CN1482275A - Method for preparing diamond/carbon or nitride nano mix phase gradient composite material - Google Patents
Method for preparing diamond/carbon or nitride nano mix phase gradient composite material Download PDFInfo
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- CN1482275A CN1482275A CNA021328854A CN02132885A CN1482275A CN 1482275 A CN1482275 A CN 1482275A CN A021328854 A CNA021328854 A CN A021328854A CN 02132885 A CN02132885 A CN 02132885A CN 1482275 A CN1482275 A CN 1482275A
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Abstract
The preparation process of nano mixed phase gradient composite diamond/carbide or diamond/nitride film features that H2 and multiple-phase organic or inorganic gas mixture capable of forming carbide XC or nitride XN used as materials in the ratio of H: C(N): X equal to 1 to 0.005-0.1 to 0.005-0.02, with X being Si or Ti, are produced into the nano mixed phase gradient composite diamond/carbide or diamond/nitride film via chemical vapor deposit process. The present invention can solve the problem of binding diamond film and metal substrate effectively to makes it possible for diamond film to be applied in industry.
Description
Technical field:
The present invention relates to diamond and cross membrane technique, the method and the industrial application thereof of a kind of chemical vapor deposition (CVD) growing diamond/carbide or nitride nano mix phase gradient composite material is provided especially.
Background technology:
In recent years, diamond thin receives much concern in the application of industrial sector, but owing to there are some still unresolved problems, these application are restricted always.Diamond thin is owing to having different thermal expansivity with many body materials, so cohesive strength is relatively poor.On the other hand, for some metallic matrixes, as base steel, cobalt-based and nickel-base material because these metallic elements easily have an effect with reactant such as methane, formation graphite phase, thus diamond thin be difficult on these matrixes sedimentary.
A kind ofly may be, prepare a kind of diamond and second mutually material of containing,, thereby improve bonding strength with the toughness that improves film not only as matrix but also as key coat as transition layer.Perhaps,, avoid contact reacts therebetween to isolate diamond and matrix as the blocking layer.This effort has obtained some effects.Yet the growth for Thin Film complex process needs a plurality of processes usually.
The technology contents of invention:
The object of the present invention is to provide the preparation method of a kind of diamond/carbon or nitride nano mix phase gradient composite material, this film can solve the problem that combines between diamond thin and metallic matrix effectively, thereby makes the application of diamond thin in industry become possibility.
The invention provides the preparation method of a kind of diamond/carbon or nitride nano mix phase gradient composite material, it is characterized in that: with H
2, contain the organic gas that can form carbide XC or nitride XN or the heterogeneous mixed gas of inorganic gas is a raw material, H: C (N): X=1: 0.005～0.1: 0.005～0.02 wherein, X is selected from silicon or titanium, adopts chemical vapor deposition processes to prepare diamond/carbon thing nano mix phase gradient composite material.
In preparation method's deposition process of diamond/carbon of the present invention or nitride nano mix phase gradient composite material, can form diamond/carbon thing or nitride nano mixed phase laminated film by regulating the chemical composition of multi-phase gas along the depth direction graded.
Among the preparation method of diamond/carbon of the present invention or nitride nano mix phase gradient composite material, can adopt microwave plasma to strengthen chemical vapour deposition MWCVD or heated filament enhancing chemical vapour deposition HFCVD, when adopting microwave plasma to strengthen chemical vapour deposition MWCVD, 100 watts-100 kilowatts of microwave powers.When adopting heated filament to strengthen chemical vapour deposition HFCVD, hot-wire temperature 1500-2800 degree.
Among the preparation method of diamond/carbon of the present invention or nitride nano mix phase gradient composite material, diamond/carbon thing nano mix phase gradient composite material wherein is that its biphase grain fineness number is in nanometer scale by the polycrystal membrane of diamond and β-SiC two phase composites.The processing parameter of its preparation method is:
H
2The 95%-99.8% atomic percent
CH
4The 0.2%-5% atomic percent
X 0%-5% atomic percent
Temperature 400-1000 ℃
Pressure 5-100 millibar.
Among the preparation method of diamond/carbon of the present invention or nitride nano mix phase gradient composite material, the visual application requiring of the thickness of nano mix phase gradient composite material and realizing by the control growing time.
The preparation method of diamond/carbon thing nano mix phase gradient composite material of the present invention is applied to the cutter plated film, diamond conductive film electrode and transition layer thereof etc.
The growth mechanism of diamond/carbon of the present invention or nitride nano mix phase gradient composite material is the selective deposition of gasiform X and C or N atom on diamond and carbide or nitride surface, promptly only deposits the C atom and only deposits the X atom at carbon or nitride surface at diamond surface.Therefore can form the laminated film that inlay diamond and carbide inside mutually, pass through adjusting simultaneously, can obtain the composite membrane of the composition of diamond and carbide with graded to technology in the deposition process.
As everyone knows, for diamond thin, when finishing thin film deposition, when reducing to room temperature, big thermal expansivity deviation will cause a very large THERMAL STRESS IN THIN FILMS between diamond and the matrix from depositing temperature (500 to 900 degree) with matrix.For different body materials and temperature, according to Theoretical Calculation, this stress can reach 10GPa.This will cause film to be peeled off from matrix.This problem can only obtain by the way of using transition layer.Core content of the present invention adopts chemical vapor deposition method depositing diamond/carbide nanometer mix phase gradient composite material exactly, because diamond and carbide inside tessellation mutually, owing to the good bonding strength of carbide, make that diamond/carbon thing nano mix phase gradient composite material is buffer layer material very likely technically simultaneously with metal base.This can reduce film interface thermal stresses peak value on the one hand, improves the film bonding strength, can increase the hardness of film by the crystal grain nanometer on the other hand, and can play diffusion barrier layer.
Use finite element method the cutter corner angle stress distribution of plated film has been carried out analog calculation, and to two kinds of membrane systems, promptly diamond/carbon titanium/steel and diamond/mix phase gradient composite material/steel compares.Diamond/carbon titanium/steel membrane system in showing at the interface of diamond and titanium carbide a high thermal stresses peak, and the thermal stress distribution of diamond/mix phase gradient composite material/steel membrane system is in whole transition layer, this makes the thermal stresses peak reduce by 80%.
Description of drawings:
Fig. 1 strengthens the chemical vapor deposition unit synoptic diagram for microwave plasma;
Fig. 2 be diamond-silicon carbide mixed phase nano compound film the SEM pattern;
Fig. 3 is that the EDX of diamond-β-SiC gradient composite scans the analysis of components result;
Fig. 4 is the SEM transverse section pattern picture of gradient film-pure diamond film.
Embodiment:
Adopt microwave plasma to strengthen chemical vapor deposition method, at first developed diamond/carbon silicon mixed phase nano compound film.The unit type of using is ASTEX 1.5 kW, and operating power is 800W.Fig. 1 has provided the synoptic diagram of this equipment.The reactant gases that uses is a hydrogen, the mixed gas of methane and tetramethylsilane (TMS).The deposition matrix is a silicon single-crystal.Other processing parameter is identical with the depositing pure gold diamond thin film.Before depositing diamond/β-SiC composite material film, matrix immerses to fill in the diamond nano particulate slurries and has carried out ultrasonic pretreatment.Total gas flow rate is 100-1000sccm, and operating pressure is 10-100mbar.Matrix places on the graphite sample platform, is heated by induction.Temperature is measured by heat radiation pyrometer.Film thickness is the 1-20 micron.
Embodiment 1
Mode of deposition is 0.7% methane and 0.007%TMS, and matrix is a silicon.Obviously, film is by two phase composites.A phase that is black is arranged between diamond crystals.X-ray diffraction and IR absorption spectrum analysis revealed Here it is a cube SiC.The crystal grain of diamond and SiC phase is very little, has only about 10 nanometers.Fig. 2 provided film the SEM pattern.
Embodiment 2
Mode of deposition is that 0～1vol% methane is regulated, and 0.007%TMS, matrix are silicon.Fig. 4 is the SEM transverse section pattern picture that gradient film adds the pure diamond film, can more clearly see the distribution of β-SiC phase.
As can be seen, the growth mechanism of diamond/carbon silicon mixed phase nano compound film is the selective deposition of gasiform Si and C atom on diamond and silicon carbide, promptly only deposits the C atom and only deposits the Si atom at silicon carbide at diamond surface.The growth for Thin Film precondition comprises (1) diamond island growth, (2) β-SiC phase nucleation and growth, and (3) adopt different Si, the gas of C content according to different matrixes (Si, WC, SiC and diamond).If H, C concentration is not enough to growing diamond, and then β-SiC growth is preferential.Along with H, C concentration increases the corresponding increase of (in the 0-1vol% scope) growth of diamond probability.To certain concentration value, growth of diamond will be preferential.In this case, the Si atom is adsorbed by diamond surface, has no chance to transfer to adjacent β-SiC island.As Si, WC and β-SiC surface is because diamond is difficult to nucleation, so can not deposit on a lot of non-diamonds surface.β-SiC will be first-selected.
Embodiment 3
Mode of deposition 0.7% methane, 0～0.007%TMS regulates, and the EDX that Fig. 3 has provided diamond-β-SiC gradient composite scans the analysis of components result.
The result shows, the molar content of diamond and β-SiC is to TMS content dependence in the gas phase in laminated film, increase along with the TMS flow, adamantine molar content is reduced to 0% continuously from 100% in the laminated film, and the composition of film becomes almost pure β-SiC film from the pure diamond film in other words.This shows that it is feasible preparing gradient film by TMS gas flow in the change thin film growth process.
Embodiment 4
Mode of deposition is 0.7% methane and 0.007%TMS, and matrix is a silicon, and substrate bias 0-300 lies prostrate variation.Tissue obviously becomes the gradient alligatoring.
Claims (8)
1, the preparation method of a kind of diamond/carbon or nitride nano mix phase gradient composite material is characterized in that: with H
2, contain the organic gas that can form carbide XC or nitride XN or the heterogeneous mixed gas of inorganic gas is a raw material, H: C (N): X=1: 0.005～0.1: 0.005～0.02 wherein, X is selected from silicon or titanium, adopts chemical vapor deposition processes to prepare diamond/carbon thing nano mix phase gradient composite material.
2, according to the preparation method of described diamond/carbon of claim 1 or nitride nano mix phase gradient composite material, it is characterized in that: in deposition process, by regulating the chemical composition of multi-phase gas, form the laminated film that diamond/carbon thing or nitride nano mixed phase change along concentration gradient.
3, according to the preparation method of described diamond/carbon of claim 1 or nitride nano mix phase gradient composite material, it is characterized in that: when adopting microwave plasma to strengthen chemical vapour deposition MWCVD, 100 watts-100 kilowatts of microwave powers.
4, according to the preparation method of described diamond/carbon of claim 1 or nitride nano mix phase gradient composite material, it is characterized in that: when adopting heated filament to strengthen chemical vapour deposition HFCVD, hot-wire temperature 1500-2800 degree.
5, according to the preparation method of described diamond/carbon of claim 2 or nitride nano mix phase gradient composite material, it is characterized in that: described diamond/carbon thing nano mix phase gradient composite material is that its biphase grain fineness number is in nanometer scale by the polycrystal membrane of diamond and β-SiC two phase composites.
6,, it is characterized in that processing parameter is according to the preparation method of described diamond/carbon of claim 5 or nitride nano mix phase gradient composite material:
H
2The 95%-99.8% atomic percent
CH
4The 0.2%-5% atomic percent
X 0%-5% atomic percent
Temperature 400-1000 ℃
Pressure 5-100 millibar.
7,, it is characterized in that the visual application requiring of thickness of described nano mix phase gradient composite material and realize by the control growing time according to the preparation method of described diamond/carbon of claim 1 or nitride nano mix phase gradient composite material.
8, the preparation method of the described diamond/carbon thing of claim 5 nano mix phase gradient composite material is applied to the cutter plated film, diamond conductive film electrode and transition layer thereof etc.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434353C (en) * | 2006-01-24 | 2008-11-19 | 南京大学 | Gas phase synthesis process of nanometer particle array with one-dimensional diameter and number density gradient |
| CN101899713A (en) * | 2009-05-31 | 2010-12-01 | 北京清大微纳科技有限公司 | Polycrystalline superhard material with gradient nano-micro structure and synthesis method thereof |
| CN101899661A (en) * | 2009-05-27 | 2010-12-01 | 通用汽车环球科技运作公司 | High hardness nanocomposite coatings on the Wimet |
| CN101671808B (en) * | 2009-10-16 | 2011-06-01 | 江苏大学 | Method for preparing ultralow elasticity modulus high-wearing feature shell microstructural membrane on surface of titanium |
| CN104178745A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院金属研究所 | Method for manufacturing porous diamond or porous cubic silicon carbide self-supporting film |
| CN105039928A (en) * | 2015-06-17 | 2015-11-11 | 姜辛 | Preparation method of diamond/silicon carbide three-dimensional composite structure and prepared product |
| CN106835064A (en) * | 2016-12-16 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of instrument with diamond/silicon carbide composite coating and preparation method thereof |
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2002
- 2002-09-09 CN CN 02132885 patent/CN1219911C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434353C (en) * | 2006-01-24 | 2008-11-19 | 南京大学 | Gas phase synthesis process of nanometer particle array with one-dimensional diameter and number density gradient |
| CN101899661A (en) * | 2009-05-27 | 2010-12-01 | 通用汽车环球科技运作公司 | High hardness nanocomposite coatings on the Wimet |
| US8383200B2 (en) | 2009-05-27 | 2013-02-26 | GM Global Technology Operations LLC | High hardness nanocomposite coatings on cemented carbide |
| CN101899661B (en) * | 2009-05-27 | 2013-09-25 | 通用汽车环球科技运作公司 | High hardness nanocomposite coatings on cemented carbide |
| CN101899713B (en) * | 2009-05-31 | 2014-09-24 | 北京清大微纳科技有限公司 | Polycrystalline superhard material with gradient nano-micro structure and synthesis method thereof |
| CN101899713A (en) * | 2009-05-31 | 2010-12-01 | 北京清大微纳科技有限公司 | Polycrystalline superhard material with gradient nano-micro structure and synthesis method thereof |
| CN101671808B (en) * | 2009-10-16 | 2011-06-01 | 江苏大学 | Method for preparing ultralow elasticity modulus high-wearing feature shell microstructural membrane on surface of titanium |
| CN104178745A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院金属研究所 | Method for manufacturing porous diamond or porous cubic silicon carbide self-supporting film |
| CN104178745B (en) * | 2013-05-28 | 2016-07-27 | 中国科学院金属研究所 | A kind of porous diamond or the preparation method of porous cubic silicon carbide self-supported membrane |
| CN105039928A (en) * | 2015-06-17 | 2015-11-11 | 姜辛 | Preparation method of diamond/silicon carbide three-dimensional composite structure and prepared product |
| CN105039928B (en) * | 2015-06-17 | 2017-06-30 | 姜辛 | A kind of preparation method of diamond/silicon carbide three dimensional composite structure and its product of preparation |
| CN106835064A (en) * | 2016-12-16 | 2017-06-13 | 中国科学院深圳先进技术研究院 | A kind of instrument with diamond/silicon carbide composite coating and preparation method thereof |
| CN106835064B (en) * | 2016-12-16 | 2019-06-25 | 中国科学院深圳先进技术研究院 | A kind of tool and preparation method thereof with diamond/silicon carbide composite coating |
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| CN1219911C (en) | 2005-09-21 |
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