite.
Compared with other diamonds dispersion patent, the method is simple and environmentally-friendly, low cost for this specific embodiment step 3.
Diamond size prepared by plasma etching graphite reaches micron order, and growth rate is apparently higher than with Si as substrate
The diamond of preparation, and purity is high, substantially without the impurity such as graphite and amorphous carbon；And the diamond for generating easily disperses, without
By plant equipment or chemical reagent, simple hand is only needed to be disperseed by grinding.Experimental implementation is also relatively easy, without it
His hydrocarbon gas are used as carbon source.
The beneficial effect of this specific embodiment is：Using solid graphite as carbon source and substrate, in hydrogen plasma
Under bombardment etching, diamond particles directly can be grown on graphite.Diamond is grown compared to using gaseous carbon source, graphite was both made
Carbon source can make matrix again, save the trouble of selection backing material, and simple to operate, raising prepares the quality and quantity of diamond, with
Natural diamond composition is almost identical, and size can reach micron order.And the reunion diamond for preparing only need to be by simple treatment
Dispersible.Compared with other processing methods for preparing diamond, with Buddha's warrior attendant prepared by hydrogen plasma etching solid graphite method
Stone, processing method is simpler, quick, economical, environment-friendly.
Specific embodiment two：Present embodiment from unlike specific embodiment one：Graphite described in step one
Piece is highly oriented pyrolytic graphite piece, crystalline flake graphite piece, amorphous graphite piece or polycrystalline graphite piece.Other and the phase of specific embodiment one
Together.
Specific embodiment three：Unlike one of present embodiment and specific embodiment one or two：Institute in step one
The size of the graphite flake stated is 10 × 10 × 1mm to 30 × 30 × 10mm.Other are identical with specific embodiment one or two.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Will in step 2
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, is that 200sccm, temperature are in hydrogen flow rate
200 DEG C~1200 DEG C, pressure be deposition under conditions of 100mbar~500mbar and microwave power are 1800W~5000W
30min~24h.Other are identical with specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Will in step 2
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, hydrogen flow rate be 50sccm~
1000sccm, temperature are 900 DEG C, pressure is under conditions of 100mbar~500mbar and microwave power are 1800W~5000W,
Deposition 30min~24h.Other are identical with specific embodiment one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Will in step 2
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, hydrogen flow rate be 50sccm~
1000sccm, temperature are 200 DEG C~1200 DEG C, pressure is under conditions of 200mbar and microwave power are 1800W~5000W, to sink
Product 30min~24h.Other are identical with specific embodiment one to five.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Will in step 2
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, hydrogen flow rate be 50sccm~
1000sccm, temperature are 200 DEG C~1200 DEG C, pressure is 100mbar~500mbar and microwave power is 1800W~5000W
Under the conditions of, deposit 12h.Other are identical with specific embodiment one to six.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：Will in step 2
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, is that 200sccm, temperature are in hydrogen flow rate
900 DEG C, pressure be under conditions of 200mbar and microwave power are 1800W~5000W, to deposit 12h.Other and specific embodiment party
Formula one to seven is identical.
Specific embodiment nine：Unlike one of present embodiment and specific embodiment one to eight：Will in step 2
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, hydrogen flow rate be 50sccm~
1000sccm, temperature are 200 DEG C~900 DEG C, pressure is 100mbar~200mbar and microwave power is 1800W~5000W
Under the conditions of, deposit 30min~12h.Other are identical with specific embodiment one to eight.
Specific embodiment ten：Unlike one of present embodiment and specific embodiment one to nine：Will in step 2
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, hydrogen flow rate be 50sccm~
1000sccm, temperature are 900 DEG C~1200 DEG C, pressure is 200mbar~500mbar and microwave power is 1800W~5000W
Under the conditions of, deposit 12h~24h.Other are identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：
A kind of method that plasma etching graphite prepares diamond particles is followed the steps below：
First, the surface treatment of graphite flake：
Graphite flake adhesive tape is glued and goes to top layer, then surpassed respectively using absolute ethyl alcohol, acetone and deionized water successively
Sound cleans 10min, and be placed in the graphite flake after cleaning in vacuum drying chamber and dry by the graphite flake after being cleaned, drying temperature
It is 80 DEG C, the time is 30min, dried graphite flake is cooled to room temperature, the graphite flake after being surface-treated；
Described graphite flake is polycrystalline graphite piece；
2nd, diamond is prepared on graphite using plasma etching method：
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, is in hydrogen flow rate
200sccm, temperature are 900 DEG C, pressure is under conditions of 200mbar and microwave power are 3000W, to deposit 12h, obtain plasma
Diamond prepared by body etching graphite；
3rd, diamond particles are disperseed：
Diamond prepared by plasma etching graphite is scraped from graphite flake surface, the diamond particles reunited,
With stainless steel mortar grinder and beat the diamond particles 30min of reunion, the diamond particles after being ground, in heating water bath
Temperature be 80 DEG C under conditions of, the diamond particles after grinding are placed in 30min in the sulfuric acid that mass percent is 50%, then use
Deionized water cleans diamond particles, until the pH of cleaning solution is 7, is then cleaned by ultrasonic respectively using acetone and alcohol successively
Finally be placed in the diamond particles after cleaning in vacuum drying chamber and done by 30min, the diamond particles after being cleaned
It is dry, obtain the diamond particles of high degree of dispersion, that is, complete the method that plasma etching graphite prepares diamond particles.
Buddha's warrior attendant prepared by the plasma etching graphite for characterizing the preparation of the present embodiment step 2 using SEM
The surface topography of stone, Fig. 1 is the amplification 10000 of diamond prepared by plasma etching graphite prepared by the step 2 of embodiment one
Times scanning electron microscope diagram；Fig. 2 is putting for diamond prepared by plasma etching graphite prepared by the step 2 of embodiment one
Big 1300 times of scanning electron microscope diagrams；The material that can be seen that generation by Fig. 1 and Fig. 2 test results has obvious Buddha's warrior attendant
Stone pattern, size reaches tens microns, hence it is evident that more than the size (several microns) of the diamond particles prepared with gaseous carbon source.
The plasma prepared using X-ray diffraction (X-Ray Diffraction, XRD) detection the present embodiment step 2
The crystalline component of diamond prepared by etching graphite, crystal orientation and thin film crystallization integrity degree；Fig. 3 is the step 2 system of embodiment one
The X-ray diffractogram of diamond prepared by standby plasma etching graphite；1 is (111) crystal face of diamond, and 2 is diamond
(220) crystal face, 3 for diamond (311) crystal face, 4 for diamond (400) crystal face, 5 for diamond (331) crystal face；By
Fig. 3 test results see, (111), (220) of diamond, (311), (400), the characteristic peak of (331), almost without non-diamond
The XRD peaks of phase.
The present embodiment step 2 system is characterized using laser Raman spectroscopy (Laser Raman Spectroscopy, Raman)
The composition content and the problem of integrality of diamond prepared by standby plasma etching graphite, will not destroy material structure；Fig. 4
It is laser Raman spectroscopy figure, 1 is natural diamond, and 2 is prepared by plasma etching graphite prepared by the step 2 of embodiment one
Diamond, 3 is the polycrystalline graphite piece described in the step one of embodiment one；Seen by Fig. 4 test results, 1332cm-1Place is typical case
Diamond peak, in 1323cm-1And 1567cm-1Place is respectively the D peaks and G peaks of graphite, and the diamond Raman peaks of generation are
1331cm-1, the 1332cm with natural diamond-1Raman peaks are almost identical.
As known from the above, diamond quality prepared by the plasma etching graphite that prepared by the present embodiment step 2 is higher,
Almost identical with natural diamond composition, size can reach micron order.
The diamond particle surfaces pattern of high degree of dispersion manufactured in the present embodiment, Fig. 5 are characterized using SEM
Amplify 1500 times of scanning electron microscope diagram for the diamond particles of the high degree of dispersion of the preparation of embodiment one, Fig. 6 is embodiment
The diamond particles of one high degree of dispersion for preparing amplify 10000 times of scanning electron microscope diagram；As seen from the figure, the present embodiment system
Standby diamond particles easily disperse, and dispersion effect is good.
Claims (10)
1. a kind of a kind of method that plasma etching graphite prepares diamond particles, it is characterised in that plasma etching graphite
The method for preparing diamond particles is followed the steps below：
First, the surface treatment of graphite flake：
Graphite flake adhesive tape is glued and goes to top layer, then ultrasound is clear respectively using absolute ethyl alcohol, acetone and deionized water successively
10min~20min is washed, be placed in the graphite flake after cleaning in vacuum drying chamber and dry by the graphite flake after being cleaned, and dries temperature
It is 60 DEG C~80 DEG C to spend, and the time is 15min~30min, dried graphite flake is cooled into room temperature, after being surface-treated
Graphite flake；
2nd, diamond is prepared on graphite using plasma etching method：
Graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus, hydrogen flow rate be 50sccm~
1000sccm, temperature are 200 DEG C~1200 DEG C, pressure is 100mbar~500mbar and microwave power is 1800W~5000W
Under the conditions of, 30min~24h is deposited, obtain the diamond of plasma etching graphite preparation；
3rd, diamond particles are disperseed：
Diamond prepared by plasma etching graphite is scraped from graphite flake surface, the diamond particles reunited, with not
Rust steel mortar grinds and beats the diamond particles 25min~35min of reunion, the diamond particles after being ground, in water-bath
Heating-up temperature is under conditions of 50 DEG C~80 DEG C, it is 20%~70% that the diamond particles after grinding are placed in into mass percent
30min~1h in sulfuric acid, then diamond particles are cleaned with deionized water, until the pH of cleaning solution is 7, acetone is then utilized successively
And alcohol is cleaned by ultrasonic 25min~35min respectively, the diamond particles after being cleaned, finally by the diamond after cleaning
Grain is placed in vacuum drying chamber and is dried, that is, complete the method that plasma etching graphite prepares diamond particles.
2. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
Graphite flake described in step one is highly oriented pyrolytic graphite piece, crystalline flake graphite piece, amorphous graphite piece or polycrystalline graphite piece.
3. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
The size of the graphite flake described in step one is 10 × 10 × 1mm to 30 × 30 × 10mm.
4. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
The graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus in step 2, is in hydrogen flow rate
200sccm, temperature are 200 DEG C~1200 DEG C, pressure is 100mbar~500mbar and microwave power is 1800W~5000W
Under the conditions of, deposit 30min~24h.
5. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
The graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus in step 2, is in hydrogen flow rate
50sccm~1000sccm, temperature are 900 DEG C, pressure is 100mbar~500mbar and microwave power is 1800W~5000W
Under the conditions of, deposit 30min~24h.
6. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
The graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus in step 2, is in hydrogen flow rate
50sccm~1000sccm, temperature are 200 DEG C~1200 DEG C, pressure is 200mbar and microwave power is 1800W~5000W
Under the conditions of, deposit 30min~24h.
7. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
The graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus in step 2, is in hydrogen flow rate
50sccm~1000sccm, temperature are 200 DEG C~1200 DEG C, pressure is 100mbar~500mbar and microwave power is 1800W
Under conditions of~5000W, 12h is deposited.
8. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
The graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus in step 2, is in hydrogen flow rate
200sccm, temperature are 900 DEG C, pressure is under conditions of 200mbar and microwave power are 1800W~5000W, to deposit 12h.
9. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
The graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus in step 2, is in hydrogen flow rate
50sccm~1000sccm, temperature are 200 DEG C~900 DEG C, pressure be 100mbar~200mbar and microwave power be 1800W~
Under conditions of 5000W, 30min~12h is deposited.
10. the method that a kind of plasma etching graphite according to claim 1 prepares diamond particles, it is characterised in that
The graphite flake after surface treatment is placed in microwave plasma chemical vapor phase growing apparatus in step 2, is in hydrogen flow rate
50sccm~1000sccm, temperature are 900 DEG C~1200 DEG C, pressure is 200mbar~500mbar and microwave power is 1800W
Under conditions of~5000W, 12h~24h is deposited.
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| CN107557858A (en) * | 2017-09-19 | 2018-01-09 | 武汉普迪真空科技有限公司 | The method of isoepitaxial growth single-crystal diamond based on II a type natural diamonds |
| CN108505018A (en) * | 2018-05-14 | 2018-09-07 | 哈尔滨工业大学 | A method of growth excellent diamonds particle and diamond thin |
| CN110112013A (en) * | 2019-05-28 | 2019-08-09 | 北京工业大学 | A kind of preparation method of carbon micro-nano spherical structure and supercapacitor |
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