CN102586762B - The method of preparing diamond film through multiple-doped hot filament chemical vapor deposition - Google Patents
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Abstract
The invention discloses a kind of preparing diamond film through multiple-doped hot filament chemical vapor deposition method and for reactant gases e Foerderanlage wherein.Described method with silicon, silicon carbide or silicon nitride ceramics, Wimet and high melting point metal materials (tungsten, tantalum, molybdenum, titanium etc.) for substrate, take CVD as deposition approach, add containing Si in reactant gases hydrogen and acetone (or acetone and methyl alcohol) steam simultaneously, containing Si with containing N, containing Si with containing B or containing Si, containing N and the organic compound containing B, form multi-element doping system; Be obtained by reacting submicron or nano-diamond film coating, coat-thickness can regulate between 10 ~ 50 μm.This film has wear-resisting, corrosion-resistant, the feature such as insulation resistance is high (not boron-doping occasion), smooth surface, frictional coefficient are little, easy grinding polishing, namely has the two-fold advantage of micron diamond and nano diamond coating concurrently.
Description
Technical field
The present invention relates to a kind of preparation method of thin film technique field, be specifically related to a kind of method and reactant gases e Foerderanlage of preparing diamond film through multiple-doped hot filament chemical vapor deposition.
Background technology
Chemical vapour deposition (is called for short CVD, Chemical Vapor Deposition) diamond thin has various excellent process based prediction model, its extreme hardness, and the frictional coefficient between metal and pottery is very little, the heat conductivility of existing excellence, has again excellent chemical stability.Intrinsic diamond film is good insulating body, is a kind of excellent semiconductor material after doping, and in addition, the optical transmission of diamond film coating layer is also fine.At present, cvd diamond technology obtains practical application, as the coating mold of field of tool, cutter and wear resistant appliance, and the corrosion-resistant anode of water treatment electrochemistry etc.In the application of cvd diamond coating mold and cutter, adhesion of thin film and surface smoothness are key factors.Traditional films crystal grain too greatly counts micron-sized diamond coatings, and there is certain internal stress, cause coating adhesion to decline, this situation is particularly evident in the occasion of the outside deposition diamond coatings such as cutter.Because underlayer temperature during CVD depositing diamond film is very high, about about 850 DEG C, and adamantine thermal expansivity is less, generally be only 1/3 ~ 1/4 of substrate material, larger internal stress can be produced in coating after cooling meat and (in external surface coating occasions such as cutters, show as tensile stress; In mould internal coating occasion, show as stress).In addition, the non-diamond component (as graphite or amorphous carbon) in diamond film coating layer, cavity and defect etc., can produce " growth stress " in the coating, these stress all can have a negative impact to adhesive force.On the other hand, traditional films coatingsurface, due to adamantine crystal habit, it is uneven that film surface presents height, and diamond hardness is high, and grinding and polishing is very difficult, thus in the application scenario such as coating mold and wear resistant appliance, the workload of grinding and polishing is very large.Chinese invention patent (ZL01113027.X) adopts routine and nano diamond coating compounding technology can reduce diamond thin polishing work amount, but because nano diamond coating has larger internal stress, the phenomenon of nano coating localized delamination is there will be in polishing, in diamond-coated tools application scenario, the coarse cutting resistance that makes of film surface increases, coating is easily peeled off, and tool life obviously declines, and also has disadvantageous effect to working accuracy and surface smoothness.In addition, at film fine manufacture field, diamond film surface is uneven, causes its photolithography resolution to be difficult to improve, also hampers the application of diamond thin in micro electro mechanical system field always.
Summary of the invention
The object of the invention is to the defect overcoming the existence of above-mentioned prior art, the reactant gases e Foerderanlage a kind of method of preparing diamond film through multiple-doped hot filament chemical vapor deposition being provided and wherein adopting.Submicron prepared by method of the present invention or nano-diamond film coating had both had the adamantine wear resistance of traditional films, had better sticking power and surface smoothness again than conventional PCD film; The features such as coating has low-friction coefficient, easy polishing, make diamond coatings be more suitable for various application scenario, as coating mold, cutter and wear resistant appliance and diamond thin microfabrication etc.
For realizing such object, gordian technique how can reduce diamond coatings stress and increase Strong coating adhesion, can promote secondary nucleation and growth again, promote coatingsurface planarization.Technical solution of the present invention is as follows:
The present invention relates to a kind of method of preparing diamond film through multiple-doped hot filament chemical vapor deposition, described method comprises after substrate material pre-treatment, be placed in the reaction chamber of hot-wire chemical gas-phase deposition device, at its surface deposition diamond thin, the reactant gases passed in described reaction chamber comprises hydrogen and carbon-source gas, and described carbon-source gas is doped with the one in following atom combination: Si, Si and N, Si and B, Si and N and B atom.
Preferably, described carbon-source gas only adulterates the Si atomic time, and the atomic ratio of Si/C is 0.1 ~ 3: 100;
When described carbon-source gas doping Si and atom N, Si/C, N/C atomic ratio is 0.1 ~ 3: 100;
Described carbon-source gas doping Si and the B atomic time, the atomic ratio of Si/C, B/C is 0.1 ~ 3: 100;
Described 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, described carbon source is acetone or the mixture for acetone and methyl alcohol, to be taken out of by the steam of carbon source form carbon-source gas and be delivered to reaction chamber by hydrogen by Bubbling method.
Preferably, described carbon-source gas only adulterates the Si atomic time, and described carbon-source gas for mixing silicon compound and obtaining in carbon source;
When described carbon-source gas doping Si and atom N, described carbon-source gas obtains for mixing silicon compound and nitrogen compound in carbon source;
Described carbon-source gas doping Si and the B atomic time, described carbon-source gas obtains for mixing silicon compound and boron compound in carbon source;
Described carbon-source gas doping Si and N and B atomic time, described carbon-source gas obtains for mixing silicon compound, nitrogen compound and boron compound in carbon source;
Described silicon compound, nitrogen compound, boron compound and carbon source are dissolved each other.
Preferably, described silicon compound is tetraethoxysilane, dimethyldiethoxysilane or ethyl triethoxysilane; Described nitrogen compound is urea; Described boron compound is trimethyl borate.
Preferably, described substrate material is Wimet, silicon or silicon carbide ceramics.
The invention still further relates to a kind of for the reactant gases e Foerderanlage in the method for above-mentioned preparing diamond film through multiple-doped hot filament chemical vapor deposition, the carbon-source gas transfer passage that described reactant gases e Foerderanlage comprises shielding gas transfer passage, hydrogen transfer passage and is connected with hydrogen storer; On described carbon-source gas transfer passage, nearly hydrogen storer end rises and is disposed with the first valve, carbon source storer and the 3rd flow director; Described carbon source storer is provided with bubbling device.Described carbon source storer is built with the carbon source of doped silicon compound, silicon compound and nitrogen compound, silicon compound and boron compound or silicon compound, nitrogen compound and boron compound
Preferably, be provided with protection bottle between described first valve, carbon source storer, described protection bottle and carbon source storer are provided with backflow preventer; Described backflow preventer is close when depositing diamond film operating mode, is open under rest working conditions.
Principle of work of the present invention is: based on silicon atom in diamond coatings, simultaneously nitrating (or boron-doping), forms multi-element doping system.During silicon atom, be 4 valencys because Siliciumatom is the same with carbon atom, it can form C-Si key with bond with carbon, but Si atomic ratio C atom is many greatly, its introducing makes diamond film growth produce defect, easy formation secondary nucleation, this secondary nucleation constantly produced at diamond deposition process, makes grain refining just, form submicron order diamond coatings structure, decrease intercrystalline cavity, change the stressed condition of coating, be conducive to the raising of sticking power, insulating property and smooth finish.Silicon atom and nitrogen-atoms simultaneously, can make diamond crystals thinner finer and close, can reach the degree of nano-diamond film; When mixing silicon and boron, diamond coatings can be made to have electroconductibility simultaneously; Mix silicon, boron and nitrogen simultaneously, then diamond coatings can be made to be the nano-diamond film coating with electroconductibility.
The present invention realizes adulterating the atoms such as Si, N and B in diamond coatings by adulterate in reactant gases Si, Si and N, Si and B or Si, N and B atom.Si/C atom in reactant gases is too little, and namely Si atom very little, doping DeGrain; If Si/C atomic ratio is too large, impurity Siliciumatom is too many, then the quality (wear resistance etc.) of diamond film coating layer can decline; Similarly, N/C and B/C atomic ratio is also like this; Therefore in reactant gases of the present invention, the atomic ratio of Si/C, N/C, B/C is all adjusted to 0.1 ~ 3: 100.The chemical vapor deposition method condition of root Ju routine, 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.) only has the order of magnitude of about 1% of carbon atom, namely doped source is only ten thousand/left and right of hydrogen, because gas ratio differs greatly, hydrogen, carbon source material and doped source all adopt gas source, can be difficult to realize in actual production; Therefore, the present invention with hydrogen and acetone (or acetone, methyl alcohol mixed liquor) for primitive reaction raw material, the compound (Si/C, N/C or B/C atomic ratio of root Ju setting calculates) of a certain proportion of silicon-containing compound or simultaneously siliceous, nitrogenous (boracic) is dissolved in acetone simultaneously, or these compounds are first dissolved in methyl alcohol, then by dissolve with methanol in acetone; These compounds and methyl alcohol, acetone have certain structural similarity, and mutual solubility is good, when acetone and methanol molecules evaporation, can take it to reaction chamber together in the ratio of dissolving.It is to be noted: siliceous, nitrogenous (or boracic) compound that the present invention adds in reactant gases, does not adopt silane SiH
4with ammonia NH
3(or borine B
2h
6), this is because silane is explosive material, lack security.Ammonia has corrodibility, is unfavorable for environment protection and HUMAN HEALTH.And borine is toxic gas, 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 were both convenient to scale production, turn avoid the use in poisonous, explosive, perishable gas doping source.
2, silicon atom in diamond coatings, changes the stressed condition of coating, is conducive to the raising of sticking power, insulating property and smooth finish.
3, the while of in diamond coatings when silicon atom and nitrogen-atoms, diamond crystals can be made thinner finer and close, reach the degree of nano-diamond film; When mixing silicon and boron, diamond coatings can be made to have electroconductibility simultaneously; Be mixed with silicon, boron and nitrogen three kinds of impurity, then diamond coatings is the nano-diamond film coating of conduction simultaneously.
Accompanying drawing explanation
Fig. 1 is reactant gases e Foerderanlage schematic diagram;
Fig. 2 is the shape appearance figure mixing silicon diamond film coating layer, and wherein, (a) is CVD deposition diamond film surface pattern in mid-term, and (b) is cvd diamond deposition later stage surface topography;
Fig. 3 is for mixing silicon diamond film coating layer Raman spectrogram;
Wherein, 1, first flow controller, 2, second amount controller, the 3, the 3rd flow director, the 4, first valve, 5, backflow preventer, 6, protection bottle, 7, carbon source storer.
Embodiment
Elaborate to embodiments of the invention below in conjunction with accompanying drawing, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The method of preparing diamond film through multiple-doped hot filament chemical vapor deposition of the present invention, comprises the steps:
(1) substrate material pre-treatment: substrate material is silicon, silicon carbide, silicon nitride ceramics, Wimet or high melting point metal materials (tungsten, tantalum, molybdenum, titanium etc.) etc., necessary pre-treatment is carried out before depositing diamond film, as removed cobalt, diadust grinding 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, the reactant gases passed in described reaction chamber comprises the carbon-source gas of hydrogen and doping Si, Si and N, Si and B or Si, N and B atom; Make in sedimentation products diamond film coating layer except C atom, also containing the impurity atoms such as minute quantity Si, N or B.
For realizing adulterating the object of the impurity atomss such as Si, N or B in reactant gases, the present invention adopt reactant gases e Foerderanlage as shown in Figure 1: the hydrogen flowed out from hydrogen storer (hydrogen gas cylinder), one tunnel directly flows to reaction chamber through second amount controller 2 (mass flow controller or float typeflowmeter add needle valve and control), is designated as S2, another road first valve 4, carbon source storer (carbon source vial, in order to hold acetone) and the 3rd flow director 3 flow to reaction chamber, be designated as S3, the hydrogen on this road is taken out of by the steam of Bubbling method by acetone, bubbling makes the acetone in vial be in accurate boiling state, the ratio of the amounts of hydrogen on acetone steam Liang Yugai road is main relevant with the temperature of acetone, for convenience of meter, the temperature of acetone is controlled 0 DEG C (carbon source bottle being placed in the vacuum flask of frozen water mixing), in such a situa-tion, the saturated vapor pressure of root Ju acetone 0 DEG C time, acetone/hydrogen (mol ratio) theoretical value in S3 flow can be calculated and should be about 9%, take into account the dilution of above-mentioned S2 hydrogen again, total acetone/hydrogen (mol ratio) flowing to reaction chamber equals 9 × S3/ (S2+S3), the flow of adjustment S2 and S3, just be easy to reach 1 ~ 3: 100 required for technique.In addition, by first flow controller 1, a certain amount of shielding gas (argon gas) can be regulated to flow to reaction chamber, and its flow is designated as S1, to meet the demand preparing the techniques such as Nano diamond.
Flow backwards to prevent that acetone occurs in operational process of craft; take binomial measure: one is between the first valve 4, carbon source bottle 7, filled individual protection bottle 6; two is filled individual backflow preventer 5 between protection bottle 6 and carbon source bottle 7; this valve 5 is close when sedimentation state; to ensure carrying out smoothly of bubbling; and all the other times open, to keep the air pressure at carbon source bottle 7 two ends identical, thus avoid the refluence of acetone.
embodiment 1
Polishing high resistant silicon chip when substrate is 3, pre-treatment adopts 15 minutes, W1 diamond micro mist grinding and polishing face, washes Net post-drying with pure Net, is placed on the platform of reaction chamber rotation, starts the deposition of cvd diamond film.The parallel vertical pulling tantalum wire (heated filament) of 6 Φ 6 is had, at a distance of 10 millimeters between tantalum wire and silicon chip above rotatable platform.The deposition process conditions of diamond thin is: carbon source is acetone, tetraethoxysilane is dissolved with in acetone, wherein Si/C atomic ratio is 1: 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, tantalum wire temperature is about 2100 DEG C, after 8 hours depositions, obtaining thickness is 16 microns, intrinsic diamond film when area is 3.Compared with not mixing the diamond film coating layer of silicon, one is that surface is more smooth, and Ra is reduced to about 0.2 μm from original 1 ~ 2 μm; Two is that the thermal distortion of substrate Si sheet is little, and this reduces relevant with stress in diamond thin.These two results are all conducive to the microfabrication of diamond thin.
The present embodiment mixes the shape appearance figure of the diamond film coating layer of silicon as shown in Figure 2, and when Fig. 2 .a. is cvd diamond thin film deposition mid-term, the surface topography of coating, comparatively (the low-lying place of concavo-convex pattern) between large grain size, also exists much little crystal grain.The comparatively large grain size of early growth is to appear (111) crystal face, and the little crystal grain of secondary generation is that to appear (100) face be main.Can think, at active H atom concentration and carbon-containing group (the such as CH at low-lying place
3, C
2h
2deng) all higher, and impurity Si atom makes diamond crystals produce certain defect, therefore easily produces 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 having sticked thickly dotted little crystal grain, size about 100 ~ 300 nanometer of little crystal grain on the large grain size of a number micron.The Raman spectrogram of diamond film coating layer when Fig. 3 illustrates that Si/C atomic ratio is 1: 100, has sharp-pointed diamond peak at 1338cm-1 place, though illustrate that to mix Si diamond crystals little, diamond lattice structure is very complete.This is very beneficial for the raising of diamond coatings film quality.
embodiment 2
Get 10, Φ 5mm Wimet (YG6) milling cutter, respectively the knife edge part of milling cutter is placed in Murakami agent and carries out ultrasonic erosion, formula (weight ratio) Tripotassium iron hexacyanide of corrosive fluid: potassium hydroxide: water is 1: 1: 10, about 20 minutes time, be placed in hydrochloric acid hydrogen peroxide solution (volume ratio 1: 4) after taking-up washes again and corroded for 20 ~ 30 seconds, water is placed in diadust (granularity 20 microns) alcohol suspension sonic oscillation process 20 minutes after cleaning again, then clean and dry up, 10 milling cutters are evenly inserted into and cool socket and the deposition starting cvd diamond film coating after being placed into CVD reaction chamber, processing parameter is: carbon source is based on acetone, be dissolved with tetraethoxysilane and trimethyl borate simultaneously, wherein Si/C atomic ratio is 3: 100, B/C atomic ratio is 1: 100, chamber pressure 3KPa, gas always flows heavy 700 ml/min, acetone/hydrogen volume ratio is 1.5: 100, tantalum wire temperature is about 2200 DEG C, after 6 hours depositions, blade place deposition obtains the diamond coatings of the light of about 8 micron thickness, surface diamond crystal grain is 0.1 ~ 0.3 μm.This milling cutter is used for machining aluminum silicon alloy, and service life as compared carbide-tipped milling cutter improves more than 10 times, and the working accuracy of workpiece and surface smoothness have also been obtained very large raising.
In the present embodiment, because at high temperature B nuclear power and many substrates form chemical bonds, facilitate the raising of coating adhesion; Therefore, on this basis, with the mixture of hydrogen, acetone for reactant gases, to be dissolved in trimethyl borate in acetone soln for doped with boron source, in the interface of diamond coatings and Wimet, the element such as boron and cobalt generation chemical reaction, the boron cobalt compound etc. produced is gathered in the interface of diamond coatings and Wimet, and be present in diamond coatings, prevent the further diffusion of cobalt element in tool matrix, alleviate coating internal stress, reach the sticking power object improved between diamond coatings and Wimet further.
embodiment 3
Get 5, Φ 15mm Wimet (YG6) milling cutter, respectively the knife edge part of milling cutter is placed in Murakami agent and carries out ultrasonic erosion, formula (weight ratio) Tripotassium iron hexacyanide of corrosive fluid: potassium hydroxide: water is 1: 1: 10, about 20 minutes time, be placed in the dioxysulfate aqueous solution (volume ratio 1: 10) after taking-up washes again and corroded for 20 ~ 30 seconds, water is placed in diadust (granularity 20 microns) alcohol suspension sonic oscillation process 20 minutes after cleaning again, then clean and dry up, 5 milling cutters are evenly inserted into and cool socket and the deposition starting cvd diamond film coating after being placed into CVD reaction chamber, processing parameter is: carbon source is based on acetone, be dissolved with dimethyldiethoxysilane simultaneously, trimethyl borate and urea, wherein Si/C atomic ratio is 0.1: 100, B/C atomic ratio is 0.1: 100, N/C atomic ratio is 1: 100, chamber pressure 3KPa, gas always flows heavy 700 ml/min, acetone/hydrogen volume ratio is 2: 100, tantalum wire temperature is about 2300 DEG C, after 8 hours depositions, blade place deposition obtains the diamond coatings of about 10 micron thickness, surface diamond crystal grain is 0.7 ~ 1 μm.This milling cutter is used for processing graphite electrode, and service life as compared carbide-tipped milling cutter improves more than 10 times, and the working accuracy of workpiece and surface smoothness have also been obtained very large raising.
embodiment 4
Get 20, the miniature Wimet of Φ 0.24mm (YG6) milling cutter, respectively the knife edge part of milling cutter is placed in Murakami agent and carries out ultrasonic erosion, formula (weight ratio) Tripotassium iron hexacyanide of corrosive fluid: potassium hydroxide: water is 1: 1: 10, about 20 minutes time, be placed in hydrochloric acid hydrogen peroxide solution (volume ratio 1: 4) after taking-up washes again and corroded for 5 ~ 10 seconds, water is placed in diadust (granularity 20 microns) alcohol suspension sonic oscillation process 20 minutes after cleaning again, then clean and dry up, 20 milling cutters are evenly inserted into and cool socket and the deposition starting cvd diamond film coating after being placed into CVD reaction chamber, processing parameter is: carbon source is based on acetone, be dissolved with tetraethoxysilane and urea simultaneously, wherein Si/C atomic ratio is 0.5: 100, N/C atomic ratio is 0.1: 100, chamber pressure 3KPa, gas always flows heavy 700 ml/min, acetone/hydrogen volume ratio is 2: 100, , tantalum wire temperature is about 2100 DEG C, after 3 hours depositions, blade place deposition obtains the diamond coatings of about 5 micron thickness, surface diamond crystal grain is 0.3 ~ 0.6 μm.This milling cutter is for processing high performance graphite, and service life as compared carbide-tipped milling cutter improves more than 10 times, and the working accuracy of workpiece and surface smoothness have also been obtained very large raising.
embodiment 5
Not polishing low resistance silicon chip when substrate is 3, pre-treatment adopts 5 minutes, W10 diamond micro mist grinding and polishing face, washes Net post-drying with pure Net, is placed on the platform of reaction chamber rotation, starts the deposition of cvd diamond film.The parallel vertical pulling tantalum wire (heated filament) of 6 Φ 6 is had, at a distance of 10 millimeters between tantalum wire and silicon chip above rotatable platform.The deposition process conditions of diamond thin is: carbon source to be volume ratio be 1: 1 acetone and methyl alcohol, be dissolved with ethyl triethoxysilane in carbon source simultaneously, trimethyl borate and urea, wherein Si/C atomic ratio is 2: 100, B/C atomic ratio is 3: 100, N/C atomic ratio is 3: 100, chamber pressure is 4.5KPa, gas always flows heavy 700 ml/min, the volume ratio of acetone/hydrogen is 1 ~ 2: 100, tantalum wire temperature is about 2100 DEG C, after 6 hours depositions, obtaining thickness is 10 microns, conductive diamond film when surface diamond crystal grain is 0.2 ~ 0.4 μm 3.
embodiment 6
Substrate is external diameter Φ 55, internal diameter Φ 42, the silicon carbide sealed ring of thick 8 millimeters, single-sided polishing, polished surface depositing diamond film.The method of surface preparation is identical with the silicon slice processing method in embodiment 1.After process, substrate is placed on the platform of reaction chamber rotation, starts the deposition of cvd diamond film.The parallel vertical pulling tantalum wire (heated filament) of 4 Φ 6 is had, at a distance of 10 millimeters between tantalum wire and silicon carbide sealed ring polished surface above rotatable platform.Containing 80 milliliters, acetone in carbon source, methyl alcohol 20 milliliters, is dissolved with tetraethoxysilane, trimethyl borate and urea simultaneously, and wherein Si/C atomic ratio is 1: 100, B/C atomic ratio is 1: 100, N/C atomic ratio is 0.8: 100, and chamber pressure is 4.5KPa, and gas always flows heavy 700 ml/min, the volume ratio of acetone/hydrogen is 1 ~ 2: 100, tantalum wire temperature is about 2100 DEG C, after 6 hours depositions, obtains the annular diamond thin that thickness is the surface-brightening of 12 microns.The diamond crystals of coatingsurface is about 50 ~ 100 nanometers.Because coatingsurface smooth finish is better, significantly reduce the polishing work amount of diamond coatings, through the mechanical mill polishing of 2 hours, the diamond coatings of wear ring end face can reach minute surface degree, and Ra can reach 0.05 μm.
From the various embodiments described above, in order to reach in diamond coatings the object of mixing silicon, siliceous organic low molecular compounds need be added, as Trisilicopropane, tetrasilane, tetraethoxysilane, dimethyldiethoxysilane, ethyl triethoxysilane etc., the first two structural similarity of planting the silanes of liquid and acetone is poor, mutual solubility is also poor, is not suitable for dissolving carrying in acetone; Several afterwards have certain structural similarity with methyl alcohol, acetone, can be dissolved in the mixed solution of acetone or acetone and methyl alcohol, the evaporation of acetone and methyl alcohol can be utilized will to bring reaction chamber into together with it, in CVD sedimentation products thin diamond membrane structure outside carbon atom, also have impurity atoms silicon, thus the object of mixing silicon can be reached.The diamond coatings only mixing silicon is electric insulation, if also dissolve trimethyl borate similarly in acetone or acetone and methyl alcohol mixed liquor simultaneously, is then both doped with silicon in diamond coatings, and is doped with boron again, makes film coating be electroconductibility.If dissolve siliceous organic low molecular compounds and urea (nitrogenous) in carbon source (acetone or acetone and methyl alcohol mixed liquor) simultaneously, then the crystal grain of diamond film coating layer is just thinner finer and close, can reach the degree of nano-diamond film.If be mixed with silicon, boron or nitrogen three kinds of impurity in carbon source simultaneously, then reaction product is the nano-diamond film coating of conduction.
Claims (2)
1. the method for a preparing diamond film through multiple-doped hot filament chemical vapor deposition, described method comprises after substrate material pre-treatment, be placed in the reaction chamber of hot-wire chemical gas-phase deposition device, at its surface deposition diamond thin, it is characterized in that, the reactant gases passed in described reaction chamber comprises hydrogen and carbon-source gas, and described carbon source is acetone or the mixture for acetone and methyl alcohol, to be taken out of by the steam of carbon source form carbon-source gas and be delivered to reaction chamber by hydrogen by Bubbling method; Described carbon-source gas is doped with the one in following atom combination: Si and N, Si and B, Si and N and B atom; Doping Si atom obtains by mixing silicon compound in carbon source, and described silicon compound is tetraethoxysilane, dimethyldiethoxysilane or ethyl triethoxysilane;
When described carbon-source gas doping Si and atom N, Si/C, N/C atomic ratio is 0.1 ~ 3:100;
Described carbon-source gas doping Si and the B atomic time, the atomic ratio of Si/C, B/C is 0.1 ~ 3:100;
Described 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.
When described carbon-source gas doping Si and atom N, described carbon-source gas obtains for mixing silicon compound and nitrogen compound in carbon source;
Described carbon-source gas doping Si and the B atomic time, described carbon-source gas obtains for mixing silicon compound and boron compound in carbon source;
Described carbon-source gas doping Si and N and B atomic time, described carbon-source gas obtains for mixing silicon compound, nitrogen compound and boron compound in carbon source;
Described silicon compound, nitrogen compound, boron compound and carbon source are dissolved each other.
2. the method for preparing diamond film through multiple-doped hot filament chemical vapor deposition according to claim 1, is characterized in that, described nitrogen compound is urea; Described boron compound is trimethyl borate.
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| TW200538574A (en) * | 2002-11-27 | 2005-12-01 | Toppan Printing Co Ltd | Nanocrystalline diamond film, method for manufacturing the same, and apparatus using the nanocrystalline diamond film |
| CN101476113A (en) * | 2009-01-22 | 2009-07-08 | 上海交通大学 | Method for preparing boron doped conductive diamond thin film by chemical vapor deposition |
| CN101736323A (en) * | 2009-12-21 | 2010-06-16 | 上海交通大学 | Device for preparing boron-doped diamond composite coating on surface of cutter |
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2012
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| US6281037B1 (en) * | 1997-07-14 | 2001-08-28 | Forschungszentrum Rossendorf E.V. | Method for the targeted production of N-type conductive areas in diamond layers by means of ion implantation |
| TW200538574A (en) * | 2002-11-27 | 2005-12-01 | Toppan Printing Co Ltd | Nanocrystalline diamond film, method for manufacturing the same, and apparatus using the nanocrystalline diamond film |
| CN101476113A (en) * | 2009-01-22 | 2009-07-08 | 上海交通大学 | Method for preparing boron doped conductive diamond thin film by chemical vapor deposition |
| CN101736323A (en) * | 2009-12-21 | 2010-06-16 | 上海交通大学 | Device for preparing boron-doped diamond composite coating on surface of cutter |
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| 陶瓷基CVD金刚石薄膜的制备、摩擦试验及其应用研究;杨国栋;《中国优秀硕士论文数据库》;20101031;第21页图2-2 * |
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