CN104164659A - Preparation method of seed crystal-free fine monocrystal diamond micro-powder - Google Patents
Preparation method of seed crystal-free fine monocrystal diamond micro-powder Download PDFInfo
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- CN104164659A CN104164659A CN201410390626.8A CN201410390626A CN104164659A CN 104164659 A CN104164659 A CN 104164659A CN 201410390626 A CN201410390626 A CN 201410390626A CN 104164659 A CN104164659 A CN 104164659A
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Abstract
The invention discloses a preparation method for seed crystal-free fine monocrystal diamond micro-powder. The preparation method comprises the following steps of: uniformly and independently dispersing nuclear bodies on a silicon-based substrate by adopting a matrix self-nucleation substrate pre-treatment method; depositing the pre-treated silicon-based substrate by using a hot filament chemical vapour deposition method which comprise two phases, namely diamond nucleation and diamond grain growth, so as to obtain diamond monocrystal grains with regular crystalline forms; and treating the obtained diamond monocrystal grains by combining the process of chemical corrosion to the silicon-based substrate and a high-speed grain centrifugal sedimentation process so as to obtain the fine monocrystal diamond micro-powder. The proportion of crystals of high-grade hexahedral to octahedral poly-crystal shapes or icosahedral poly-crystal shape in the fine monocrystal diamond micro-powder obtained by the preparation method disclosed by the invention is high; the fine micro-powder obtained by the method is preponderant in terms of crystalline form and surface quality; and moreover, the process flow is simple, the obtained micro-powder has intensive size distribution, and a granularity screening process for the micro-powder can be omitted.
Description
Technical field
The present invention relates to diamond fabrication technical field, relate in particular to a kind of preparation method without the meticulous diamond single crystal micro mist of crystal seed.
Background technology
Diadust is often referred to the diamond particles of granularity between 0.1 μ m～54 μ m, and what be less than 5 μ m is called again fine powder.Diadust is mainly used in the ultraprecise polishing processing of workpiece surface---in grinding and polishing process.Along with the development of electronic technology, needs to accurate device polishings such as all kinds of Opto-Electronics Crystals, computer hard disc substrate, optical component and semiconductor integrated circuit silicon chips are increasing, in order to meet the processing request of these accurate devices, more and more to the demand of the trickle powder of diamond, also the crystalline form to diadust, homogeneity and mechanical property are had higher requirement simultaneously, to reach high-level efficiency, high-precision grinding and polishing requirement.Therefore, the growth technique of research high-quality high grade diamond micro mist, the synthetic technology level that improves diadust has become the focus that Synthetic Diamond Industry is paid close attention to.
Utilize the granularity of particles diamonds prepared by static pressure method to be generally greater than 38 μ m, because the diamond nucleation rate of this method is low and growth velocity is too fast, cause fine grain diamond to be difficult to form, the synthetic diamond micropowder overwhelming majority (more than 90%) is to adopt mechanical crushing method to process at present, and also having abroad a small amount of diadust is to adopt explosion method to produce.Comminuting method refers to taking two sides top, the coarsness diamond of cubic apparatus static high pressure high temperature service manufacture is as raw material, be processed into through operations such as ball mill crushing, pulverizing the diadust that granularity is 0.5～54 μ m, its globule size can be controlled by disintegrating process.But the preparation technology of mechanical crushing method is extremely loaded down with trivial details, purification and granularity sieving work are consuming time longer, and production efficiency is subject to serious restriction.What is more important, this method obtains monocrystalline form and depends primarily on broken disintegrating process, therefore particle crystalline form is poor, crystal face is imperfect, corner angle are sharp-pointed, and pin, platy shaped particle are also difficult to eliminate, above-mentioned these shortcomings all directly affect the surface quality of work piece, are especially difficult to meet the polishing requirement of sophisticated product.Dynamic high-pressure method (claiming again explosion method) is prepared diadust and is referred to that the intense impact ripple that utilizes the blast of the powerful explosive such as TNT (trotyl) and RDX (hexogen) to produce afterwards acts on graphite, obtain the high temperature of a hundreds of thousands of normal atmosphere and several thousand degree in the moment of several microseconds, make graphite change diamond into, its synthetic granularity generally can be controlled between 0.01～50 μ m.The synthetic micro mist of explosion method is polycrystal structure, although there is no the sharp corners of comminuting method single crystal particle, but grade purity is lower, the specific surface area of polycrystalline particle is than the large 3 times of left and right of one-size single crystal particle, impurity is more easily adsorbed on its surface, and the diamond grit difference of formation is also larger, thus the recycling of micro mist and purification sorting more difficult, and the adamantine transformation efficiency of explosion method is extremely low, and production efficiency is restricted.
At the beginning of the eighties in last century, people's reported first such as Japanese scholars Setaka, Matsumoto adopt chemical vapour deposition (English Chemical Vapor Deposition, CVD) method to grow diamond film on dissimilar materials surface under low pressure condition.Subsequently, worldwide start the research boom of diamond film, through the effort of nearly 30 years, diamond film deposition technique obtained rapid progress.Since CVD Diamond Synthesizing Technology occurs, research field attempts to utilize technique always, the single-crystal diamond of synthetic high grade high-quality crystalline form, and obtained many achievements.With high temperature and high pressure method (English high temperature-ultra high pressure process, be abbreviated as HPHT) method compares, the standby diamond of CVD legal system has following significant advantage: 1. the standby diamond purity of CVD legal system is high, and impurity and defect are few.In CVD method, as long as use high-pure gas, the high purity diamond of just growing in principle.2. the diamond that prepared by CVD is good.The single-crystal diamond of CVD growth has complete crystalline form and smooth idiomorphism face conventionally, can synthesize cube single crystal structure that crystal face is clear, crystalline form is outstanding.3. CVD equipment relatively simple, consume energy low, synthesis technique simple and be easy to control, running cost is low.Although the synthetic method of CVD diamond is a lot, but except traditional hot-wire chemical gas-phase deposition (English Hot Filament CVD, be abbreviated as HFCVD) method, microwave plasma chemical vapour deposition (English Microwave Plasma CVD, be abbreviated as MPCVD) method, DC arc plasma jet CVD (English DC arc Plasma Jet CVD, be abbreviated as DPJCVD) beyond method, other CVD methods also reach far away practical degree of stability.Wherein, hot-wire chemical gas-phase deposition (HFCVD) method because equipment is simple, be easy to control, the large and diamond synthesis quality of depositional area better gains great popularity, and become the main direction of CVD diamond compound industry.
Through the literature search of prior art is found, in " The CVD growth of micro crystals of diamond " document that Taiwan KINIK company delivers on " Diamond and Related Materials " periodical, record a kind of synthetic method without seed crystal diamond single crystal particle of the HFCVD of utilization Diamond Equipment, the method is taking oxygen free copper as substrate, under the condition without diamond seeds, by controlling the distance between heated filament and substrate, realize the good adamantine preparation of ultra-fine grain of 6-7 μ m crystalline form, but it has ignored carbon source concentration, reaction pressure, bias current intensity is the impact without the particle growth of seed crystal diamond single crystal on CVD, make synthetic single crystal particle have the crystalline form quality problems such as lattice distortion, and for how realizing different grain size how can't harm collection without the preparation of seed crystal diamond single crystal micro mist and particle and all fail to propose effective solution route.
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 without the meticulous diamond single crystal micro mist of crystal seed is provided, adopt matrix from forming core substrate pretreatment process, can obtain lower Enhancing Nucleation Density, and make nucleome realize homodisperse object; On this basis, adopt hot filament CVD, adjust diamond nucleation and growth processing parameter, can prepare the meticulous diamond single crystal particle of high grade of crystalline form rule; Finally, adopt the technique of chemical corrosion silicon-based substrate in conjunction with high speed centrifugation sedimented particle, realize effective desorption and the collection of substrate particle, can obtain the meticulous diamond single crystal micro mist of the high grade of pure self-supporting.
The present invention realizes by following technical proposal: a kind of preparation method without the meticulous diamond single crystal micro mist of crystal seed, and wherein, step is:
(a): adopt matrix from forming core substrate pretreatment process, in silicon-based substrate, make evenly independent dispersion of nucleome;
(b): application hot filament CVD, to depositing through the pretreated described silicon-based substrate of described step (a), comprises diamond nucleation and two stages of diamond grain growth, obtains the diamond single crystal particle of crystalline form rule;
(c): adopt chemical corrosion silicon-based substrate in conjunction with the described diamond single crystal particle obtaining in step (b) described in high speed centrifugation sedimented particle art breading, to obtain meticulous diamond single crystal micro mist.
Preferably, matrix described in described step (a) refers to and adopts silicon-based substrate surface 0.5～1min described in 0.5～5.0 μ m diadust even mechanical mill from forming core substrate pretreatment process, then by described silicon-based substrate successively ultrasonic cleaning 3～5min in deionized water and acetone soln.
Preferably, the deposition process parameters that adopts is the described diamond nucleation stage in described step (b): 2～3kPa reaction pressure, 1.3～1.5% carbon source concentrations, 700～800 DEG C of underlayer temperatures, 1.0A bias current intensity, 40min nucleated time.
Preferably, the deposition process parameters that adopts is the described diamond grain growth stage in described step (b): 3～4kPa reaction pressure, 2.0～3.0% carbon source concentrations, 900～950 DEG C of underlayer temperatures, 2.0～4.0A bias current intensity, 30～140min growth time.
Preferably, the described chemical corrosion silicon-based substrate in described step (c) comprises in conjunction with the technique of high speed centrifugation sedimented particle: matrix is removed technique, mixed acid solution is removed technique and particle distil process.
Preferably, described matrix removal technique refers to: it is ultrasonic cleaning 10～15min in the nitric acid of 1:1 and the mixed acid solution of hydrofluoric acid that post-depositional described silicon-based substrate is immersed in to volume ratio, to remove described silicon-based substrate.
Preferably, described mixed acid solution removal technique refers to: utilize supercentrifuge to carry out particles settling to the mixed acid solution immersed with described silicon-based substrate, it is 10000r/min that described supercentrifuge rotating speed is set, and duration is 5min; After described particle separates with described mixed acid solution, by slow mixed acid solution described in upper strata sucking-off, and inject distilled water in remaining particle suspension liquid, auxiliary clean to obtain the particle suspension liquid that is neutral with ultrasonic vibration.
Preferably, described particle distil process refers under dustfree environment, and the particle suspension liquid of described neutrality is poured in matrass, adds the heat abstraction aqueous solution, obtains the meticulous diamond single crystal micro mist of self-supporting.
Compared with the prior art, the present invention has substantive distinguishing features and marked improvement are:
1. in the meticulous diadust that employing the present invention obtains, 60～80% particle all has high grade six-octahedron or icosahedron combinate form crystal habit, has high shock resistance, will particularly be applicable to the polishing of high-accuracy device.
2. with respect to mechanical disintegration or Detonation Process fine powder, the fine powder that the method obtains occupies greater advantage in crystalline form and surface quality, and technical process is simple, and the micro mist distribution of sizes obtaining is concentrated, and can save the granularity sieving technique of micro mist.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the preparation method's without the meticulous diamond single crystal micro mist of crystal seed of the present invention flow chart of steps.
Fig. 2 is the surface topography map without the meticulous diamond single crystal micro mist of crystal seed obtaining according to the embodiment of the present invention 4.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Fig. 1 is the preparation method's without the meticulous diamond single crystal micro mist of crystal seed of the present invention flow chart of steps.With reference to Fig. 1,
First, step S10: silicon-based substrate is carried out to pre-treatment.Adopt matrix from forming core substrate pretreatment process, in silicon-based substrate, make nucleome reach even independent effect of disperseing.Specifically refer to: adopt 0.5～5 μ m diadust to carry out even mechanical mill 0.5～1min to silicon-based substrate surface, then by the silicon-based substrate after mechanical mill successively ultrasonic cleaning 3～5min in deionized water and acetone soln.
Then, step S20: deposit pretreated silicon-based substrate.Application hot filament CVD, to depositing through the pretreated silicon-based substrate of step S10, comprises diamond nucleation and two stages of diamond grain growth, obtains the diamond single crystal particle of crystalline form rule.Wherein, the deposition process parameters that adopts is the diamond nucleation stage: 2～3kPa reaction pressure, 1.3～1.5% carbon source concentrations, 700～800 DEG C of underlayer temperatures, 1.0A bias current intensity, 40min nucleated time.The deposition process parameters that the diamond grain growth stage adopts is: 3～4kPa reaction pressure, 2.0～3.0% carbon source concentrations, 900～950 DEG C of underlayer temperatures, 2.0～4.0A bias current intensity, 30～140min growth time.
Finally, step S30: the diamond single crystal particle that adopts chemical corrosion silicon-based substrate to obtain in conjunction with high speed centrifugation sedimented particle art breading.Adopt chemical corrosion silicon-based substrate in conjunction with the diamond single crystal particle obtaining in high speed centrifugation sedimented particle art breading step S20, to obtain meticulous diamond single crystal micro mist.Specifically comprise: matrix is removed technique, mixed acid solution is removed technique and particle distil process.Matrix is removed technique and is referred to: it is to carry out ultrasonic cleaning 10～15min in the nitric acid of 1:1 and the mixed acid solution of hydrofluoric acid that post-depositional silicon-based substrate is immersed in to volume ratio, to remove silicon-based substrate.Mixed acid solution is removed technique and is referred to: utilize supercentrifuge to carry out particles settling to the mixed acid solution immersed with silicon-based substrate, it is 10000r/min that supercentrifuge rotating speed can be set, duration is 5min, after particle separates with mixed acid solution, by slow upper strata mixed acid solution sucking-off, and inject distilled water in remaining particle suspension liquid, auxiliary clean to obtain the particle suspension liquid that is neutral with ultrasonic vibration, certainly to mixed acid solution centrifugal-washing process can repeatable operation 7～8 times, until obtain the particle suspension liquid that is neutral.Particle distil process refers to: under dustfree environment, neutral particle suspension liquid is poured in matrass, added the heat abstraction aqueous solution, obtain the meticulous diamond single crystal micro mist of self-supporting.
Embodiment 1
It is the preparation of carrying out the meticulous diamond single crystal micro mist of the high grade of CVD of M0/0.5 granularity on bright finished monocrystalline silicon piece at substrate.
First, adopt 0.5 μ m diadust to carry out even mechanical mill 0.5min to silicon-based substrate surface, then by the silicon-based substrate after mechanical mill successively ultrasonic cleaning 3min in deionized water and acetone soln.
Next, the reaction chamber of putting into heated filament CVD device through pretreated silicon-based substrate is deposited, it is Φ 0.4mm twisted-pair feeder tantalum wire that heated filament adopts diameter, on silicon-based substrate, and utilize high temperature resistant spring to make heated filament in deposition process, remain straight and upright horizontality heated filament parallel arrangement.After vacuumizing, question response chamber passes into reactant gases (hydrogen and acetone), after adjusting the pressure of reaction chamber, start depositing diamond monocrystalline nucleome in silicon-based substrate, the depositing operation in this diamond nucleation (i.e. depositing diamond monocrystalline nucleome in silicon-based substrate) stage is: reaction gas pressure 2kPa, carbon source concentration are 1.3%, hot-wire temperature is about 1800 DEG C, substrate surface temperature and is about 700 DEG C, bias current intensity 1.0A, nucleated time 40min.After diamond nucleation finishes, enter the diamond grain growth stage, regulate each deposition process parameters in this stage to be: reaction gas pressure 3kPa, carbon source concentration are 2.0%, hot-wire temperature is about 2000 DEG C, and substrate surface temperature is about 950 DEG C, bias current intensity 2.0A, growth time 30min.Can in silicon-based substrate, obtain thus homodisperse high grade diamond single crystal particle, particle size mainly concentrates on 0.3～1.0 μ m.
Finally, will from CVD reaction chamber, take out through the post-depositional silicon-based substrate of CVD, and to be immersed in volume ratio be to carry out ultrasonic cleaning 10～15min in the nitric acid of 1:1 and the mixed solution of hydrofluoric acid.Recycling supercentrifuge, the rotating speed that supercentrifuge can be set is 10000r/min, duration is 5min, carry out particles settling mixing acid separation test, after success to be separated, by slow upper strata mixed acid solution sucking-off, and inject distilled water in remaining particle suspension liquid, assist and clean with ultrasonic vibration, after this centrifugal-washing process repeatable operation approximately 7～8 times, can obtain the particle suspension liquid that is neutral.Under dustfree environment, the neutral particle suspension liquid obtaining is poured in matrass, add the heat abstraction aqueous solution, can obtain self-supporting ultra-fine diamond monocrystalline micro mist.
Adopt aforesaid method can obtain the meticulous diamond single crystal micro mist that mean sizes is 0.46 μ m, and more than 80.1% particle all has six-octahedron or icosahedro height grade combinate form crystal habit, there is high shock resistance, there is greater advantage compared with traditional micro mist; And this micro mist distribution of sizes is concentrated, need not pass through granularity sieving technique, can meet every size index of M0/0.5 granularity micro mist in mechanical crushing method diadust industry standard (JB/T7990-2012), this advantage can be reduced preparation technology's flow process of micro mist, thereby improves the production efficiency of micro mist.
Embodiment 2
It is the preparation of carrying out the meticulous diamond single crystal micro mist of the high grade of CVD of M0/1 granularity on bright finished monocrystalline silicon piece at substrate.
First, adopt 2.0 μ m diadusts to carry out even mechanical mill 1min to silicon-based substrate surface, then by the ultrasonic cleaning 5min in deionized water and acetone soln respectively of the silicon-based substrate after mechanical mill.
Next, the reaction chamber of putting into heated filament CVD device through pretreated silicon-based substrate is deposited, it is Φ 0.4mm twisted-pair feeder tantalum wire that heated filament adopts diameter, on silicon-based substrate, and utilize high temperature resistant spring to make heated filament in deposition process, remain straight and upright horizontality heated filament parallel arrangement.After vacuumizing, question response chamber passes into reactant gases (hydrogen and acetone), after adjusting the pressure of reaction chamber, start depositing diamond monocrystalline nucleome in silicon-based substrate, the depositing operation in this diamond nucleation (i.e. depositing diamond monocrystalline nucleome in silicon-based substrate) stage is: reaction gas pressure 2.5kPa, carbon source concentration 1.3%, hot-wire temperature are about 1900 DEG C, substrate surface temperature and are about 700 DEG C, bias current intensity 1.0A, nucleated time 40min.After diamond nucleation finishes, enter the diamond grain growth stage, regulate each deposition process parameters in this stage to be: reaction gas pressure 3kPa, carbon source concentration 2.0%, hot-wire temperature are about 2100 DEG C, substrate surface temperature is about 950 DEG C, bias current intensity 3.0A, growth time 45min.Can in silicon-based substrate, obtain thus homodisperse high grade diamond single crystal particle, particle size mainly concentrates on 0.5～1.2 μ m.
Finally, will from CVD reaction chamber, take out through the post-depositional silicon-based substrate of CVD, and to be immersed in volume ratio be to carry out ultrasonic cleaning 10～15min in the nitric acid of 1:1 and the mixed solution of hydrofluoric acid.Recycling supercentrifuge, the rotating speed that supercentrifuge can be set is 10000r/min, duration is 5min, carry out particles settling mixing acid separation test, after success to be separated, by slow upper strata mixed acid solution sucking-off, and inject distilled water in remaining particle suspension liquid, assist and clean with ultrasonic vibration, after this centrifugal-washing process repeatable operation approximately 7～8 times, can obtain the particle suspension liquid that is neutral.Under dustfree environment, the neutral particle suspension liquid obtaining is poured in matrass, add the heat abstraction aqueous solution, can obtain self-supporting ultra-fine diamond monocrystalline micro mist.
Adopt aforesaid method can obtain the meticulous diamond single crystal micro mist that mean sizes is 0.75 μ m, and more than 75.8% particle all has six-octahedron or icosahedro height grade combinate form crystal habit, there is high shock resistance, there is absolute predominance compared with traditional micro mist; And this micro mist distribution of sizes is concentrated, need not pass through granularity sieving technique, can meet every size index of M0/1 granularity micro mist in mechanical crushing method diadust industry standard (JB/T7990-2012), this advantage can be reduced preparation technology's flow process of micro mist, thereby improves the production efficiency of micro mist.
Embodiment 3
It is the preparation of carrying out the meticulous diamond single crystal micro mist of the high grade of CVD of M0.5/1 granularity on bright finished monocrystalline silicon piece at substrate.
First, adopt 2.0 μ m diadusts to carry out even mechanical mill 0.7min to silicon-based substrate surface, then by the ultrasonic cleaning 4min in deionized water and acetone soln respectively of the silicon-based substrate after mechanical mill.
Next, the reaction chamber of putting into heated filament CVD device through pretreated silicon-based substrate is deposited, it is Φ 0.4mm twisted-pair feeder tantalum wire that heated filament adopts diameter, on silicon-based substrate, and utilize high temperature resistant spring to make heated filament in deposition process, remain straight and upright horizontality heated filament parallel arrangement.After vacuumizing, question response chamber passes into reactant gases (hydrogen and acetone), after adjusting the pressure of reaction chamber, start depositing diamond monocrystalline nucleome in silicon-based substrate, the depositing operation in this diamond nucleation (i.e. depositing diamond monocrystalline nucleome in silicon-based substrate) stage is: reaction gas pressure 3kPa, carbon source concentration 1.3%, hot-wire temperature are about 1850 DEG C, substrate surface temperature and are about 750 DEG C, bias current intensity 1.0A, nucleated time 40min.After diamond nucleation finishes, enter the diamond grain growth stage, regulate each deposition process parameters in this stage to be: reaction gas pressure 3kPa, carbon source concentration 2.2%, hot-wire temperature are about 2050 DEG C, substrate surface temperature is about 950 DEG C, bias current intensity 3.0A, growth time 55min.Can in silicon-based substrate, obtain thus homodisperse high grade diamond single crystal particle, particle size mainly concentrates on 1～3 μ m.
Finally, will from CVD reaction chamber, take out through the post-depositional silicon-based substrate of CVD, and to be immersed in volume ratio be to carry out ultrasonic cleaning 10～15min in the nitric acid of 1:1 and the mixed solution of hydrofluoric acid.Recycling supercentrifuge, the rotating speed that supercentrifuge can be set is 10000r/min, duration is 5min, carry out particles settling mixing acid separation test, after success to be separated, by slow upper strata mixed acid solution sucking-off, and inject distilled water in remaining particle suspension liquid, assist and clean with ultrasonic vibration, after this centrifugal-washing process repeatable operation approximately 7～8 times, can obtain the particle suspension liquid that is neutral.Under dustfree environment, the neutral particle suspension liquid obtaining is poured in matrass, add the heat abstraction aqueous solution, can obtain self-supporting ultra-fine diamond monocrystalline micro mist.
Adopt aforesaid method can obtain the meticulous diamond single crystal micro mist that mean sizes is 0.85 μ m, and more than 71.0% particle all has six-octahedron or icosahedro height grade combinate form crystal habit, there is high shock resistance, there is absolute predominance compared with traditional micro mist; And this micro mist distribution of sizes is concentrated, need not pass through granularity sieving technique, can meet every size index of M0.5/1 granularity micro mist in mechanical crushing method diadust industry standard (JB/T7990-2012), this advantage can be reduced preparation technology's flow process of micro mist, thereby improves the production efficiency of micro mist.
Embodiment 4
It is the preparation of carrying out the meticulous diamond single crystal micro mist of the high grade of CVD of M1/2 granularity on bright finished monocrystalline silicon piece at substrate.
First, adopt 4.0 μ m diadusts to carry out even mechanical mill 0.5min to silicon-based substrate surface, then by the ultrasonic cleaning 3min in deionized water and acetone soln respectively of the silicon-based substrate after mechanical mill.
Next, the reaction chamber of putting into heated filament CVD device through pretreated silicon-based substrate is deposited, it is Φ 0.4mm twisted-pair feeder tantalum wire that heated filament adopts diameter, on silicon-based substrate, and utilize high temperature resistant spring to make heated filament in deposition process, remain straight and upright horizontality heated filament parallel arrangement.After vacuumizing, question response chamber passes into reactant gases (hydrogen and acetone), after adjusting the pressure of reaction chamber, start depositing diamond monocrystalline nucleome in silicon-based substrate, the depositing operation in this diamond nucleation (i.e. depositing diamond monocrystalline nucleome in silicon-based substrate) stage is: reaction gas pressure 3kPa, carbon source concentration 1.4%, hot-wire temperature are about 1800 DEG C, substrate surface temperature and are about 750 DEG C, bias current intensity 1.0A, nucleated time 40min.After diamond nucleation finishes, enter the diamond grain growth stage, regulate each deposition process parameters in this stage to be: reaction gas pressure 3.5kPa, carbon source concentration 2.5%, hot-wire temperature are about 2000 DEG C, substrate surface temperature is about 900 DEG C, bias current intensity 4.0A, growth time 80min.Can in silicon-based substrate, obtain thus homodisperse high grade diamond single crystal particle, particle size mainly concentrates on 1～2.5 μ m.
Finally, will from CVD reaction chamber, take out through the post-depositional silicon-based substrate of CVD, and to be immersed in volume ratio be to carry out ultrasonic cleaning 10～15min in the nitric acid of 1:1 and the mixed solution of hydrofluoric acid.Recycling supercentrifuge, the rotating speed that supercentrifuge can be set is 10000r/min, duration is 5min, carry out particles settling mixing acid separation test, after success to be separated, by slow upper strata mixed acid solution sucking-off, and inject distilled water in remaining particle suspension liquid, assist and clean with ultrasonic vibration, after this centrifugal-washing process repeatable operation approximately 7～8 times, can obtain the particle suspension liquid that is neutral.Under dustfree environment, the neutral particle suspension liquid obtaining is poured in matrass, add the heat abstraction aqueous solution, can obtain self-supporting ultra-fine diamond monocrystalline micro mist.
Fig. 2 is the surface topography map without the meticulous diamond single crystal micro mist of crystal seed obtaining according to the embodiment of the present invention 4.With reference to Fig. 2, adopt aforesaid method can obtain the meticulous diamond single crystal micro mist that mean sizes is 1.45 μ m, and more than 70.0% particle all has six-octahedron or icosahedro height grade combinate form crystal habit, has high shock resistance, has absolute predominance compared with traditional micro mist; And this micro mist distribution of sizes is concentrated, need not pass through granularity sieving technique, can meet every size index of M1/2 granularity micro mist in mechanical crushing method diadust industry standard (JB/T7990-2012), this advantage can be reduced preparation technology's flow process of micro mist, thereby improves the production efficiency of micro mist.
Embodiment 5
It is the preparation of carrying out the meticulous diamond single crystal micro mist of the high grade of CVD of M2/4 granularity on bright finished monocrystalline silicon piece at substrate.
First, adopt 5.0 μ m diadusts to carry out even mechanical mill 1min to silicon-based substrate surface, then by the ultrasonic cleaning 5min in deionized water and acetone soln respectively of the silicon-based substrate after mechanical mill.
Next, the reaction chamber of putting into heated filament CVD device through pretreated silicon-based substrate is deposited, it is Φ 0.4mm twisted-pair feeder tantalum wire that heated filament adopts diameter, on silicon-based substrate, and utilize high temperature resistant spring to make heated filament in deposition process, remain straight and upright horizontality heated filament parallel arrangement.After vacuumizing, question response chamber passes into reactant gases (hydrogen and acetone), after adjusting the pressure of reaction chamber, start depositing diamond monocrystalline nucleome in silicon-based substrate, the depositing operation in this diamond nucleation (i.e. depositing diamond monocrystalline nucleome in silicon-based substrate) stage is: reaction gas pressure 3kPa, carbon source concentration 1.5%, hot-wire temperature are about 1900 DEG C, substrate surface temperature and are about 800 DEG C, bias current intensity 1.0A, nucleated time 40min.After diamond nucleation finishes, enter the diamond grain growth stage, regulate each deposition process parameters in this stage to be: reaction gas pressure 4kPa, carbon source concentration 3.0%, hot-wire temperature are about 2100 DEG C, substrate surface temperature is about 900 DEG C, bias current intensity 4.0A, growth time 140min.Can in silicon-based substrate, obtain thus homodisperse high grade diamond single crystal particle, particle size mainly concentrates on 2.0～3.5 μ m.
Finally, will from CVD reaction chamber, take out through the post-depositional silicon-based substrate of CVD, and to be immersed in volume ratio be to carry out ultrasonic cleaning 10～15min in the nitric acid of 1:1 and the mixed solution of hydrofluoric acid.Recycling supercentrifuge, the rotating speed that supercentrifuge can be set is 10000r/min, duration is 5min, carry out particles settling mixing acid separation test, after success to be separated, by slow upper strata mixed acid solution sucking-off, and inject distilled water in remaining particle suspension liquid, assist and clean with ultrasonic vibration, after this centrifugal-washing process repeatable operation approximately 7～8 times, can obtain the particle suspension liquid that is neutral.Under dustfree environment, the neutral particle suspension liquid obtaining is poured in matrass, add the heat abstraction aqueous solution, can obtain self-supporting ultra-fine diamond monocrystalline micro mist.
Adopt aforesaid method can obtain the meticulous diamond single crystal micro mist that mean sizes is 2.67 μ m, and more than 60.2% particle all has six-octahedron or icosahedro height grade combinate form crystal habit, there is high shock resistance, there is absolute predominance compared with traditional micro mist; And this micro mist distribution of sizes is concentrated, need not pass through granularity sieving technique, can meet every size index of M2/4 granularity micro mist in mechanical crushing method diadust industry standard (JB/T7990-2012), this advantage can be reduced preparation technology's flow process of micro mist, thereby improves the production efficiency of micro mist.
Compared with the prior art, the present invention has substantive distinguishing features and marked improvement are:
1. in the meticulous diadust that employing the present invention obtains, 60～80% particle all has high grade six-octahedron or icosahedron combinate form crystal habit, has high shock resistance, will particularly be applicable to the polishing of high-accuracy device.
2. with respect to mechanical disintegration or Detonation Process fine powder, the fine powder that the method obtains occupies greater advantage in crystalline form and surface quality, and technical process is simple, and the micro mist distribution of sizes obtaining is concentrated, and can save the granularity sieving technique of micro mist.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. without a preparation method for the meticulous diamond single crystal micro mist of crystal seed, it is characterized in that, step is:
(a): adopt matrix from forming core substrate pretreatment process, in silicon-based substrate, make evenly independent dispersion of nucleome;
(b): application hot filament CVD, to depositing through the pretreated described silicon-based substrate of described step (a), comprises diamond nucleation and two stages of diamond grain growth, obtains the diamond single crystal particle of crystalline form rule;
(c): adopt chemical corrosion silicon-based substrate in conjunction with the described diamond single crystal particle obtaining in step (b) described in high speed centrifugation sedimented particle art breading, to obtain meticulous diamond single crystal micro mist.
2. the preparation method without the meticulous diamond single crystal micro mist of crystal seed as claimed in claim 1, it is characterized in that, matrix described in described step (a) refers to and adopts silicon-based substrate surface 0.5～1min described in 0.5～5.0 μ m diadust even mechanical mill from forming core substrate pretreatment process, then by described silicon-based substrate successively ultrasonic cleaning 3～5min in deionized water and acetone soln.
3. the preparation method without the meticulous diamond single crystal micro mist of crystal seed as claimed in claim 1, it is characterized in that, the deposition process parameters that the described diamond nucleation stage in described step (b) adopts is: 2～3kPa reaction pressure, 1.3～1.5% carbon source concentrations, 700～800 DEG C of underlayer temperatures, 1.0A bias current intensity, 40min nucleated time.
4. the preparation method without the meticulous diamond single crystal micro mist of crystal seed as claimed in claim 1, it is characterized in that, the deposition process parameters that the described diamond grain growth stage in described step (b) adopts is: 3～4kPa reaction pressure, 2.0～3.0% carbon source concentrations, 900～950 DEG C of underlayer temperatures, 2.0～4.0A bias current intensity, 30～140min growth time.
5. the preparation method without the meticulous diamond single crystal micro mist of crystal seed as described in claim 1 to 4 any one, it is characterized in that, the described chemical corrosion silicon-based substrate in described step (c) comprises in conjunction with the technique of high speed centrifugation sedimented particle: matrix is removed technique, mixed acid solution is removed technique and particle distil process.
6. the preparation method without the meticulous diamond single crystal micro mist of crystal seed as claimed in claim 5, it is characterized in that, described matrix is removed technique and is referred to: it is ultrasonic cleaning 10～15min in the nitric acid of 1:1 and the mixed acid solution of hydrofluoric acid that post-depositional described silicon-based substrate is immersed in to volume ratio, to remove described silicon-based substrate.
7. the preparation method without the meticulous diamond single crystal micro mist of crystal seed as claimed in claim 6, it is characterized in that, described mixed acid solution is removed technique and is referred to: utilize supercentrifuge to carry out particles settling to the mixed acid solution immersed with described silicon-based substrate, it is 10000r/min that described supercentrifuge rotating speed is set, and duration is 5min; After described particle separates with described mixed acid solution, by slow mixed acid solution described in upper strata sucking-off, and inject distilled water in remaining particle suspension liquid, auxiliary clean to obtain the particle suspension liquid that is neutral with ultrasonic vibration.
8. the preparation method without the meticulous diamond single crystal micro mist of crystal seed as claimed in claim 7, it is characterized in that, described particle distil process refers under dustfree environment, the particle suspension liquid of described neutrality is poured in matrass, add the heat abstraction aqueous solution, obtain the meticulous diamond single crystal micro mist of self-supporting.
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