CN102586762A - Method for preparing diamond film through multiple-doped hot filament chemical vapor deposition - Google Patents
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Abstract
The invention discloses a method for preparing a diamond film through multiple-doped hot filament chemical vapor deposition and a reaction gas conveying device for the method. The method uses silicon, silicon carbide or silicon nitride ceramics, hard alloy and high-melting-point metal materials (including tungsten, tantalum, molybdenum, titanium and the like) as a substrate and adopts a chemical vapor deposition (CVD) method as the deposition means, an organic compound containing Si, an organic compound containing Si and N, an organic compound containing Si and B or an organic compound containing Si, N and B are simultaneously added into reaction gas hydrogen and acetone (or acetone and carbinol) steam to form a multiple-doped system. a submicron or nanoscale diamond film coating is obtained through the reaction, and the coating thickness can be adjusted in a range of 10-50 mum. The diamond film has the characteristics of abrasion resistance, corrosion resistance, high insulation resistance (in a boron-free occasion), smooth surface, small friction coefficient, easy grinding and polishing and the like, namely has the double advantages of a micro-diamond coating and a nano-diamond coating.
Description
Technical field
The present invention relates to the preparation method in a kind of thin film technique field, be specifically related to method and reactant gases e Foerderanlage that a kind of multi-element doping hot-wire chemical gas-phase deposition prepares diamond thin.
Background technology
Chemical vapour deposition (is called for short the CVD method; Chemical Vapor Deposition) diamond thin has various good physics and chemical property, its extreme hardness, and the frictional coefficient between metal and pottery is very little; The heat conductivility of existing excellence has excellent chemical stability again.The intrinsic diamond film is the good insulation performance body, is a kind of good semiconductor material after the doping, and in addition, the optical transmission of diamond film coating layer is also fine.At present, CVD diamond technology has obtained practical application, like coating mold, cutter and the wear resistant appliance of field of tool, and the corrosion-resistant anode of water treatment electrochemistry etc.In the application of CVD diamond coatings mould and cutter, adhesion of thin film and surface smoothness are key factors.Conventional film crystal grain is too greatly counted micron-sized diamond coatings, has certain internal stress, causes coating adhesion to descend, and this situation is particularly evident in the occasion of cutter outer surface deposition of diamond coatings.Because the underlayer temperature during CVD method depositing diamond film is very high; About about 850 ℃, and adamantine thermal expansivity is less, generally is merely 1/3～1/4 of substrate material; Can produce bigger internal stress in coating after cooling is shunk and (, show as tensile stress in cutter outer surface coating occasion; In mould internal coating occasion, show as stress).In addition, the non-diamond composition in the diamond film coating layer (like graphite or amorphous carbon), cavity and defective etc. can produce " growth stress " in coating, and these stress all can have a negative impact to adhesive force.On the other hand, conventional film coating surface is because adamantine crystal habit; It is uneven that film surface presents height, and diamond hardness is high, and grinding and polishing is difficulty very; Thereby in application scenarios such as coating mold and wear resistant appliances, the workload of grinding and polishing is very big.Chinese invention patent (ZL01113027.X) adopts conventional and the nano diamond coating compounding technology can reduce diamond thin polishing work amount; But because nano diamond coating has big internal stress, the phenomenon of nano coating localized delamination can appear, in the diamond-coated tools application scenario in polishing; The coarse cutting resistance that makes of film surface increases; Coating is peeled off easily, and tool life obviously descends, and working accuracy and surface smoothness are also had disadvantageous effect.In addition, at the film fine manufacture field, diamond film surface is uneven, causes its photolithography resolution to be difficult to improve, and also hampers the application of diamond thin in the MEMS field always.
Summary of the invention
The objective of the invention is to overcome the defective that above-mentioned prior art exists, the method that provides a kind of multi-element doping hot-wire chemical gas-phase deposition to prepare diamond thin reaches the reactant gases e Foerderanlage that wherein adopts.Submicron that method of the present invention is prepared or nano-diamond film coating had both had the wear resistance of conventional thin film diamond, than conventional diamond thin better sticking power and surface smoothness were arranged again; Coating has low-friction coefficient, and characteristics such as easy polishing are more suitable in various application scenarios diamond coatings, like coating mold, cutter and wear resistant appliance and diamond thin microfabrication etc.
For realizing such purpose, key technology is how to reduce diamond coatings stress and enhancement coating adhesive force, can promote secondary nucleation and growth again, promotes the coating surface planarization.Technical solution of the present invention is following:
The present invention relates to the method that a kind of multi-element doping hot-wire chemical gas-phase deposition prepares diamond thin; Said method comprises after the substrate material pre-treatment; Place in the reaction chamber of hot-wire chemical gas-phase deposition device; At its surface deposition diamond thin, the reactant gases that feeds in the said reaction chamber comprises hydrogen and carbon-source gas, and said carbon-source gas is doped with a kind of in the combination of following atom: Si, Si and N, Si and B, Si and N and B atom.
Preferably, said carbon-source gas only mixes the Si atomic time, and the atomic ratio of Si/C is 0.1～3: 100;
Said carbon-source gas doping Si and N atomic time, Si/C, N/C atomic ratio are 0.1～3: 100;
Said carbon-source gas doping Si and B atomic time, the atomic ratio of Si/C, B/C is 0.1～3: 100;
Said carbon-source gas doping Si and N and B atomic time, the atomic ratio of Si/C, N/C, B/C is 0.1～3: 100.
Preferably, said carbon source is acetone, or for acetone and methanol mixture, the steam of carbon source taken out of through Bubbling method by hydrogen to form carbon-source gas and be delivered to reaction chamber.
Preferably, said carbon-source gas only mixes the Si atomic time, and said carbon-source gas gets in carbon source, mixing silicon compound;
Said carbon-source gas doping Si and N atomic time, said carbon-source gas is for mixing silicon compound and nitrogen compound gets in carbon source;
Said carbon-source gas doping Si and B atomic time, said carbon-source gas is for mixing silicon compound and boron cpd gets in carbon source;
Said carbon-source gas doping Si and N and B atomic time, said carbon-source gas gets in carbon source, mixing silicon compound, nitrogen compound and boron cpd;
Said silicon compound, nitrogen compound, boron cpd and carbon source are dissolved each other.
Preferably, said silicon compound is tetraethoxysilane, dimethyldiethoxysilane or ethyl triethoxysilane; Said nitrogen compound is a urea; Said boron cpd is a trimethyl borate.
Preferably, said substrate material is wimet, silicon or silicon carbide ceramics.
The invention still further relates to a kind of reactant gases e Foerderanlage that above-mentioned multi-element doping hot-wire chemical gas-phase deposition prepares the method for diamond thin that is used for, said reactant gases e Foerderanlage comprises shielding gas transfer passage, hydrogen transfer passage and the carbon-source gas transfer passage that links to each other with the Hydrogen Storage device; Nearly Hydrogen Storage device end rises and is disposed with first valve, carbon source storer and the 3rd flow director on the said carbon-source gas transfer passage; Said carbon source storer is provided with bubbling device.The carbon source of doped silicon compound, silicon compound and nitrogen compound, silicon compound and boron cpd or silicon compound, nitrogen compound and boron cpd is housed in the said carbon source storer
Preferably, be provided with the protection bottle between said first valve, the carbon source storer, said protection bottle is provided with backflow preventer with the carbon source storer; Said backflow preventer is closed when the depositing diamond film operating mode, opens under the rest working conditions.
Principle of work of the present invention is: be the basis with silicon atom in diamond coatings, nitrating (or boron-doping) forms the multi-element doping system simultaneously.During silicon atom, be 4 valencys owing to Siliciumatom is the same with carbon atom, it can form the C-Si key with bond with carbon; But Si atomic ratio C atom is many greatly, and its introducing makes diamond film growth produce defective, forms secondary nucleation easily; This just secondary nucleation that constantly produces in the diamond deposition process makes grain refining, forms submicron order diamond coatings structure; Reduce the intercrystalline cavity, changed the stressed condition of coating, helped the raising of sticking power, insulating property and smooth finish.Silicon atom and nitrogen-atoms can make diamond crystals more carefully finer and close simultaneously, can reach the degree of nano-diamond film; When mixing silicon and boron simultaneously, can make diamond coatings have electroconductibility; Mix silicon, boron and nitrogen simultaneously, then can make diamond coatings is the nano-diamond film coating with electroconductibility.
The present invention is implemented in the atoms such as Si, N and B that mix in the diamond coatings through the Si that in reactant gases, mixes, Si and N, Si and B or Si, N and B atom.Si/C atom in the reactant gases is too little, promptly the Si atom very little, the doping DeGrain; If the Si/C atomic ratio is too big, the impurity Siliciumatom is too many, and then the quality of diamond film coating layer (wear resistance etc.) can descend; Similarly, N/C and B/C atomic ratio are also like this; Therefore the atomic ratio of Si/C, N/C, B/C all is adjusted into 0.1～3: 100 in the reactant gases of the present invention.The chemical vapor deposition method condition that the root a tree name is conventional; Carbon source (methane or acetone etc.) molecule only accounts for 1～3: 100 (mol ratios) of hydrogen molecule; And foreign atom (silicon, boron, nitrogen etc.) has only about 1% the order of magnitude of carbon atom, promptly doped source be merely ten thousand of hydrogen/about because gas ratio differs greatly; Hydrogen, carbon source material and doped source all adopt gas source, in actual production, can be difficult to realize; Therefore; The present invention is the primitive reaction raw material with hydrogen and acetone (or acetone, methyl alcohol mixed liquor); Simultaneously a certain proportion of silicon-containing compound or the compound of while siliceous, nitrogenous (boracic) (Si/C, N/C or the calculating of B/C atomic ratio that the root a tree name is set) are dissolved in the acetone; Or these compounds are dissolved in methyl alcohol earlier, then through dissolve with methanol in acetone; These compounds and methyl alcohol, acetone have the certain structure similarity, and mutual solubility is good, when acetone and methanol molecules evaporation, can take it to reaction chamber together in the dissolved ratio.It is to be noted: siliceous, nitrogenous (or boracic) compound that the present invention adds in reactant gases, do not adopt silane SiH
4With ammonia NH
3(or borine B
2H
6), this is because silane is explosive material, lacks security.Ammonia has corrodibility, is unfavorable for environment protection and HUMAN HEALTH.And borine is a toxic gas, and is unfavorable to human body.
Compared with prior art, the present invention has following beneficial effect:
1, gas flow of the present invention and mode of movement both be convenient to scale prodn, had avoided the use in poisonous, explosive, perishable gas doping source again.
2, silicon atom in diamond coatings has changed the stressed condition of coating, helps the raising of sticking power, insulating property and smooth finish.
3, in diamond coatings, simultaneously when silicon atom and nitrogen-atoms, can make diamond crystals more carefully finer and close, reach the degree of nano-diamond film; When mixing silicon and boron simultaneously, can make diamond coatings have electroconductibility; Be mixed with silicon, boron and three kinds of impurity of nitrogen simultaneously, then diamond coatings is the nano-diamond film coating of conduction.
Description of drawings
Fig. 1 is a reactant gases e Foerderanlage synoptic diagram;
Fig. 2 is a shape appearance figure of mixing the silicon diamond film coating layer, wherein, (a) for CVD deposition diamond film surface pattern in mid-term, (b) is CVD diamond deposition later stage surface topography;
Fig. 3 is for mixing silicon diamond film coating layer Raman spectrogram;
Wherein, 1, the first flow unit, 2, second flow director, the 3, the 3rd flow director, 4, first valve, 5, backflow preventer, 6, the protection bottle, 7, the carbon source storer.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Multi-element doping hot-wire chemical gas-phase deposition of the present invention prepares the method for diamond thin, comprises the steps:
(1) substrate material pre-treatment: substrate material is silicon, silit, silicon nitride ceramics, wimet or high melting point metal materials (tungsten, tantalum, molybdenum, titanium etc.) etc.; Carry out necessary pre-treatment before the depositing diamond film; As removing cobalt; Diadust grindings etc. to increase nucleation density, improve coating quality;
(2) depositing diamond film: pretreated substrate material is placed in the reaction chamber of hot-wire chemical gas-phase deposition device; At its surface deposition diamond thin, feed the carbon-source gas that reactant gases in the said reaction chamber comprises hydrogen and doping Si, Si and N, Si and B or Si, N and B atom; Make in the sedimentation products diamond film coating layer and except the C atom, also to contain impurity atomss such as minute quantity Si, N or B.
For being implemented in the purpose of the impurity atomss such as Si, N or B that mix in the reactant gases; The reactant gases e Foerderanlage that the present invention adopts is as shown in Figure 1: the hydrogen that flows out from Hydrogen Storage device (hydrogen gas cylinder); One road warp, second flow director 2 (mass flow controller or float typeflowmeter add needle valve control) directly flows to reaction chamber, is designated as S2; Another road first valve 4, carbon source storer (the carbon source vial is in order to hold acetone) and the 3rd flow director 3 flow to reaction chamber, are designated as S3; The hydrogen on this road is taken the steam of acetone out of through Bubbling method; Bubbling makes the acetone in the vial be in accurate boiling state, and the acetone steam amount is relevant with the ratio of the amounts of hydrogen on this road temperature main and acetone, is convenient meter; The temperature of acetone is controlled at 0 ℃ (the carbon source bottle is placed in the frozen water blended vacuum flask); Under such condition, the saturated vapor pressure of root a tree name acetone in the time of 0 ℃ can calculate acetone/hydrogen in the S3 flow (mol ratio) theoretical value and should be about 9%; Take into account the dilution of above-mentioned S2 hydrogen again; Total acetone/hydrogen that flows to reaction chamber (mol ratio) equals 9 * S3/ (S2+S3), and the flow of adjustment S2 and S3 just is easy to reach technology needed 1～3: 100.In addition, through first flow unit 1, can regulate a certain amount of shielding gas (argon gas) and flow to reaction chamber, its flow is designated as S1, to satisfy the demand of technologies such as preparation Nano diamond.
In order to prevent that acetone takes place in the operational process of craft to flow backwards; Taked the binomial measure: the one, between first valve 4, carbon source bottle 7, adorned individual protection bottle 6, two, between protection bottle 6 and carbon source bottle 7, adorned individual backflow preventer 5, this valve 5 is closed when sedimentation state; To guarantee carrying out smoothly of bubbling; And all the other times open, and are identical with the air pressure that keeps carbon source bottle 7 two ends, thereby avoided the refluence of acetone.
It is as shown in Figure 2 that present embodiment is mixed the shape appearance figure of diamond film coating layer of silicon, and Fig. 2 .a. is the surface topography of CVD deposition of diamond thin films coating during mid-term, at big intergranule (the low-lying place of concavo-convex pattern), exists many little crystal grain.The big crystal grain of early growth is main to appear (111) crystal face, and the little crystal grain of secondary generation is that to appear (100) face be main.Can think, at the active H atomic percent at low-lying place and carbon-containing group (CH for example
3, C
2H
2Deng) all than higher, and impurity Si atom makes diamond crystals produce certain defective, therefore is easy to generate subgrain at low-lying place.Fig. 2 .b. illustrates the surface topography of CVD diamond deposition later stage coating, and generally speaking surface ratio is more smooth, just as on the big crystal grain of a number micron, having sticked thickly dotted little crystal grain, about 100～300 nanometers of the size of little crystal grain.Fig. 3 illustrates that the Si/C atomic ratio is the Raman spectrogram of 1: 100 o'clock diamond film coating layer, has sharp-pointed diamond peak at the 1338cm-1 place, though explain that to mix the Si diamond crystals little, the diamond lattice structure is very complete.This is very beneficial for the raising of diamond coatings film quality.
Get 10 on Φ 5mm wimet (YG6) milling cutter, the knife edge part with milling cutter places the Murakami agent to carry out ultrasonic erosion respectively, and the prescription of corrosive fluid (weight ratio) Tripotassium iron hexacyanide: Pottasium Hydroxide: water is 1: 1: 10; About 20 minutes of time placed hydrochloric acid hydrogen peroxide solution (volume ratio 1: 4) to corrode for 20～30 seconds after taking-up washes again, placed diadust (20 microns of granularities) alcohol suspension sonic oscillation to handle again 20 minutes after washing is clean; Clean then and dry up, the deposition of beginning CVD diamond film coating layer after 10 milling cutters evenly are inserted into the cooling socket and are placed into the CVD reaction chamber, processing parameter is: carbon source is main with acetone; Be dissolved with tetraethoxysilane and trimethyl borate simultaneously; Wherein the Si/C atomic ratio is 3: 100, and the B/C atomic ratio is 1: 100, chamber pressure 3KPa; The total stream of gas weighs 700 ml/min; Acetone/hydrogen volume ratio is 1.5: 100, and the tantalum wire temperature is about 2200 ℃, after depositing through 6 hours; Blade place deposition obtains the diamond coatings of the light of about 8 micron thick, and surface diamond crystal grain is 0.1～0.3 μ m.This milling cutter is used for machining aluminum silicon alloy, and the service life as compared carbide-tipped milling cutter improves more than 10 times, and the working accuracy and the surface smoothness of workpiece also are greatly improved.
In the present embodiment,, promoted the raising of coating adhesion owing to the chemical bonded refractory of B nuclear power and many substrates formation at high temperature closes; Therefore, on this basis, be reactant gases with the mixture of hydrogen, acetone; Trimethyl borate to be dissolved in the acetone soln is the doped with boron source; At diamond coatings and wimet at the interface, element generation chemical reactions such as boron and cobalt, the boron cobalt cpd of generation etc. are gathered in diamond coatings and wimet at the interface; And be present in the diamond coatings; Stop the further diffusion of cobalt element in the tool matrix, alleviated the coating internal stress, further reached the sticking power purpose that improves between diamond coatings and the wimet.
Get 5 on Φ 15mm wimet (YG6) milling cutter, the knife edge part with milling cutter places the Murakami agent to carry out ultrasonic erosion respectively, and the prescription of corrosive fluid (weight ratio) Tripotassium iron hexacyanide: Pottasium Hydroxide: water is 1: 1: 10; About 20 minutes of time placed the dioxysulfate aqueous solution (volume ratio 1: 10) to corrode for 20～30 seconds after taking-up washes again, placed diadust (20 microns of granularities) alcohol suspension sonic oscillation to handle again 20 minutes after washing is clean; Clean then and dry up, the deposition of beginning CVD diamond film coating layer after 5 milling cutters evenly are inserted into the cooling socket and are placed into the CVD reaction chamber, processing parameter is: carbon source is main with acetone; Be dissolved with dimethyldiethoxysilane, trimethyl borate and urea simultaneously, wherein the Si/C atomic ratio is 0.1: 100, and the B/C atomic ratio is 0.1: 100; The N/C atomic ratio is 1: 100; Chamber pressure 3KPa, gas always flow heavy 700 ml/min, and acetone/hydrogen volume ratio is 2: 100; The tantalum wire temperature is about 2300 ℃; Through after 8 hours depositions, blade place deposition obtains the diamond coatings of about 10 micron thick, and surface diamond crystal grain is 0.7～1 μ m.This milling cutter is used for the processing graphite electrode, and the service life as compared carbide-tipped milling cutter improves more than 10 times, and the working accuracy and the surface smoothness of workpiece also are greatly improved.
Embodiment 4
Get 20 on the miniature wimet of Φ 0.24mm (YG6) milling cutter, the knife edge part with milling cutter places the Murakami agent to carry out ultrasonic erosion respectively, and the prescription of corrosive fluid (weight ratio) Tripotassium iron hexacyanide: Pottasium Hydroxide: water is 1: 1: 10; About 20 minutes of time placed hydrochloric acid hydrogen peroxide solution (volume ratio 1: 4) to corrode for 5～10 seconds after taking-up washes again, placed diadust (20 microns of granularities) alcohol suspension sonic oscillation to handle again 20 minutes after washing is clean; Clean then and dry up, the deposition of beginning CVD diamond film coating layer after 20 milling cutters evenly are inserted into the cooling socket and are placed into the CVD reaction chamber, processing parameter is: carbon source is main with acetone; Be dissolved with tetraethoxysilane and urea simultaneously, wherein the Si/C atomic ratio is 0.5: 100, and the N/C atomic ratio is 0.1: 100; Chamber pressure 3KPa; The total stream of gas weighs 700 ml/min, and acetone/hydrogen volume ratio is 2: 100; The tantalum wire temperature is about 2100 ℃; Through after 3 hours depositions, blade place deposition obtains the diamond coatings of about 5 micron thick, and surface diamond crystal grain is 0.3～0.6 μ m.This milling cutter is used to process high-performance graphite, and the service life as compared carbide-tipped milling cutter improves more than 10 times, and the working accuracy and the surface smoothness of workpiece also are greatly improved.
Embodiment 5
3 is not a substrate resistivity silicon wafer polishing, pre-grinding and polishing using diamond powder W10 surface 5 minutes after washing with pure water, dried, placed in a reaction chamber rotating platform, starting CVD diamond film deposition.There is the parallel vertical pulling tantalum wire (heated filament) of 6 Φ 6 rotatable platform top, between tantalum wire and silicon chip at a distance of 10 millimeters.The deposition process conditions of diamond thin is: carbon source is that volume ratio is 1: 1 acetone and a methyl alcohol, is dissolved with ethyl triethoxysilane, trimethyl borate and urea in the carbon source simultaneously, and wherein the Si/C atomic ratio is 2: 100; The B/C atomic ratio is 3: 100, and the N/C atomic ratio is 3: 100, and chamber pressure is 4.5KPa; The total stream of gas weighs 700 ml/min; The volume ratio of acetone/hydrogen is 1～2: 100, and the tantalum wire temperature is about 2100 ℃, after depositing through 6 hours; Having obtained thickness is 10 microns, and surface diamond crystal grain is 3 o'clock conductive diamond films of 0.2～0.4 μ m.
Embodiment 6
Substrate is external diameter Φ 55, internal diameter Φ 42, thick 8 millimeters silicon carbide sealed ring, single-sided polishing, polished surface depositing diamond film.The method of surface preparation is identical with silicon slice processing method among the embodiment 1.After the processing substrate is placed on the platform of reaction chamber rotation the deposition of beginning CVD diamond thin.There is the parallel vertical pulling tantalum wire (heated filament) of 4 Φ 6 rotatable platform top, between tantalum wire and silicon carbide sealed ring polished surface apart 10 millimeters.Contain 80 milliliters in acetone in the carbon source, 20 milliliters of methyl alcohol are dissolved with tetraethoxysilane, trimethyl borate and urea simultaneously; Wherein the Si/C atomic ratio is 1: 100, and the B/C atomic ratio is 1: 100, and the N/C atomic ratio is 0.8: 100; Chamber pressure is 4.5KPa, and gas always flows heavy 700 ml/min, and the volume ratio of acetone/hydrogen is 1～2: 100; The tantalum wire temperature is about 2100 ℃, and after depositing through 6 hours, having obtained thickness is the annular diamond thin of 12 microns surface-brightening.The diamond crystals of coatingsurface is about 50～100 nanometers.Because coatingsurface smooth finish is better, significantly reduced the polishing work amount of diamond coatings, through 2 hours mechanical mill polishing, the diamond coatings of wear ring end face can reach the minute surface degree, and Ra can reach 0.05 μ m.
Can know by above-mentioned each embodiment; In order to reach the purpose of mixing silicon in the diamond coatings; Need to add siliceous organic low molecular compounds, like Trisilicopropane, tetrasilane, tetraethoxysilane, dimethyldiethoxysilane, ethyl triethoxysilane etc., the organic silicide of the first two kind liquid and the structural similarity of acetone are poor; Mutual solubility is also poor, and unsuitable being dissolved in the acetone carried; Several kinds of backs and methyl alcohol, acetone have certain structure property similarity; Can be dissolved in the mixed solution of acetone or acetone and methyl alcohol; Can utilize the evaporation of acetone and methyl alcohol to bring it into reaction chamber together; Except that carbon atom, also have impurity atoms silicon, thereby can reach the purpose of mixing silicon in the CVD sedimentation products diamond thin structure.The diamond coatings of only mixing silicon is an electric insulation, if in acetone or acetone and methyl alcohol mixed liquor, also dissolve trimethyl borate similarly simultaneously, and the silicon that then both mixed in the diamond coatings, the boron that mixed again makes film coating be electroconductibility.If dissolve siliceous organic low molecular compounds and urea (nitrogenous) in the carbon source (acetone or acetone and methyl alcohol mixed liquor) simultaneously, then the crystal grain of diamond film coating layer is just more carefully finer and close, can reach the degree of nano-diamond film.If be mixed with silicon, boron or three kinds of impurity of nitrogen in the carbon source simultaneously, then reaction product is the nano-diamond film coating of conduction.
Claims (8)
1. a multi-element doping hot-wire chemical gas-phase deposition prepares the method for diamond thin; Said method comprises after the substrate material pre-treatment; Place in the reaction chamber of hot-wire chemical gas-phase deposition device,, it is characterized in that at its surface deposition diamond thin; The reactant gases that feeds in the said reaction chamber comprises hydrogen and carbon-source gas, and said carbon-source gas is doped with a kind of in the combination of following atom: Si, Si and N, Si and B, Si and N and B atom.
2. multi-element doping hot-wire chemical gas-phase deposition according to claim 1 prepares the method for diamond thin, it is characterized in that, said carbon-source gas only mixes the Si atomic time, and the atomic ratio of Si/C is 0.1～3: 100;
Said carbon-source gas doping Si and N atomic time, Si/C, N/C atomic ratio are 0.1～3: 100;
Said carbon-source gas doping Si and B atomic time, the atomic ratio of Si/C, B/C is 0.1～3: 100;
Said carbon-source gas doping Si and N and B atomic time, the atomic ratio of Si/C, N/C, B/C is 0.1～3: 100.
3. multi-element doping hot-wire chemical gas-phase deposition according to claim 2 prepares the method for diamond thin; It is characterized in that; Said carbon source is acetone, or for acetone and methanol mixture, the steam of carbon source is taken out of through Bubbling method by hydrogen and to be formed carbon-source gas and be delivered to reaction chamber.
4. multi-element doping hot-wire chemical gas-phase deposition according to claim 2 prepares the method for diamond thin, it is characterized in that, said carbon-source gas only mixes the Si atomic time, and said carbon-source gas gets in carbon source, mixing silicon compound;
Said carbon-source gas doping Si and N atomic time, said carbon-source gas is for mixing silicon compound and nitrogen compound gets in carbon source;
Said carbon-source gas doping Si and B atomic time, said carbon-source gas is for mixing silicon compound and boron cpd gets in carbon source;
Said carbon-source gas doping Si and N and B atomic time, said carbon-source gas gets in carbon source, mixing silicon compound, nitrogen compound and boron cpd;
Said silicon compound, nitrogen compound, boron cpd and carbon source are dissolved each other.
5. multi-element doping hot-wire chemical gas-phase deposition according to claim 2 prepares the method for diamond thin, it is characterized in that, said silicon compound is tetraethoxysilane, dimethyldiethoxysilane or ethyl triethoxysilane; Said nitrogen compound is a urea; Said boron cpd is a trimethyl borate.
6. multi-element doping hot-wire chemical gas-phase deposition according to claim 2 prepares the method for diamond thin, it is characterized in that, said substrate material is wimet, silicon or silicon carbide ceramics.
7. one kind is used for the reactant gases e Foerderanlage that the described multi-element doping hot-wire chemical gas-phase deposition of claim 1 prepares the method for diamond thin; It is characterized in that said reactant gases e Foerderanlage comprises shielding gas transfer passage, hydrogen transfer passage and the carbon-source gas transfer passage that links to each other with the Hydrogen Storage device; Nearly Hydrogen Storage device end rises and is disposed with first valve, carbon source storer and the 3rd flow director on the said carbon-source gas transfer passage; Said carbon source storer is provided with bubbling device.
8. reactant gases e Foerderanlage according to claim 7 is characterized in that, is provided with the protection bottle between said first valve, the carbon source storer, and said protection bottle is provided with backflow preventer with the carbon source storer; Said backflow preventer is closed when the depositing diamond film operating mode, opens under the rest working conditions.
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| CN104789937A (en) * | 2015-02-15 | 2015-07-22 | 河北一缆通电子商务有限公司 | Production method for drawing mold with nano-scale diamond coating on inner hole surface |
| CN109722649A (en) * | 2017-10-31 | 2019-05-07 | 深圳先进技术研究院 | A kind of hard alloy and preparation method thereof with diamond coatings |
| CN108103476A (en) * | 2017-12-05 | 2018-06-01 | 富耐克超硬材料股份有限公司 | The preparation method and its preparation facilities of a kind of diamond coatings |
| CN108565124B (en) * | 2018-03-27 | 2019-12-31 | 天津理工大学 | Preparation method of sodium ion supercapacitor based on boron-doped graphene/boron-doped diamond composite electrode |
| CN108565124A (en) * | 2018-03-27 | 2018-09-21 | 天津理工大学 | A kind of preparation method of the sodium ion ultracapacitor based on boron-doped graphite alkene/boron-doped diamond compounded electrode |
| CN109023293A (en) * | 2018-08-21 | 2018-12-18 | 四川旗丰新材科技有限公司 | Diamond coatings mechanical seal ring manufacturing method with cold frictional behavior |
| CN109023293B (en) * | 2018-08-21 | 2021-01-29 | 四川旗丰新材科技有限公司 | Method for manufacturing diamond-coated mechanical seal ring with cold friction characteristic |
| WO2020118510A1 (en) * | 2018-12-11 | 2020-06-18 | 深圳先进技术研究院 | Boron-silicon co-doped diamond electrode, preparation method therefor and use thereof |
| CN111304690A (en) * | 2018-12-11 | 2020-06-19 | 深圳先进技术研究院 | Boron-silicon co-doped diamond electrode and preparation method and application thereof |
| CN111304690B (en) * | 2018-12-11 | 2022-04-12 | 深圳先进技术研究院 | Boron-silicon co-doped diamond electrode and preparation method and application thereof |
| CN111593318A (en) * | 2020-07-13 | 2020-08-28 | 内蒙古科技大学 | Diamond nanocrystalline/nitrogen-doped silicon carbide interface phase n-type semiconductor composite film and preparation method thereof |
| CN114751408A (en) * | 2022-03-25 | 2022-07-15 | 浙江工业大学 | Method for preparing diamond based on graphite under low pressure |
| CN114751408B (en) * | 2022-03-25 | 2023-09-05 | 浙江工业大学 | Method for preparing diamond based on graphite at low pressure |
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