CN103938182B - Boron nitrogen is mixed the preparation method of nano based oriented diamond film altogether - Google Patents
Boron nitrogen is mixed the preparation method of nano based oriented diamond film altogether Download PDFInfo
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- CN103938182B CN103938182B CN201410138529.XA CN201410138529A CN103938182B CN 103938182 B CN103938182 B CN 103938182B CN 201410138529 A CN201410138529 A CN 201410138529A CN 103938182 B CN103938182 B CN 103938182B
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Abstract
The invention discloses the preparation method that a kind of boron nitrogen is mixed nano based oriented diamond film altogether; Taking heated filament CVD device as depositing device, in traditional hydrogen and acetone reaction system, add middle boracic and nitrogen-containing compound, form codope system, regulate reaction process parameter, prepare the film that Nano diamond particle and oriented diamond particle coexist. The method technological process is simple, and the film of acquisition has than random orientation micron order diamond thin even curface, the high and homogeneous of mar proof, the low and film base adhesive force high of easily polishing, internal stress.
Description
Technical field
The present invention relates to the preparation method in a kind of thin film technique field, be specifically related to a kind of boron nitrogen and mix altogether the directed Buddha's warrior attendant of nano basedThe preparation method of stone film.
Background technology
Chemical vapour deposition (CVD) (be called for short CVD method, ChemicalVaporDeposition) diamond film growth pattern withVolmev-weber island growth is main, makes its structure be generally columnar growth structure. Propose according to VanderDriftSelect growth theory, the formation of film is the result of competitive growth between different crystal different orientation diamond crystals, film tableIt is relevant with the growth rate of crystal face that the crystal of face appears face, and the slower crystal face of growing finally can be appeared. At common chemistryUnder the condition of vapour deposition, { growth rate of 111} face is the slowest, so the diamond thin obtaining great majority are { 111} faceThe diamond thin appearing. { diamond that 111} face appears has sharp-pointed corner angle conventionally, the diamond table therefore obtainingSurface roughness is larger. Due to columnar growth structure, diamond particles increases along with the increase of film thickness, fromAnd surface roughness is further significantly increased with the increase of thin diamond film thickness. Constant at other growth conditionsIn situation, along with the reduction of reaction pressure, the particle of the diamond thin of generation can obtain refinement gradually, finally develops intoParticle size is less than 100nm, there is no the diamond thin of obvious high preferred orientation, i.e. nano-diamond film. With micron orderDiamond thin is compared, and Nano diamond surface smoothness is good, but because its second nucleation is more, inner in growth courseCompetition between nucleome is comparatively fierce, thereby makes its internal stress larger, and film base adhesive force is poor, and its wearability phasePoor concerning oarse-grained micron order diamond.
Through the literature search of prior art is found, Chinese patent 03151295.X " hard alloy substrate complicated shape cutterTool diamond coatings preparation method " disclose a kind of nanometer with micron composite diamond film deposition process, this invention isBy first depositing one deck micron order diamond thin, then on described micron order diamond thin in-situ deposition one deck nanometerGrade diamond film, although composite coating prepared by this kind of method can obtain smooth diamond film surface and goodAdhesive force, but the nano-diamond on top layer reduces coating abrasion performance. In addition because conventional diamond deposition obtainsAdhesive force is poor, and this patent is processed and improved adhesive force by microwave decarburization reduction, has increased treatment facility and step. AndAnd in growth course, want growth regulation technique to realize the transformation of micron deposition to nano-precipitation, make technology become multipleAssorted.
Summary of the invention
The object of the invention is to overcome the deficiency that above-mentioned prior art exists, a kind of depositing nano base oriented diamond is providedThe preparation method of film. The method depositing operation is simple, and growth rate is fast. In the process of depositing diamond film, introduceDoped source, can reach the object that improves adhesive force. Again combining nano with the 100} bulky diamond thought of simultaneously growing,Can obtain smooth film surface, alleviate growth internal stress, further improve adhesive force. And deposition obtain thinFilm also has higher surface quality, the features such as the high and homogeneous of wearability and excellent 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: will be pre-The matrix material of processing is placed in heated filament CVD equipment, has adopted the nitrogen co-doped depositing operation of boron, in 0.5kPa～1.5Under the substrate temperature of the reaction pressure of kPa and 850～1000 DEG C, deposit, can obtain boron nitrogen and mix altogether the directed gold of nano basedDiamond thin film; That is: { 100} face appears the diamond thin that diamond and nano-scale diamond particles coexist. More preferablyReaction pressure be 0.8kPa～1.5kPa, substrate temperature is 870～1000 DEG C.
Preferably, the nitrogen co-doped depositing operation of described boron is to pass into hydrogen in the reative cell of described heated filament CVD equipmentAnd carbon-source gas is as reacting gas, 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 trimethylborate.
Preferably, described nitrogen compound is urea.
Operation principle 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. Boron elementDoping efficiency in diamond is higher than the doping efficiency of nitrogen, and boron active group is easier to realize chemistry on diamond surfaceAbsorption, and the absorption of boracic active group will further promote the absorption of nitrogenous active group and carbon-containing group, thereby containThe effect that also can play the adding of boron compound the adamantine growth of stable orientation and improve growth rate. Work as reaction pressureTime on the low side, can make active particle free path in reative cell become large, reduce active group and carried to matrix surface from heated filamentGroup collision and restructuring in journey, reduced the loss of active particle energy, makes more high energy active particle continuousBombardment matrix surface, causes the second nucleation in a large amount of diamond film processes, has promoted the generation of Nano diamond. CauseAnd under the acting in conjunction of doping and air pressure, generated oriented diamond and Nano diamond simultaneously. Nano based oriented film because ofOarse-grained diamond and nano-diamond are grown simultaneously, have alleviated growth inside competition, have reduced internal stress, therebyCan obtain the higher diamond thin of film base adhesive force. In addition, boron element can occur anti-with cemented carbide substrate surfaces cobalt elementShould generate stable boron cobalt compound, prevention cobalt element to the diffusion of matrix surface, reduces Buddha's warrior attendant in high temperature deposition processIn stone growth course cobalt urge graphited impact, thereby can further greatly promote between hard alloy substrate and diamondAdhesive force. The common growth of nanometer composition and oriented film, is improved crystal face quality, surface smoothness is high,There is easy polishing, wear-resistant, and the feature such as abrasiveness 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 auxiliary equipment, 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 qualityHigher, surface smoothness increases and changes not quite with film thickness, and can accomplish the flat of surface smoothness and abrasion resistance propertiesWeighing apparatus, top layer diamond and bottom diamond wear proof performance homogeneous.
Brief description of the drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, other spy of the present inventionLevy, object and advantage will become more obvious:
Fig. 1 is the boron nitrogen co-doped nano based oriented diamond film surface topography map of substrate temperature while being 950 DEG C;
Fig. 2 is the boron nitrogen co-doped nano based oriented diamond film surface topography map of substrate temperature while being 870 DEG C;
Fig. 3 is the nitrogen co-doped nano based oriented diamond film of boron impression figure;
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail. Following examples will contribute to the technology people of this areaMember further understands the present invention, but does not limit in any form the present invention. It should be pointed out that the common skill to this areaArt personnel, without departing from the inventive concept of the premise, can also make some distortion and improvement. These all belong toProtection 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, carbide alloy (YG6) matrix is carried out to the pretreatment of soda acid two-step method, concrete steps are: by carbide alloyMatrix is placed in Murakami solution and carries out the ultrasonic cleaning of 30 minutes, and the tungsten carbide particle in etched the matrix, makes surfaceAlligatoring. The composition of Murakami solution is potassium hydroxide (KOH), the potassium ferricyanide (K3Fe(CN)6)) and water (H2O)，Its quality proportioning is 1: 1: 10. Subsequently, taking out matrix, to be placed in volume ratio after washing be the concentrated sulfuric acid (H of 1: 10 again2SO4)And hydrogen peroxide (H2O2) in mixed acid solution to remove the cobalt element on its top layer, reduce cobalt element and urge graphited impact.
Finally, will be immersed in the ultrasonic cleaning of carrying out in acetone soln 5 minutes through pretreated hard alloy cutter, withThe soda acid of removing matrix surface participates in material and gaseous impurity, and taking-up is placed in heated filament CVD equipment reaction after drying immediatelyIn chamber, deposit the film of embodiment 1～4 and comparative example 1～9. The mist that the reacting gas using is hydrogen and acetone,Wherein acetone soln utilizes hydrogen partial to use Bubbling method to bring reative cell into. Acetone is interior doped with trimethylborate and urineElement. Hydrogen and acetone flow that embodiment and comparative example are used are respectively 200 ml/min and 80 ml/min. Hot-wire temperatureBe 2000～2200 DEG C, sedimentation time is 6h, and between heated filament and matrix, applying bias current value is 3A. Each embodiment andIn comparative example, the content of doped chemical and other deposition parameter are as shown in table 1.
Table 1
When use in protection domain of the present invention deposition parameter time, as embodiment 1～4, all can obtain Nano diamond particleWith { 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 that embodiment 1 deposits the diamond thin obtaining, through 6It is the diamond thin of 21 microns that hour depositing base surface deposition obtains thickness, its growth rate be about 3.5 microns/littleTime. As can be seen from Figure 1, it is few that film surface manifests defect, and average-size is square { the 100} face gold of 6 micronsHard rock particle, around oarse-grained diamond, round many tiny Nano diamond particles. Its of embodiment 2His preparation condition is identical with embodiment 1, and different is its substrate temperature is reduced to 870 DEG C from 950 DEG C, is prepared into from itTo the surperficial SEM figure (Fig. 2) of diamond thin can find out, film still has nano based oriented diamond filmStructure, but oriented diamond particle diminishes, and its mean size is 1 micron. When the deposition parameter using outside the present invention's protectionTime, as shown in comparative example 1～9, all cannot prepare nano based oriented diamond film. Comparative example 1 other preparation conditionsIdentical with embodiment 1, comparative example 1 that different is is not used boron compound and nitrogen compound doping, when reaction pressure betweenWhen 0.5～2kPa, all generate nano-diamond film, the appearance of omnidirectional diamond thin. And comparative example 2 and enforcementExample 1 difference is that its underlayer temperature is too high, is 1100 DEG C, and the oriented diamond now obtaining is etched, surfaceSecond-rate.
The adhesive force of the diamond thin that the present invention of use indentation method qualitative detection prepares, employing equipment is Rockwell HardnessMeter, pressure head is diamond penetrator (angle 120, radius 0.2mm), its load is 100kgf, keeps the load time approximately5 seconds. Its testing result as shown in Figure 3. As can be seen from Figure 3, diamond thin has only occurred at pressure head loading zoneSubside, but do not occur diamond drop-off and also flawless. Demonstrate nano based oriented diamond film excellenceAdhesive force. 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 toState specific implementations, those skilled in the art can make various distortion or amendment within the scope of the claims,This does not affect flesh and blood of the present invention.
Claims (5)
1. boron nitrogen is mixed a preparation method for nano based oriented diamond film altogether, it is characterized in that, described method comprises:Pretreated matrix material is placed in to heated filament CVD equipment, has adopted the nitrogen co-doped depositing operation of boron, 0.5kPa～Under the substrate temperature of the reaction pressure of 1.5kPa and 850～1000 DEG C, deposit, can obtain described boron nitrogen and mix altogether nano basedOriented diamond film; Described boron nitrogen mix nano based oriented diamond film altogether: { 100} face appears diamond and nanometerThe diamond thin that size diamond particles coexists;
The nitrogen co-doped depositing operation of described boron is to pass into hydrogen and carbon source in the reative cell of described heated filament CVD equipmentGas is as reacting gas, and described carbon-source gas is doped with B and N atom, and wherein doping ratio is: boron carbon atomNumber ratio is 0.03%～0.08%; Nitrogen is 0.05%～0.15% with the atom number ratio of carbon.
2. the preparation method that boron nitrogen according to claim 1 is mixed nano based oriented diamond film altogether, its feature existsIn, described carbon source is the mixture of acetone or acetone and methyl alcohol.
3. the preparation method that boron nitrogen according to claim 1 is mixed nano based oriented diamond film altogether, its feature existsIn, described B atom is obtained by boron compound, and described N atom is obtained by nitrogen compound.
4. the preparation method that boron nitrogen according to claim 3 is mixed nano based oriented diamond film altogether, its feature existsIn, described boron compound is trimethylborate.
5. the preparation method that boron nitrogen according to claim 3 is mixed nano based oriented diamond film altogether, its feature existsIn, described nitrogen compound is urea.
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| CN105688971B (en) * | 2016-02-29 | 2018-04-10 | 大连理工大学 | A kind of electrochemical reduction CO based on the nitrogen co-doped Nano diamond of boron2Catalyst, preparation method and applications |
| 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 |
| CN113777142B (en) * | 2021-09-15 | 2024-10-01 | 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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| CN102586762A (en) * | 2012-03-27 | 2012-07-18 | 上海交通大学 | Method for preparing diamond film through multiple-doped hot filament chemical vapor deposition |
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| JP4784915B2 (en) * | 2005-02-03 | 2011-10-05 | 独立行政法人産業技術総合研究所 | N-type (100) oriented diamond semiconductor single crystal film doped with phosphorus atoms and method for producing the same |
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| CN102586762A (en) * | 2012-03-27 | 2012-07-18 | 上海交通大学 | Method for preparing diamond film through multiple-doped hot filament chemical vapor deposition |
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