CN103938182A - Preparation method of boron-nitrogen co-doped nano-based oriented diamond film - Google Patents
Preparation method of boron-nitrogen co-doped nano-based oriented diamond film Download PDFInfo
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- CN103938182A CN103938182A CN201410138529.XA CN201410138529A CN103938182A CN 103938182 A CN103938182 A CN 103938182A CN 201410138529 A CN201410138529 A CN 201410138529A CN 103938182 A CN103938182 A CN 103938182A
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Abstract
The invention discloses a preparation method of a boron-nitrogen co-doped nano-based an oriented diamond film. The preparation method comprises the following steps: by taking a heater CVD (Chemical Vapor Deposition) device as deposition equipment, adding boron-nitrogen-containing compounds into a conventional hydrogen and acetone reaction system to form a co-doped system; adjusting the reaction technical parameters; preparing the film where diamond particle particles and oriented diamond particles co-exist. The method is simple in process flow. The obtained film has the characteristics that the film has the surface which is leveler than a randomly oriented micron order diamond film, high and uniform wear resistance, easiness in polishing, low internal stress, high adhesive force of the film base and the like.
Description
Technical field
The present invention relates to the preparation method in a kind of thin film technique field, be specifically related to the preparation method that a kind of boron nitrogen is mixed nano based oriented diamond film altogether.
Background technology
Chemical vapour deposition (being called for short CVD method, Chemical Vapor Deposition) diamond film growth pattern be take Volmev-weber island growth as main, makes its structure be generally columnar growth structure.The selection growth theory proposing according to Van der Drift, the formation of film is the result of competitive growth between different crystal different orientation diamond crystals, it is relevant with the growth velocity of crystal face that the crystal of film surface appears face, and the slower crystal face of growing finally can be appeared.Under the condition of chemical vapour deposition conventionally, { growth velocity of 111} face is the slowest, so the diamond thin obtaining great majority are the { diamond thin that 111} face appears.{ diamond that 111} face appears has sharp-pointed corner angle conventionally, and the diamond surface roughness therefore obtaining is larger.Due to columnar growth structure, diamond particles increases along with the increase of film thickness, thereby surfaceness is further significantly increased with the increase of thin diamond film thickness.In the situation that other growth conditions is constant, along with the reduction of reaction pressure, the particle of the diamond thin of generation can obtain refinement gradually, finally develops into particle size and is less than 100nm, there is no the diamond thin of obvious high preferred orientation, i.e. nano-diamond film.Compare with micron order diamond thin, Nano diamond surface smoothness is good, but because its second nucleation is more, competition in process of growth between inner nucleome is comparatively fierce, thereby make its internal stress larger, film base sticking power is poor, and the relatively oarse-grained micron order diamond of its wear resistance is poor.
Through the literature search of prior art is found, Chinese patent 03151295.X " hard alloy matix complex shape cutter diamond coating preparation method " discloses the deposition method of a kind of nanometer and micron composite diamond film, this invention is by first depositing one deck micron order diamond thin, in-situ deposition one deck nano-diamond film on described micron order diamond thin again, although compound coating prepared by this kind of method can obtain smooth diamond film surface and good sticking power, the nano-diamond on top layer reduces coating abrasion performance.Because the sticking power of conventional diamond deposition acquisition is poor, this patent is processed and is improved sticking power by microwave decarburization reduction, has increased treatment facility and step in addition.And in process of growth, want growth regulation technique to realize micron deposition to the transformation of nano-precipitation, make Technology become complicated.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, a kind of preparation method of depositing nano base oriented diamond film is provided.The method depositing operation is simple, and growth velocity is fast.In the process of depositing diamond film, introduce doped source, can reach the object that improves sticking power.Combining nano is with { the 100} bulky diamond thought of growing, can obtain smooth film surface, alleviates growth internal stress, further improves sticking power simultaneously again.And the film that obtains of deposition also has higher surface quality, wear resistance high and homogeneous and the excellent features such as tribological property.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to the preparation method that a kind of boron nitrogen is mixed nano based oriented diamond film altogether, described method comprises: pretreated body material is placed in to heated filament CVD equipment, adopted the nitrogen co-doped depositing operation of boron, under the substrate temperature of the reaction pressure of 0.5kPa～1.5kPa and 850～1000 ℃, deposit, can obtain boron nitrogen and mix altogether nano based oriented diamond film; That is: { 100} face appears the diamond thin that diamond and nano-scale diamond particles coexist.Preferred reaction pressure is 0.8kPa～1.5kPa, and substrate temperature is 870～1000 ℃.
Preferably, the nitrogen co-doped depositing operation of described boron for passing into hydrogen and carbon-source gas as reactant gases in the reaction chamber of described heated filament CVD equipment, described carbon-source gas is doped with B and N atom, and wherein doping ratio is: boron carbon atom number ratio is 0.03%～0.08%; Nitrogen is 0.05%～0.15% with the atom number ratio of carbon.
Preferably, described carbon source is the mixture of acetone or acetone and methyl alcohol.
Preferably, described B atom comes from boron compound, and described N atom comes from nitrogen compound.
Preferably, described boron compound is trimethyl borate.
Preferably, described nitrogen compound is urea.
Principle of work of the present invention is:
Having of nitrogen element is beneficial to that { 100} face is adamantine to be appeared, but its growth conditions scope is conventionally narrower.The doping efficiency of boron in diamond is higher than the doping efficiency of nitrogen, boron active group is easier to realize chemisorption on diamond surface, and the absorption of boracic active group, to further promote the absorption of nitrogenous active group and carbon-containing group, thus boron-containing compound add the effect that also can play the adamantine growth of stable orientation and improve growth velocity.When reaction pressure is on the low side, can make active particle free path in reaction chamber become large, reduced the group collision and restructuring of active group from heated filament to matrix surface course of conveying, reduced the loss of active particle energy, make more high energy active particle constantly bombard matrix surface, cause the second nucleation in a large amount of diamond film processes, promoted the generation of Nano diamond.Thereby under the acting in conjunction of doping and air pressure, oriented diamond and Nano diamond have been generated simultaneously.Nano based oriented film is grown because of oarse-grained diamond and nano-diamond simultaneously, has alleviated growth inside competition, has reduced internal stress, thereby can obtain the higher diamond thin of film base sticking power.In addition, boron can react and generate stable boron cobalt compound with cemented carbide substrate surfaces cobalt element, stop cobalt element diffusion to matrix surface in high temperature deposition process, reduce the graphited impact of urging of cobalt in diamond film process, thereby can further greatly promote the sticking power between hard alloy substrate and diamond.The common growth of nanometer composition and oriented film, is improved crystal face quality, and surface finish is high, have easy polishing, wear-resistant, and the feature such as abradability is consistent on thickness direction.
Compared with prior art, the present invention has following beneficial effect:
1, except heated filament CVD depositing device, without other utility appliance, preparation technology is simple.
2, { 100} oriented diamond particle is compared with { 111} face is that master's random orientation diamond surface defect is few, surface quality is higher, surface smoothness increases and changes not quite with film thickness, and can accomplish the balance of surface smoothness and abrasion resistance properties, top layer diamond and bottom diamond wear proof performance homogeneous.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is the boron nitrogen co-doped nano based oriented diamond film surface topography map of substrate temperature while being 950 ℃;
Fig. 2 is the boron nitrogen co-doped nano based oriented diamond film surface topography map of substrate temperature while being 870 ℃;
Fig. 3 is the nitrogen co-doped nano based oriented diamond film of boron impression figure;
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
By embodiment, the present invention being prepared to film is now compared with the comparative example outside protection domain of the present invention.
First, Wimet (YG6) matrix is carried out to the pre-treatment of soda acid two-step approach, concrete steps are: hard alloy substrate is placed in to Murakami solution and carries out the ultrasonic cleaning of 30 minutes, the tungsten carbide particle in etched the matrix, makes surface coarsening.The composition of Murakami solution is potassium hydroxide (KOH), the Tripotassium iron hexacyanide (K
3fe (CN)
6)) and water (H
2o), its quality proportioning is 1: 1: 10.Subsequently, take out that after matrix washes, to be placed in volume ratio be the vitriol oil (H of 1: 10 again
2sO
4) and hydrogen peroxide (H
2o
2) in mixed acid solution to remove the cobalt element on its top layer, reduce cobalt element and urge graphited impact.
Finally, to be immersed in and in acetone soln, carry out the ultrasonic cleaning of 5 minutes through pretreated inserted tool, to remove the soda acid of matrix surface, participate in material and gaseous impurities, taking-up is placed in the film that heated filament CVD equipment reaction chamber deposits embodiment 1～4 and comparative example 1～9 after drying immediately.The mixed gas that the reactant gases using is hydrogen and acetone, wherein acetone soln utilizes hydrogen partial to use Bubbling method to bring reaction chamber into.Acetone is interior doped with trimethyl borate and urea.Hydrogen and acetone flow that embodiment and comparative example are used are respectively 200 ml/min and 80 ml/min.Hot-wire temperature is 2000～2200 ℃, and depositing time is 6h, and between heated filament and matrix, applying bias current value is 3A.In each embodiment and comparative example, the content of doped element and other deposition parameter are as shown in table 1.
Table 1
During deposition parameter in using protection domain of the present invention, as embodiment 1～4, all can obtain Nano diamond particle and { 100} appears the diamond thin that face diamond particles coexists, i.e. nano based oriented diamond film of the present invention.Fig. 1 is surperficial field emission scanning electron microscope (FESEM) figure of the diamond thin that obtains of embodiment 1 deposition, and through 6 hours depositing base surface depositions, obtaining thickness is the diamond thin of 21 microns, and its growth velocity is about 3.5 micro-ms/h.As can be seen from Figure 1, it is few that film surface manifests defect, and mean sizes is that { 100} face diamond particles, around oarse-grained diamond, round many tiny Nano diamond particles for the square of 6 microns.Other preparation conditions of embodiment 2 are identical with embodiment 1, different is that its substrate temperature is reduced to 870 ℃ from 950 ℃, the surperficial SEM figure (Fig. 2) of the diamond thin preparing from it can find out, film still has nano based oriented diamond film structure, but oriented diamond particle diminishes, its mean size is 1 micron.During deposition parameter outside using the present invention's protection, as shown in comparative example 1～9, all cannot prepare nano based oriented diamond film.Comparative example 1 other preparation conditions are identical with embodiment 1, and comparative example 1 that different is is not used boron compound and nitrogen compound doping, when reaction pressure is during between 0.5～2kPa, all generate nano-diamond film, the appearance of omnidirectional diamond thin.And comparative example 2 difference from Example 1 are that its underlayer temperature is too high, be 1100 ℃, the oriented diamond now obtaining is etched, and surface quality is poor.
The sticking power of the diamond thin that the present invention of use pressing in method qualitative detection prepares, employing equipment is Rockwell Hardness meter, and pressure head is diamond penetrator (angle 120, radius 0.2mm), and its load is 100kgf, keeps approximately 5 seconds load time.Its detected result as shown in Figure 3.As can be seen from Figure 3, diamond thin has only occurred to subside at pressure head loading zone, but does not occur diamond drop-off and also flawless.Demonstrated the sticking power of nano based oriented diamond film excellence.But the film that the diamond thin that comparative example obtains shows in various degree in indentation test comes off and crackle.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (6)
1. the preparation method that boron nitrogen is mixed nano based oriented diamond film altogether, it is characterized in that, described method comprises: pretreated body material is placed in to heated filament CVD equipment, adopted the nitrogen co-doped depositing operation of boron, under the substrate temperature of the reaction pressure of 0.5kPa～1.5kPa and 850～1000 ℃, deposit, can obtain described boron nitrogen and mix altogether nano based oriented diamond film.
2. the preparation method that boron nitrogen according to claim 1 is mixed nano based oriented diamond film altogether, it is characterized in that, the nitrogen co-doped depositing operation of described boron for passing into hydrogen and carbon-source gas as reactant gases in the reaction chamber of described heated filament CVD equipment, described carbon-source gas is doped with B and N atom, and wherein doping ratio is: boron carbon atom number ratio is 0.03%～0.08%; Nitrogen is 0.05%～0.15% with the atom number ratio of carbon.
3. the preparation method that boron nitrogen according to claim 2 is mixed nano based oriented diamond film altogether, is characterized in that, described carbon source is the mixture of acetone or acetone and methyl alcohol.
4. the preparation method that boron nitrogen according to claim 2 is mixed nano based oriented diamond film altogether, is characterized in that, described B atom is obtained by boron compound, and described N atom is obtained by nitrogen compound.
5. the preparation method that boron nitrogen according to claim 4 is mixed nano based oriented diamond film altogether, is characterized in that, described boron compound is trimethyl borate.
6. the preparation method that boron nitrogen according to claim 4 is mixed nano based oriented diamond film altogether, is characterized in that, described nitrogen compound is urea.
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Cited By (5)
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| CN105688971A (en) * | 2016-02-29 | 2016-06-22 | 大连理工大学 | Electrochemical reduction CO2 catalyst based on boron and nitrogen co-doped nano-diamond and preparation method and application of catalyst |
| CN108110267A (en) * | 2017-12-28 | 2018-06-01 | 成都新柯力化工科技有限公司 | The Nano diamond base non-platinum catalyst and preparation method of a kind of fuel cell |
| CN110277251A (en) * | 2018-03-15 | 2019-09-24 | 深圳先进技术研究院 | A kind of supercapacitor and preparation method thereof |
| CN113777142A (en) * | 2021-09-15 | 2021-12-10 | 湖南新锋科技有限公司 | Carbon material/metal modified doped diamond particle integrated sensor and preparation method and application thereof |
| CN113913781A (en) * | 2021-10-11 | 2022-01-11 | 久钻科技(成都)有限公司 | Diamond film processing method and device |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688971A (en) * | 2016-02-29 | 2016-06-22 | 大连理工大学 | Electrochemical reduction CO2 catalyst based on boron and nitrogen co-doped nano-diamond and preparation method and application of catalyst |
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| CN108110267A (en) * | 2017-12-28 | 2018-06-01 | 成都新柯力化工科技有限公司 | The Nano diamond base non-platinum catalyst and preparation method of a kind of fuel cell |
| CN108110267B (en) * | 2017-12-28 | 2020-04-10 | 成都新柯力化工科技有限公司 | Nano-diamond-based non-platinum catalyst of fuel cell and preparation method thereof |
| CN110277251A (en) * | 2018-03-15 | 2019-09-24 | 深圳先进技术研究院 | A kind of supercapacitor and preparation method thereof |
| CN113777142A (en) * | 2021-09-15 | 2021-12-10 | 湖南新锋科技有限公司 | Carbon material/metal modified doped diamond particle integrated sensor and preparation method and application thereof |
| CN113913781A (en) * | 2021-10-11 | 2022-01-11 | 久钻科技(成都)有限公司 | Diamond film processing method and device |
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