WO2020087429A1 - 掺杂型金刚石粉的制备方法 - Google Patents

掺杂型金刚石粉的制备方法 Download PDF

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WO2020087429A1
WO2020087429A1 PCT/CN2018/113325 CN2018113325W WO2020087429A1 WO 2020087429 A1 WO2020087429 A1 WO 2020087429A1 CN 2018113325 W CN2018113325 W CN 2018113325W WO 2020087429 A1 WO2020087429 A1 WO 2020087429A1
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doped diamond
diamond powder
boron
acid
copper foil
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French (fr)
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唐永炳
陈波
王陶
欧学武
孟醒
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond

Definitions

  • the present application relates to the technical field of diamond preparation, in particular, to a method for preparing doped diamond powder.
  • diamond Although diamond has extremely excellent properties, such as a large energy gap, high electron mobility, hole mobility and high thermal conductivity, as well as negative electron affinity, it is not itself conductive and cannot be directly For semiconductor materials, P-type and N-type doping of diamond is required. Therefore, it is of great practical significance to study the P-type and N-type doping of diamond.
  • boron atoms are generally doped to achieve P-type doping, and nitrogen atoms or phosphorus atoms are doped to achieve N-type doping. Diamond films doped with different elements have been applied to different fields.
  • the diamond film doped with different elements needs to implant the substrate during the preparation, and the market generally sells undoped diamond powder, so in the implantation process, the undoped diamond powder is often used to prepare an implant solution. Replant. In this way, the diamond doped in the subsequent deposition process will nucleate on the undoped seed crystal, which will result in a poorly conductive transition layer between the substrate and the doped diamond film. Reduce the conductivity between the substrate and the film, affecting the performance of the product.
  • patent CN106119807A discloses a method for preparing boron-doped diamond powder, in which an ethanol solution of boron powder with a certain concentration is dispersed in droplets On the titanium sheet, this method is difficult to ensure uniform doping of boron. Since boron doping cannot be performed during the deposition process, and sufficient boron source cannot be guaranteed for long time deposition, the single furnace output is low and high temperature is required Annealing to obtain boron-doped diamond powder, energy consumption is large.
  • the method includes the preparation of a certain thickness of boron-doped diamond film on the silicon wafer by microwave chemical vapor deposition equipment , And then dissolve the silicon wafer to obtain a boron-doped diamond film, and then crush the boron-doped diamond film, grinding to obtain boron-doped diamond powder, but the powder obtained at this time due to the production of some amorphous carbon sp 2
  • the content of the bond is high, so it is necessary to use a hot mixture of concentrated sulfuric acid and nitric acid (9: 1) to remove the sp 2 carbon by oxidation.
  • This method requires the solution containing hydrofluoric acid to dissolve the silicon, which is more dangerous to operate.
  • it requires pretreatment of the silicon wafer with an aqueous solution of hydrogen peroxide and ammonia, and the operation is cumbersome.
  • the purpose of this application is to provide a method for preparing doped diamond powder, which can solve at least one of the above problems.
  • This application provides a method for preparing doped diamond powder, including the following steps:
  • the crushing includes grinding, preferably ball milling;
  • the ball milling material includes one or more of stainless steel balls, agate balls or tungsten carbide balls;
  • the ball milling time is 2-12 h, preferably 3-7 h, further preferably 5 h.
  • the impurity removal includes acid washing and water washing, preferably including acid washing and then water washing;
  • the acid washing includes washing with inorganic acid first and then washing with mixed inorganic acid solution;
  • the mass fraction of the inorganic acid is 3-8%, preferably the inorganic acid includes any one of hydrochloric acid, sulfuric acid or nitric acid;
  • the inorganic acid cleaning time is 5-15min;
  • the mixed inorganic acid solution includes at least two of concentrated hydrochloric acid, concentrated sulfuric acid or concentrated nitric acid, preferably a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, preferably the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 8-10: 1;
  • the cleaning temperature of the mixed inorganic acid liquid is 50-70 ° C, and the cleaning time is 20-40min;
  • the water washing time is 6-12h.
  • the method further includes a step of crushing and removing impurities of the doped diamond film that has fallen off, and then distilling off the solvent to obtain a doped diamond powder.
  • a nano-diamond powder suspension is used to seed the substrate, and then the seeded substrate is placed in a hot-wire chemical vapor deposition device for deposition to obtain a doped diamond film ;
  • the method of planting crystals is to place the substrate in a nano-diamond powder suspension for ultrasonic absorption;
  • the ultrasonic time is 20-40min, and the ultrasonic power is 3000-4000W;
  • the concentration of the nano diamond powder in the nano diamond powder suspension is 0.005-0.5 wt%.
  • the process parameters of hot wire chemical vapor deposition include:
  • the reaction gas includes hydrogen, methane, doping element-containing gas and optional inert gas, wherein the methane gas flow rate accounts for 2-8% of the total gas flow rate;
  • the air pressure in the vacuum chamber is 2-8 Pa
  • the filament temperature is 1800-2800 ° C
  • the substrate temperature is 600-900 ° C
  • the deposition time is 1-7 h.
  • the thickness of the doped diamond thin film is 2-12 ⁇ m, preferably 5-12 ⁇ m, further preferably 10-12 ⁇ m.
  • the elements doped with the doped diamond powder include one or more of boron element, group I element, group V element or group VI element, preferably including boron element, lithium One or more of element, sodium, nitrogen, phosphorus, oxygen or sulfur, preferably boron.
  • the substrate includes any one of copper foil, copper alloy foil or cemented carbide foil, preferably copper foil.
  • the doped diamond powder is boron-doped diamond powder, including the following steps:
  • the ball milling materials include stainless steel balls, agate balls or tungsten carbide One or more of the balls, the ball grinding time is 3-7h;
  • the ball milled boron-doped diamond powder is first washed in dilute sulfuric acid with a mass fraction of 3-8% for 5-15 min, then concentrated sulfuric acid and concentrated nitric acid at a temperature of 50-70 ° C and a volume ratio of 8-10: 1 Soak in the mixed acid solution for 20-40min, and then disperse the obtained boron-doped diamond powder in water, ultrasonic for 6-12 hours, and obtain boron-doped diamond powder after distillation.
  • the preparation method of the doped diamond powder of the present application grows the doped diamond thin film on the substrate by hot wire chemical vapor deposition, and utilizes the large difference in thermal expansion coefficient between the diamond and the substrate. Due to the large thermal stress during the cooling process As a result, the doped diamond film will fall off from the substrate to obtain the doped diamond film fragments. The fragments are crushed and removed to obtain the doped diamond powder.
  • This method reversely obtains the doped diamond powder by depositing the doped diamond film, and the doped elements can be uniformly incorporated during the deposition of the film, and the doped elements in the resulting diamond powder are evenly distributed.
  • the whole preparation process is simple in process, the production process is safe, and the substrate is not corroded by hydrofluoric acid.
  • the production process is easy to control. By controlling the amount of doping gas when depositing a thin film, diamond powder with different amounts of doping elements can be prepared.
  • FIG. 1 is a flowchart of a method for preparing boron-doped diamond powder according to an embodiment of the present application
  • Example 2 is a diagram of the natural peeling of the film after deposition in Example 1;
  • FIG. 3 is a Raman diagram of the boron-doped diamond powder deposited in Example 1.
  • the present application provides a method for preparing doped diamond powder, which includes the steps of depositing a doped diamond thin film on a substrate by hot wire chemical vapor deposition, and allowing the doped diamond thin film to naturally release from the substrate during the cooling process After shedding, the shattered doped diamond thin film fragments are crushed and dedoped to obtain doped diamond powder.
  • the type and material of the substrate there is no limitation on the type and material of the substrate, as long as the substrate can withstand the high temperature during hot wire chemical vapor deposition, and there is a difference in thermal expansion coefficient between the substrate and the diamond. Just drop off naturally.
  • Typical but non-limiting examples of the substrate are copper foil (or copper alloy foil) or cemented carbide foil.
  • Doped diamond is doping other elements of diamond.
  • Diamond doping elements include but are not limited to P-type and N-type doping of diamond.
  • a typical single non-limiting example of P-type doping is doping with boron (B) elements.
  • Typical non-limiting examples of N-type doping are doping group I elements (such as lithium Li element and sodium Na element), group V elements (such as nitrogen N element and phosphorus P element), group VI elements (such as oxygen O element And sulfur S element) or other elements (such as hydrogen H element, potassium K element and arsenic As element) and so on.
  • the doping can be single doping (doping one element) or co-doping (doping multiple elements), such as B-O doping, B-S doping, or B-P doping.
  • the doping element includes one or more of boron element, lithium element, sodium element, nitrogen element, phosphorus element, oxygen element or sulfur element, preferably boron element.
  • Doped diamond powder and doped diamond film refer to diamond powder and diamond film with corresponding doping elements.
  • the hot wire chemical vapor deposition method is one of the chemical vapor deposition methods, and the method of the hot wire chemical vapor deposition is not limited, and it can be carried out using a conventional hot wire chemical vapor deposition device and / or process, which can be common
  • the hot wire method can also be other improved forms of the hot wire method such as electronic assistance.
  • the growth of chemical vapor deposition diamond requires implantation of diamond seeds.
  • the diamond seeds are adsorbed on the substrate, and then epitaxial growth is performed at the implanted seed points. Other elements are added during growth to form a doped diamond film.
  • the method of planting crystals is not limited, and it is preferable to use a nano-diamond powder suspension to implant diamond seeds.
  • the preferred method of seeding is to place the substrate in a suspension of diamond powder for adsorption.
  • the film will naturally fall off from the substrate during the cooling process to form doped diamond film fragments.
  • Natural peeling means that the film does not rely on external force and falls freely due to the temperature drop during the cooling process.
  • the method of pulverization is not limited, and the film fragments are pulverized into powder by pulverization.
  • a typical but non-limiting pulverization method is, for example, pulverization (such as ball milling).
  • Removal of impurities is to remove impurities introduced during crushing and to remove impurities such as amorphous carbon.
  • the method of removing impurities is not limited, including but not limited to the use of acid, alkali, etc. for treatment.
  • the doped diamond film is grown on the substrate by hot wire chemical vapor deposition. Due to the large difference in thermal expansion coefficient between the diamond and the substrate, the doped diamond film will be affected by the larger thermal stress during the cooling process. Shedding off the substrate to obtain doped diamond thin film fragments, crushing and removing impurities to obtain doped diamond powder.
  • This method reversely obtains the doped diamond powder by depositing the doped diamond film, and the doped elements can be uniformly incorporated during the deposition of the film, and the doped elements in the resulting diamond powder are evenly distributed.
  • the whole preparation process is simple in process, the production process is safe, and the substrate is not corroded by hydrofluoric acid.
  • the production process is easy to control. By controlling the amount of doping gas when depositing a thin film, diamond powder with different amounts of doping elements can be prepared.
  • the crushing method is ball milling
  • the ball milling material includes one or more of stainless steel balls, agate balls or tungsten carbide balls;
  • the ball milling time is 2-12 h, preferably 3-7 h, further preferably 5 h.
  • Typical but non-limiting ball milling times are, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
  • Doped diamond powder with uniform particle size distribution is obtained by ball milling.
  • the impurity removal includes acid washing and water washing
  • the exemplary impurity removal includes acid washing and then water washing
  • the acid washing includes washing with inorganic acid first and then washing with mixed inorganic acid solution;
  • the mass fraction of the inorganic acid is 3-8%, preferably the inorganic acid includes any one of hydrochloric acid, sulfuric acid or nitric acid;
  • the inorganic acid cleaning time is 5-15min;
  • Typical but non-limiting mass fractions of inorganic acids are for example 3%, 4%, 5%, 6% or 8%.
  • Typical but non-limiting cleaning times for inorganic acids are for example 5 min, 10 min or 15 min.
  • the mixed inorganic acid solution includes at least two of concentrated hydrochloric acid, concentrated sulfuric acid, or concentrated nitric acid.
  • Concentrated hydrochloric acid is generally hydrochloric acid with a mass fraction of more than 20%, and typically, for example, hydrochloric acid with a concentration of 36 to 38%.
  • Concentrated sulfuric acid is generally sulfuric acid with a mass fraction ⁇ 70%.
  • Concentrated nitric acid is generally nitric acid with a mass fraction of 65 to 70%.
  • the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 8-10: 1, for example, 8: 1, 9: 1, or 10: 1.
  • the cleaning temperature of the mixed inorganic acid liquid is 50-70 ° C, and the cleaning time is 20-40min;
  • Typical but non-limiting cleaning temperatures of the mixed inorganic acid liquid are, for example, 50 ° C, 55 ° C, 60 ° C, 65 ° C or 70 ° C.
  • the typical but non-limiting cleaning time of the mixed inorganic acid solution is, for example, 20 min, 30 min or 40 min.
  • the water washing time is 6-12h.
  • Typical but non-limiting washing times are 6h, 8h, 10h or 12h.
  • the preferred water washing method is to disperse the powder in deionized water and remove the residue by ultrasonic cleaning.
  • the method further includes a step of crushing and removing impurities of the doped diamond thin film that has fallen off, and then distilling off the solvent to obtain the doped diamond powder.
  • the water is distilled off after washing to obtain doped diamond powder.
  • the solvent is distilled off to obtain a high-quality powder.
  • the nanodiamond powder suspension includes nanodiamond powder, water and optional dispersant.
  • the concentration of the nano diamond powder in the nano diamond powder suspension is 0.005-0.5 wt%.
  • the nano-diamond powder is preferably a detonation nano-diamond powder.
  • the mass concentration of the nano diamond powder in the nano diamond powder suspension is, for example, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.01%, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%.
  • the dispersant is preferably a surfactant, including nonionic surfactant, cationic surfactant or anionic surfactant, preferably dimethyl carbonate.
  • the concentration of the dispersant in the nanodiamond powder suspension is 10 -7 -10 -4 mol / L, such as 10 -7 mol / L, 10 -6 mol / L, 10 -5 mol / L or 10 -4 mol / L.
  • the pH of the nanodiamond powder suspension is 2-8, such as pH2, pH3, pH4, pH5, pH6, pH7 or pH8.
  • the ultrasonic time during seeding is 20-40 min, such as 20 min, 30 min, or 40 min; the ultrasonic power is 3000-4000 W, such as 3000 W, 3500 W, or 4000 W.
  • the debris of the diamond micropowder after the implantation treatment can provide a nucleation core for the deposition of the diamond film by the hot-wire chemical vapor deposition method, and improve the nucleation density.
  • the process parameters of hot filament chemical vapor deposition include:
  • the reaction gas includes hydrogen, methane, doping element-containing gas and optional inert gas, wherein the methane gas flow rate accounts for 2-8% of the total gas flow rate, such as 2%, 3%, 4%, 5%, 6%, 7% or 8%;
  • the doping element is boron, the gas containing the doping element is borane; if the doping element is phosphorus, the gas containing the doping element is phosphine; if the doping element is nitrogen, the doping gas is nitrous oxide ; If the doping element is sulfur, the doping gas is hydrogen sulfide;
  • the pressure in the vacuum chamber is 2-8 Pa
  • the filament temperature is 1800-2800 ° C
  • the substrate temperature is 600-900 ° C
  • the deposition time is 1-7 h.
  • Typical but non-limiting vacuum chamber pressures are, for example, 2Pa, 3Pa, 4Pa, 5Pa, 6Pa, 7Pa or 8Pa.
  • Typical but non-limiting filament temperatures are, for example, 1800 ° C, 2000 ° C, 2200 ° C, 2400 ° C, 2600 ° C, or 2800 ° C.
  • Typical but non-limiting substrate temperatures are, for example, 600 ° C, 650 ° C, 700 ° C, 750 ° C, 800 ° C, 850 ° C or 900 ° C.
  • Typical but non-limiting deposition times are, for example, 1h, 2h, 3h, 4h, 5h, 6h or 7h.
  • the thickness of the doped diamond thin film is 2-12 ⁇ m, preferably 5-12 ⁇ m, further preferably 10-12 ⁇ m.
  • the thickness of the doped diamond thin film is typically, but not limited to, for example, 2 ⁇ m, 4 ⁇ m, 6 ⁇ m, 8 ⁇ m, 10 ⁇ m, or 12 ⁇ m.
  • the film By controlling the thickness of the doped diamond film, the film can be better peeled off from the substrate.
  • the film thickness is too small, and the film is not easy to detach after cooling.
  • the film thickness is too large, which easily leads to coarsening of diamond grains, and subsequent grinding is difficult.
  • a typical method for preparing boron-doped diamond powder includes the following steps:
  • the ball milled boron-doped diamond powder (S3) is first washed in dilute sulfuric acid with a mass fraction of 3-8% for 5-15 min, and then concentrated sulfuric acid at a temperature of 50-70 ° C and a volume ratio of 8-10: 1 Soak in the mixed acid solution with concentrated nitric acid for 20-40min, and then disperse the obtained boron-doped diamond powder in water, ultrasonic for 6-12 hours, and obtain boron-doped diamond powder after distillation (S4).
  • the preparation method of the boron-doped diamond powder uses a hot-wire chemical vapor deposition equipment to deposit a boron-doped diamond film on the copper foil, and then uses the large thermal expansion coefficient difference between the copper and the diamond film. During the cooling process, the boron-doped diamond film naturally Drop off from the copper foil substrate, and then ball mill the boron-doped diamond film that was dropped off to obtain a semi-finished product of boron-doped diamond powder, and then perform an impurity removal process on the semi-finished product to obtain a finished product of boron-doped diamond powder.
  • the preparation process is simple, safe and environmentally friendly, and the obtained boron-doped diamond powder has high purity and uniform distribution of boron elements.
  • the substrates used in the examples and comparative examples are cemented carbide tools.
  • a preparation method of boron-doped diamond powder includes the following steps:
  • a preparation method of boron-doped diamond powder includes the following steps:
  • step (3) of stainless steel ball milling The boron-doped diamond fragments obtained in step (3) of stainless steel ball milling are used, and the ball milling speed is 500 rpm and the ball milling time is 5 hours;
  • a preparation method of phosphorus-doped diamond powder includes the following steps:
  • a preparation method of nitrogen-doped diamond powder includes the following steps:
  • a preparation method of sulfur-doped diamond powder includes the following steps:
  • the ball mill speed is 500 rpm and the ball milling time is 5h;
  • a preparation method of boron-doped diamond powder includes the following steps:
  • Embodiment 1 The difference between this embodiment and Embodiment 1 is that the amount of boron doping is different, and the amount of boron doping in this embodiment is one tenth of that in Embodiment 1.
  • Table 1 lists the doping amount and conductivity of the doped diamond powder obtained in Examples and Comparative Examples.
  • the doping amount is calculated from the amount of gas, and the conductivity is measured on the diamond film deposited on the surface of the silicon wafer placed in the same furnace.
  • the measurement method is to use a multimeter to measure the uniformity of the film on the surface of the silicon wafer. The resistance.
  • Example 1 5000ppm 15.3K ⁇
  • Example 2 10000ppm 10.5K ⁇
  • Example 3 1000ppm 23.1K ⁇
  • Example 4 2000ppm 18.3K ⁇
  • Example 5 5000ppm 12.3K ⁇
  • Example 6 500ppm insulation
  • the method of the embodiment of the present application reversely obtains the doped diamond powder by depositing a doped diamond film, and can dope with different doping elements when depositing the film, and control the diamond powder by controlling the amount of doping gas
  • the amount of doping in the element is simple and easy to control.
  • doped diamond powder with different conductivity can be obtained.

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Abstract

一种掺杂型金刚石粉的制备方法，包括以下步骤：利用热丝化学气相沉积法在基体上沉积掺杂型金刚石薄膜，在冷却过程中使掺杂型金刚石薄膜从基体上自然脱落，然后对脱落的掺杂型金刚石薄膜碎片进行粉碎和去杂，得到掺杂型金刚石粉。

Description

掺杂型金刚石粉的制备方法 技术领域
本申请涉及金刚石制备技术领域，具体而言，涉及一种掺杂型金刚石粉的制备方法。
背景技术
金刚石虽然具有极为优异的性能，如具有很大的能隙，高的电子迁移率、空穴迁移率和高热导率，以及负的电子亲和势，但其本身并不导电，不能将它直接用于半导体材料，需要先进行金刚石的P型和N型掺杂。因此，研究金刚石的P型和N型掺杂具有重要的现实意义。在金刚石薄膜中掺杂时，一般是掺入硼原子以实现P型掺杂，掺入氮原子或磷原子以实现N型掺杂。掺杂不同元素的金刚石薄膜已经应用到不同领域中。
掺杂不同元素的金刚石薄膜在制备时需要对基体进行植晶，而市场上出售的一般是未掺杂的金刚石粉，因此在植晶工序中多用未掺杂的金刚石粉配制成植晶溶液进行植晶。这样植晶在后续的沉积过程中掺杂的金刚石会在未掺杂的晶种上形核生长，这就导致基体与掺杂的金刚石薄膜之间会存在一层导电性较差的过渡层，降低基体与薄膜之间的导电性，影响产品的性能。
对于掺杂不同元素的金刚石粉的获得，如掺硼金刚石粉末，现有技术中如专利CN106119807A公开了一种制备掺硼金刚石粉末的方法，其中将一定浓度的硼粉的乙醇溶液分散液滴在钛片上，这种方法很难保证硼的均匀掺杂，由于在沉积过程中无法进行掺硼，无法保证进行较长时间的沉积时充足的硼源，因此单炉产量较低，并且需要进行高温退火来得到掺硼金刚石粉，能耗较大。文献Toward Deep Blue Nano Hope Diamonds:Heavily Boron-Doped Diamond Nanoparticles.ACSNANO,2014,8(6):5757-5764报道的方法包括由微波化学气相沉积设备在硅片上制得一定厚度的掺硼金刚石薄膜，然后将硅片溶解掉，得到掺硼金刚石薄膜，然后将掺硼金刚石薄膜进行破碎，研磨得到掺硼金刚石粉末，但此时得到的粉末由于在研磨的过程中产生了一些非晶碳sp 2键的含量较高，因此需要使用浓硫酸和硝酸(9:1)的热混合物处理来进行sp 2碳的氧化去除。该方法需要用含有氢氟酸的溶液溶解硅，操作危险性较大，此外需要用双氧水和氨水的水溶液对硅片进行前处理，操作繁琐。
因此，所期望的是提供一种新的制备掺杂型金刚石粉的方法，其能够解决上述问题中的至少一个。
有鉴于此，特提出本申请。
发明内容
本申请的目在于提供一种掺杂型金刚石粉的制备方法，能够解决上述问题中的至少一个。
为了实现本申请的上述目的，特采用以下技术方案：
本申请提供了一种掺杂型金刚石粉的制备方法，包括以下步骤：
利用热丝化学气相沉积法在基体上沉积掺杂型金刚石薄膜，在冷却过程中使掺杂型金刚石薄膜从基体上自然脱落，然后对脱落的掺杂型金刚石薄膜碎片进行粉碎和去杂，得到掺杂型金刚石粉。
优选地，在本申请技术方案的基础上，所述粉碎包括研磨，优选为球磨；
优选地，球磨材料包括不锈钢球、玛瑙球或碳化钨球中的一种或几种；
优选地，球磨时间为2-12h，优选为3-7h，进一步优选为5h。
优选地，在本申请技术方案的基础上，所述去杂包括酸洗和水洗，优选包括先酸洗再水洗；
优选地，酸洗包括先用无机酸清洗再用混合无机酸液清洗；
优选地，无机酸的质量分数为3-8％，优选无机酸包括盐酸、硫酸或硝酸中的任意一种；
优选地，无机酸清洗时间为5-15min；
优选地，混合无机酸液包括浓盐酸、浓硫酸或浓硝酸中的至少两种，优选为浓硫酸和浓硝酸的混合酸液，优选浓硫酸和浓硝酸的体积比为8-10:1；
优选地，混合无机酸液清洗温度为50-70℃，清洗时间为20-40min；
优选地，水洗时间为6-12h。
优选地，在本申请技术方案的基础上，所述方法还包括对脱落的掺杂型金刚石薄膜碎片进行粉碎和去杂后进行蒸馏除去溶剂，得到掺杂型金刚石粉的步骤。
优选地，在本申请技术方案的基础上，使用纳米金刚石粉悬浮液在基体上进行植晶，然后将植晶后的基体放入热丝化学气相沉积设备中进行沉积，得到掺杂型金刚石薄膜；
优选地，植晶的方式为将基体置于纳米金刚石粉悬浮液中超声吸附；
优选地，超声时间为20-40min，超声功率为3000-4000W；
优选地，纳米金刚石粉在纳米金刚石粉悬浮液中浓度为0.005-0.5wt％。
优选地，在本申请技术方案的基础上，热丝化学气相沉积的工艺参数包括：
反应气体包括氢气、甲烷、含掺杂元素的气体和任选的惰性气体，其中甲烷气体流量占总气体流量的2-8％；
优选地，真空室气压为2-8Pa，灯丝温度为1800-2800℃，基体温度为600-900℃， 沉积时间为1-7h。
优选地，在本申请技术方案的基础上，掺杂型金刚石薄膜的厚度为2-12μm，优选为5-12μm，进一步优选为10-12μm。
优选地，在本申请技术方案的基础上，掺杂型金刚石粉掺杂的元素包括硼元素、I族元素、Ⅴ族元素或Ⅵ族元素中的一种或几种，优选包括硼元素、锂元素、钠元素、氮元素、磷元素、氧元素或硫元素中的一种或几种，优选为硼元素。
优选地，在本申请技术方案的基础上，基体包括铜箔、铜合金箔或硬质合金箔中的任意一种，优选为铜箔。
优选地，在本申请技术方案的基础上，所述掺杂型金刚石粉为掺硼金刚石粉，包括以下步骤：
(a)将铜箔用酒精超声清洗20-30min干燥备用；
(b)将清洗后的铜箔置于纳米金刚石粉悬浮液中超声20-40min；
(c)将超声后的铜箔放入热丝化学气相沉积设备中，对热丝进行碳化，向设备中通入氢气、甲烷、硼烷和任选的惰性气体，甲烷气体流量占总气体流量的2-8％，调节真空室气压为2-8Pa，灯丝温度为1800-2800℃，基体温度为600-900℃，沉积时间为1-7h，在铜箔表面形成一层厚度为2-12μm的掺硼金刚石薄膜；
(d)真空下随炉冷却，取出铜箔，掺硼金刚石薄膜从铜箔上自然脱落，将脱落的掺硼金刚石薄膜碎片装入球磨设备中球磨，球磨材料包括不锈钢球、玛瑙球或碳化钨球中的一种或几种，球磨时间为3-7h；
(e)将球磨后的掺硼金刚石粉先在质量分数为3-8％的稀硫酸中清洗5-15min，然后在温度50-70℃、体积比8-10:1的浓硫酸和浓硝酸的混合酸液中浸泡20-40min，再将所得掺硼金刚石粉分散在水中，超声6-12小时，蒸馏后得到掺硼金刚石粉。
与已有技术相比，本申请具有如下有益效果：
本申请掺杂型金刚石粉的制备方法通过热丝化学气相沉积在基体上生长掺杂型金刚石薄膜，利用金刚石与基体之间具有较大的热膨胀系数差异，在冷却过程中由于较大热应力的作用，掺杂型金刚石薄膜会从基体上脱落，从而得到掺杂型金刚石薄膜碎片，将碎片进行粉碎和除杂得到掺杂型金刚石粉。该方法通过沉积掺杂型金刚石薄膜反向得到掺杂型金刚石粉，掺杂元素在沉积薄膜时可均匀掺入，最终得到的金刚石粉体中掺杂元素分布均匀。整个制备过程工艺简单，生产过程安全、无需采用氢氟酸腐蚀基体，生产过程容易控制，通过沉积薄膜时控制掺杂气体量能够制备不同掺杂元素量的金刚石粉。
附图说明
图1为本申请一种实施方式的掺硼金刚石粉的制备方法流程图；
图2为实施例1沉积完毕后薄膜自然脱落图；
图3为实施例1沉积所得掺硼金刚石粉的拉曼图。
具体实施方式
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本申请提供了一种掺杂型金刚石粉的制备方法，包括以下步骤：利用热丝化学气相沉积法在基体上沉积掺杂型金刚石薄膜，在冷却过程中使掺杂型金刚石薄膜从基体上自然脱落，然后对脱落的掺杂型金刚石薄膜碎片进行粉碎和去杂，得到掺杂型金刚石粉。
对基体的种类和材质不作限定，只要基体能耐受热丝化学气相沉积时的高温、基体与金刚石之间存在热膨胀系数差异，基体热丝化学气相沉积掺杂型金刚石薄膜后冷却过程中薄膜能从基体上自然脱落即可。
基体典型但非限制性的例如为铜箔(或铜合金箔)或硬质合金箔。
掺杂型金刚石是对金刚石进行其他元素的掺杂，金刚石掺杂元素包括但不限于金刚石的P型和N型掺杂。P型掺杂典型单非限制性的例如为掺杂硼(B)元素。N型掺杂典型单非限制性的例如为掺杂I族元素(例如锂Li元素和钠Na元素)、Ⅴ族元素(例如氮N元素和磷P元素)、Ⅵ族元素(例如氧O元素和硫S元素)或其他元素(例如氢H元素、钾K元素和砷As元素)等。掺杂可以是单掺杂(掺杂一种元素)，也可以是共掺杂(掺杂多种元素)，例如B-O掺杂、B-S掺杂或B-P掺杂。
优选地，掺杂元素包括硼元素、锂元素、钠元素、氮元素、磷元素、氧元素或硫元素中的一种或几种，优选为硼元素。
掺杂型金刚石粉、掺杂型金刚石薄膜指具有对应掺杂元素的金刚石粉和金刚石薄膜。
热丝化学气相沉积法(热丝CVD)是化学气相沉积法中的一种，对热丝化学气相沉积方式不作限定，可采用常规的热丝化学气相沉积装置和/或工艺进行，可以是普通热丝法，也可以是电子辅助等其他改进形式的热丝法。
化学气相沉积金刚石生长需要植入金刚石晶种，金刚石晶种吸附在基体上，然后在植入的晶种点进行外延生长，生长时掺入其他元素，形成掺杂型金刚石薄膜。
对植晶的方式不作限定，优选采用纳米金刚石粉悬浮液植入金刚石晶种。优选的植晶方式为将基体置于金刚石粉悬浮液中进行吸附。
沉积形成掺杂型金刚石薄膜后冷却过程中薄膜会从基体自然脱落，形成掺杂型金刚石薄膜碎片。
自然脱落指薄膜不借助外力，由于冷却过程温度下降而自由脱落。
对掺杂型金刚石薄膜碎片进行粉碎和去杂。
对粉碎的方式不作限定，通过粉碎将薄膜碎片研磨成粉状，典型但非限制性的粉碎方式例如为研磨(例如球磨)。
去杂是对去除粉碎时引入的杂质以及去除非晶碳等杂质。
对去杂的方式不作限定，包括但不限于使用酸、碱等进行处理。
本申请通过热丝化学气相沉积在基体上生长掺杂型金刚石薄膜，利用金刚石与基体之间具有较大的热膨胀系数差异，在冷却过程中由于较大热应力的作用，掺杂型金刚石薄膜会从基体上脱落，从而得到掺杂型金刚石薄膜碎片，将碎片进行粉碎和除杂得到掺杂型金刚石粉。该方法通过沉积掺杂型金刚石薄膜反向得到掺杂型金刚石粉，掺杂元素在沉积薄膜时可均匀掺入，最终得到的金刚石粉体中掺杂元素分布均匀。整个制备过程工艺简单，生产过程安全、无需采用氢氟酸腐蚀基体，生产过程容易控制，通过沉积薄膜时控制掺杂气体量能够制备不同掺杂元素量的金刚石粉。
在一种优选的实施方式中，粉碎方式为球磨；
优选地，球磨材料包括不锈钢球、玛瑙球或碳化钨球中的一种或几种；
优选地，球磨时间为2-12h，优选为3-7h，进一步优选为5h。
球磨时间典型但非限制性的例如为2h、3h、4h、5h、6h、7h、8h、9h、10h、11h或12h。
通过球磨得到粒径分布均匀的掺杂型金刚石粉。
在一种优选的实施方式中，去杂包括酸洗和水洗，示例性去杂包括先酸洗再水洗；
优选地，酸洗包括先用无机酸清洗再用混合无机酸液清洗；
优选地，无机酸的质量分数为3-8％，优选无机酸包括盐酸、硫酸或硝酸中的任意一种；
优选地，无机酸清洗时间为5-15min；
无机酸典型但非限制性的质量分数例如为3％、4％、5％、6％或8％。
无机酸典型但非限制性的清洗时间例如为5min、10min或15min。
采用稀酸进行清洗，去除球磨中不锈钢磨球的残留。
优选地，混合无机酸液包括浓盐酸、浓硫酸或浓硝酸中的至少两种。
浓盐酸一般是质量分数超过20％的盐酸，典型的例如为浓度为36～38％的盐酸。
浓硫酸一般是质量分数≥70％的硫酸。
浓硝酸一般是质量分数在65～70％的硝酸。
优选为浓硫酸和浓硝酸的混合酸液，优选浓硫酸和浓硝酸的体积比为8-10:1，例如为8:1、9:1或10:1。
优选地，混合无机酸液清洗温度为50-70℃，清洗时间为20-40min；
混合无机酸液典型但非限制性的清洗温度例如为50℃、55℃、60℃、65℃或70℃。
混合无机酸液典型但非限制性的清洗时间例如为20min、30min或40min。
通过采用浓酸进行清洗，去除粉末中的非晶碳。
优选地，水洗时间为6-12h。
水洗时间典型但非限制性的例如为6h、8h、10h或12h。
优选的水洗方式是将粉末分散于去离子水中，超声清洗去除残留。
在一种优选的实施方式中，方法还包括对脱落的掺杂型金刚石薄膜碎片进行粉碎和去杂后进行蒸馏除去溶剂，得到掺杂型金刚石粉的步骤。
优选地，水洗后将水蒸馏去除，得到掺杂型金刚石粉。
由于金刚石粉粒径在纳米级，蒸馏除溶剂获得高质量的粉体。
在一种优选的实施方式中，纳米金刚石粉悬浮液包括纳米金刚石粉、水和任选的分散剂。
优选地，纳米金刚石粉在纳米金刚石粉悬浮液中浓度为0.005-0.5wt％。
纳米金刚石粉优选为爆轰纳米金刚石粉。
纳米金刚石粉在纳米金刚石粉悬浮液中的质量浓度例如为0.005％、0.006％、0.007％、0.008％、0.009％、0.01％、0.1％、0.2％、0.3％、0.4％或0.5％。
分散剂优选为表面活性剂，包括非离子型表面活性剂、阳离子型表面活性剂或阴离子型表面活性剂，优选为碳酸二甲酯。
优选地，分散剂在纳米金刚石粉悬浮液中浓度为10 -7-10 -4mol/L，例如10 -7mol/L、10 -6mol/L、10 -5mol/L或10 -4mol/L。
优选地，纳米金刚石粉悬浮液的pH为2-8，例如pH2、pH3、pH4、pH5、pH6、pH7或pH8。
优选地，植晶时的超声时间为20-40min，例如20min、30min或40min；超声功率为3000-4000W，例如3000W、3500W或4000W。
植晶处理后金刚石微粉的碎屑可以为热丝化学气相沉积法沉积金刚石薄膜提供成核核心，提高形核密度。
在一种优选的实施方式中，热丝化学气相沉积的工艺参数包括：
反应气体包括氢气、甲烷、含掺杂元素的气体和任选的惰性气体，其中甲烷气体流量占总气体流量的2-8％，例如2％、3％、4％、5％、6％、7％或8％；
若掺杂元素为硼，含掺杂元素的气体是硼烷；若掺杂元素为磷，含掺杂元素的气体是磷化氢；若掺杂元素为氮，掺杂气体为一氧化二氮；若掺杂元素为硫，掺杂气体为硫化氢；
优选地，真空室气压为2-8Pa，灯丝温度为1800-2800℃，基体温度为600-900℃，沉积时间为1-7h。
真空室气压典型但非限制性的例如为2Pa、3Pa、4Pa、5Pa、6Pa、7Pa或8Pa。灯丝温度典型但非限制性的例如为1800℃、2000℃、2200℃、2400℃、2600℃或2800℃。基体温度典型但非限制性的例如为600℃、650℃、700℃、750℃、800℃、850℃或900℃。沉积时间典型但非限制性的例如为1h、2h、3h、4h、5h、6h或7h。
通过控制甲烷气体和含掺杂元素的气体的流量，以控制气相掺杂原子与碳原子的比例，能够获得不同掺杂量的不同掺杂元素金刚石薄膜。
优选地，掺杂型金刚石薄膜的厚度为2-12μm，优选为5-12μm，进一步优选为10-12μm。
掺杂型金刚石薄膜的厚度典型但非限制性的例如为2μm、4μm、6μm、8μm、10μm或12μm。
通过控制掺杂型金刚石薄膜的厚度使薄膜更好地从基体上脱落下来，薄膜厚度过小，冷却后薄膜不容易脱离，薄膜厚度过大，容易导致金刚石晶粒粗化，后续研磨比较困难。
作为一种优选的实施方式，一种典型的掺硼金刚石粉的制备方法，如图1所示，包括以下步骤：
(a)将铜箔用酒精超声清洗20-30min干燥备用；
(b)将清洗后的铜箔置于纳米金刚石粉悬浮液中超声20-40min；
(c)将超声后的铜箔放入热丝化学气相沉积设备中，对热丝进行碳化，向设备中通入氢气、甲烷、硼烷和任选的惰性气体，甲烷气体流量占总气体流量的2-8％，调节真空室气压为2-8Pa，灯丝温度为1800-2800℃，基体温度为600-900℃，沉积时间为1-7h，在铜箔表面形成一层厚度为2-12μm的掺硼金刚石薄膜(S1)；
(d)真空下随炉冷却，取出铜箔，掺硼金刚石薄膜从铜箔上自然脱落，将脱落的掺硼金刚石薄膜碎片(S2)装入球磨设备中球磨，球磨材料包括不锈钢球、玛瑙球或碳化钨球中的一种或几种，球磨时间为3-7h；
(e)将球磨后的掺硼金刚石粉(S3)先在质量分数为3-8％的稀硫酸中清洗5-15min，然后在温度50-70℃、体积比8-10:1的浓硫酸和浓硝酸的混合酸液中浸泡20-40min，再将所得掺硼金刚石粉分散在水中，超声6-12小时，蒸馏后得到掺硼金刚石粉(S4)。
该掺硼金刚石粉的制备方法利用热丝化学气相沉积设备在铜箔上沉积掺硼金刚石薄膜，然后利用铜与金刚石薄膜之间较大的热膨胀系数差，在冷却过程中掺硼金刚石薄膜自然的从铜箔基体上脱落下来，然后球磨脱落下来的掺硼金刚石薄膜，得到掺硼金刚石粉半成品，然后对半成品进行去杂质工艺，得到掺硼金刚石粉成品。制备工艺简单、安全环保，得到的掺硼金刚石粉纯度高，硼元素分布均匀。
下面通过具体的实施例和对比例进一步说明本申请，但是，应当理解为，这些实施例仅是用于更详细地说明之用，而不应理解为用于以任何形式限制本申请。本申请涉及的各原料均可通过商购获取。
实施例和对比例采用的基体为硬质合金刀具。
实施例1
一种掺硼金刚石粉的制备方法，包括以下步骤：
(1)裁剪与样品台大小适应的铜箔，用酒精超声清洗20min吹干备用；
(2)将清洗后的铜箔置于金刚石粉悬浮液中超声30min，对其进行植晶处理；
(3)将植晶处理后的样品放入化学气相沉积设备中，然后对热丝进行碳化，碳化完毕后将样平台升高至于热丝间距15mm处，通入氢气800sccm，甲烷32sccm，三甲基硼烷160sccm；真空室气压2kPa；灯丝温度2200℃，基体温度800℃；处理时间为6h，在铜箔表面形成一层厚度为10μm的纳米金刚石薄膜；然后在真空下随炉冷却，取出铜箔，将铜箔上的掺硼金刚石薄膜碎片装入球磨罐中，如图2；
(4)采用不锈钢小球球磨步骤(3)所得的掺硼金刚石薄膜碎片，球磨机转速500转每分钟球磨时间为5h；
(5)将球磨得到的掺硼金刚石粉在5％的稀硫酸中清洗10min，去除不锈钢磨球的残留；
(6)将用稀硫酸清洗后的金刚石在温度为60℃的浓硫酸和浓硝酸(v:v＝9:1)中浸泡30min，以去除非晶碳，得到掺硼金刚石粉；
(7)将(6)中所得的掺硼金刚石粉分散在去离子水中，然后蒸馏得到高质量掺硼 金刚石粉，如图3所示，硼与纯金刚石的峰位不同，说明硼成功掺杂进去。
实施例2
一种掺硼金刚石粉的制备方法，包括以下步骤：
(1)裁剪与样品台大小适应的铜箔，用酒精超声清洗20min吹干备用；
(2)将清洗后的铜箔置于金刚石粉悬浮液中超声30min，对其进行植晶处理；
(3)将植晶处理后的样品放入化学气相沉积设备中，然后对热丝进行碳化，碳化完毕后将样平台升高至于热丝间距15mm处，通入氢气800sccm，甲烷32sccm，三甲基硼烷320sccm；真空室气压3kPa；灯丝温度2600℃，基体温度850℃；沉积时间为7h，在铜箔表面形成一层厚度为12μm的纳米金刚石薄膜；然后在真空下随炉冷却，取出铜箔，将铜箔上的掺硼金刚石薄膜碎片装入球磨罐中；
(4)采用不锈钢小球球磨步骤(3)所得的掺硼金刚石碎片，球磨机转速500转每分钟球磨时间为5h；
(5)将球磨得到的掺硼金刚石粉在5％的稀硫酸中清洗10min，去除不锈钢磨球的残留；
(6)将用稀硫酸清洗后的金刚石在温度为60℃的浓硫酸和浓硝酸(v:v＝9:1)中浸泡30min，以去除非晶碳，得到掺硼金刚石粉；
(7)将(6)中所得的掺硼金刚石粉分散在去离子水中，然后蒸馏得到高质量掺硼金刚石粉。
实施例3
一种掺磷金刚石粉的制备方法，包括以下步骤：
(1)裁剪与样品台大小适应的铜箔，用酒精超声清洗20min吹干备用；
(2)将清洗后的铜箔置于金刚石粉悬浮液中超声30min，对其进行植晶处理；
(3)将植晶处理后的样品放入化学气相沉积设备中，然后对热丝进行碳化，碳化完毕后将样品台升高至离热丝间距12mm处，通入氢气800sccm，甲烷32sccm，磷化氢32sccm；腔体气压2kPa；灯丝温度2400℃，基体温度800℃；沉积时间为5h，在铜箔表面形成一层厚度为10μm的纳米金刚石薄膜；然后在真空下随炉冷却，取出铜箔，将铜箔上的掺磷金刚石薄膜碎片装入球磨罐中；
(4)采用不锈钢小球球磨步骤(3)所得的掺磷金刚石碎片，球磨机转速500转每分钟球磨时间为5h；
(5)将球磨得到的掺磷金刚石粉在5％的稀硫酸中清洗10min，去除不锈钢磨球的残留；
(6)将用稀硫酸清洗后的金刚石在温度为60℃的浓硫酸和浓硝酸(v:v＝9:1)中浸泡30min，以去除非晶碳，得到掺磷金刚石粉；
(7)将(6)中所得的掺磷金刚石粉分散在去离子水中，然后蒸馏得到高质量掺磷金刚石粉。
实施例4
一种掺氮金刚石粉的制备方法，包括以下步骤：
(1)裁剪与样品台大小适应的铜箔，用酒精超声清洗20min吹干备用；
(2)将清洗后的铜箔置于金刚石粉悬浮液中超声30min，对其进行植晶处理；
(3)将植晶处理后的样品放入化学气相沉积设备中，然后对热丝进行碳化，碳化完毕后将样品台升高至于热丝间距10mm处，通入氢气800sccm，甲烷32sccm，一氧化二氮64sccm；真空室气压4kPa；灯丝温度2200℃，基体温度800℃；沉积时间为8h，在铜箔表面形成一层厚度为14μm的纳米金刚石薄膜；然后在真空下随炉冷却，取出铜箔，将铜箔上的掺氮金刚石薄膜碎片装入球磨罐中；
(4)采用不锈钢小球球磨步骤(3)所得的掺氮金刚石碎片，球磨机转速500转每分钟球磨时间为5h；
(5)将球磨得到的掺氮金刚石粉在5％的稀硫酸中清洗10min，去除不锈钢磨球的残留；
(6)将用稀硫酸清洗后的金刚石在温度为60℃的浓硫酸和浓硝酸(v:v＝9:1)中浸泡30min，以去除非晶碳，得到掺氮金刚石粉；
(7)将(6)中所得的掺氮金刚石粉分散在去离子水中，然后蒸馏得到高质量掺氮金刚石粉。
实施例5
一种掺硫金刚石粉的制备方法，包括以下步骤：
(1)裁剪与样品台大小适应的铜箔，用酒精超声清洗20min吹干备用；
(2)将清洗后的铜箔置于金刚石粉悬浮液中超声30min，对其进行植晶处理；
(3)将植晶处理后的样品放入化学气相沉积设备中，然后对热丝进行碳化，碳化完毕后将样品台升高至离热丝间距12mm处，通入氢气800sccm，甲烷32sccm，硫化氢32sccm；腔体气压2kPa；灯丝温度2400℃，基体温度800℃；沉积时间为5h，在铜箔表面形成一层厚度为10μm的纳米金刚石薄膜；然后在真空下随炉冷却，取出铜箔，将铜箔上的掺硫金刚石薄膜碎片装入球磨罐中；
(4)采用不锈钢小球球磨步骤(3)所得的掺硫金刚石碎片，球磨机转速500转每 分钟球磨时间为5h；
(5)将球磨得到的掺硫金刚石粉在5％的稀硫酸中清洗10min，去除不锈钢磨球的残留；
(6)将用稀硫酸清洗后的金刚石在温度为60℃的浓硫酸和浓硝酸(v:v＝9:1)中浸泡30min，以去除非晶碳，得到掺硫金刚石粉；
(7)将(6)中所得的掺硫金刚石粉分散在去离子水中，然后蒸馏得到高质量掺硫金刚石粉。
实施例6
一种掺硼金刚石粉的制备方法，包括以下步骤：
(1)裁剪与样品台大小适应的铜箔，用酒精超声清洗20min吹干备用；
(2)将清洗后的铜箔置于金刚石粉悬浮液中超声30min，对其进行植晶处理；
(3)将植晶处理后的样品放入化学气相沉积设备中，然后对热丝进行碳化，碳化完毕后将样品台升高至于热丝间距15mm处，通入氢气800sccm，甲烷32sccm，三甲基硼烷16sccm；真空室气压2kPa；灯丝温度2200℃，基体温度800℃；处理时间为6h，在铜箔表面形成一层厚度为10μm的纳米金刚石薄膜；然后在真空下随炉冷却，取出铜箔，将铜箔上的掺硼金刚石薄膜碎片装入球磨罐中；
(4)采用不锈钢小球球磨步骤(3)所得的掺硼金刚石薄膜碎片，球磨机转速500转每分钟球磨时间为5h；
(5)将球磨得到的掺硼金刚石粉在5％的稀硫酸中清洗10min，去除不锈钢磨球的残留；
(6)将用稀硫酸清洗后的金刚石在温度为60℃的浓硫酸和浓硝酸(v:v＝9:1)中浸泡30min，以去除非晶碳，得到掺硼金刚石粉；
(7)将(6)中所得的掺硼金刚石粉分散在去离子水中，然后蒸馏得到高质量掺硼金刚石粉。
本实施例和实施例1的区别在于，掺硼量不同，本实施例的掺硼量为实施例1的十分之一。
表1列出了实施例和对比例得到的掺杂的金刚石粉的掺杂量和导电性。其中掺杂量由气体的量计算得到，导电性在同炉所放硅片表面沉积的金刚石薄膜上测得，测量方法为用万用表测量硅片表面薄膜均匀处距离为一厘米的两点之间的电阻。
表1
实施例 掺杂量 导电性
实施例1 5000ppm 15.3KΩ
实施例2 10000ppm 10.5KΩ
实施例3 1000ppm 23.1KΩ
实施例4 2000ppm 18.3KΩ
实施例5 5000ppm 12.3KΩ
实施例6 500ppm 绝缘
由表1可以看出，本申请实施例方法通过沉积掺杂型金刚石薄膜反向得到掺杂型金刚石粉，在沉积薄膜时可掺入不同掺杂元素，通过控制掺杂气体量控制金刚石粉体中元素的掺杂量，制备过程简单、容易控制。此外，通过控制掺杂气体量来调节金刚石粉的掺杂量，从而可获得不同导电性的掺杂金刚石粉。
尽管已用具体实施例来说明和描述了本申请，然而应意识到，在不背离本申请的精神和范围的情况下可作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本申请范围内的所有这些变化和修改。

Claims (10)

  1. 一种掺杂型金刚石粉的制备方法，其特征在于，包括以下步骤：
    利用热丝化学气相沉积法在基体上沉积掺杂型金刚石薄膜，在冷却过程中使掺杂型金刚石薄膜从基体上自然脱落，然后对脱落的掺杂型金刚石薄膜碎片进行粉碎和去杂，得到掺杂型金刚石粉。
  2. 按照权利要求1所述的掺杂型金刚石粉的制备方法，其特征在于，所述粉碎包括研磨，优选为球磨；
    优选地，球磨材料包括不锈钢球、玛瑙球或碳化钨球中的一种或几种；
    优选地，球磨时间为2-12h，优选为3-7h，进一步优选为5h。
  3. 按照权利要求1所述的掺杂型金刚石粉的制备方法，其特征在于，所述去杂包括酸洗和水洗，优选包括先酸洗再水洗；
    优选地，酸洗包括先用无机酸清洗再用混合无机酸液清洗；
    优选地，无机酸的质量分数为3-8％，优选无机酸包括盐酸、硫酸或硝酸中的任意一种；
    优选地，无机酸清洗时间为5-15min；
    优选地，混合无机酸液包括浓盐酸、浓硫酸或浓硝酸中的至少两种，优选为浓硫酸和浓硝酸的混合酸液，优选浓硫酸和浓硝酸的体积比为8-10:1；
    优选地，混合无机酸液清洗温度为50-70℃，清洗时间为20-40min；
    优选地，水洗时间为6-12h。
  4. 按照权利要求1-3任一项所述的掺杂型金刚石粉的制备方法，其特征在于，所述方法还包括对脱落的掺杂型金刚石薄膜碎片进行粉碎和去杂后进行蒸馏除去溶剂，得到掺杂型金刚石粉的步骤。
  5. 按照权利要求1-3任一项所述的掺杂型金刚石粉的制备方法，其特征在于，使用纳米金刚石粉悬浮液在基体上进行植晶，然后将植晶后的基体放入热丝化学气相沉积设备中进行沉积，得到掺杂型金刚石薄膜；
    优选地，植晶的方式为将基体置于纳米金刚石粉悬浮液中超声吸附；
    优选地，超声时间为20-40min，超声功率为3000-4000W；
    优选地，纳米金刚石粉在纳米金刚石粉悬浮液中浓度为0.005-0.5wt％。
  6. 按照权利要求5所述的掺杂型金刚石粉的制备方法，其特征在于，热丝化学气相沉积的工艺参数包括：
    反应气体包括氢气、甲烷、含掺杂元素的气体和任选的惰性气体，其中甲烷气体流量占总气体流量的2-8％；
    优选地，真空室气压为2-8Pa，灯丝温度为1800-2800℃，基体温度为600-900℃，沉积时间为1-7h。
  7. 按照权利要求1-3任一项所述的掺杂型金刚石粉的制备方法，其特征在于，掺杂型金刚石薄膜的厚度为2-12μm，优选为5-12μm，进一步优选为10-12μm。
  8. 按照权利要求1-3任一项所述的掺杂型金刚石粉的制备方法，其特征在于，掺杂型金刚石粉掺杂的元素包括硼元素、I族元素、Ⅴ族元素或Ⅵ族元素中的一种或几种，优选包括硼元素、锂元素、钠元素、氮元素、磷元素、氧元素或硫元素中的一种或几种，优选为硼元素。
  9. 按照权利要求1-3任一项所述的掺杂型金刚石粉的制备方法，其特征在于，基体包括铜箔、铜合金箔或硬质合金箔中的任意一种，优选为铜箔。
  10. 按照权利要求1-3任一项所述的掺杂型金刚石粉的制备方法，其特征在于，所述掺杂型金刚石粉为掺硼金刚石粉，包括以下步骤：
    (a)将铜箔用酒精超声清洗20-30min干燥备用；
    (b)将清洗后的铜箔置于纳米金刚石粉悬浮液中超声20-40min；
    (c)将超声后的铜箔放入热丝化学气相沉积设备中，对热丝进行碳化，向设备中通入氢气、甲烷、硼烷和任选的惰性气体，甲烷气体流量占总气体流量的2-8％，调节真空室气压为2-8Pa，灯丝温度为1800-2800℃，基体温度为600-900℃，沉积时间为1-7h，在铜箔表面形成一层厚度为2-12μm的掺硼金刚石薄膜；
    (d)真空下随炉冷却，取出铜箔，掺硼金刚石薄膜从铜箔上自然脱落，将脱落的掺硼金刚石薄膜碎片装入球磨设备中球磨，球磨材料包括不锈钢球、玛瑙球或碳化钨球中的一种或几种，球磨时间为3-7h；
    (e)将球磨后的掺硼金刚石粉先在质量分数为3-8％的稀硫酸中清洗5-15min，然后在温度50-70℃、体积比8-10:1的浓硫酸和浓硝酸的混合酸液中浸泡20-40min，再将所得掺硼金刚石粉分散在水中，超声6-12小时，蒸馏后得到掺硼金刚石粉。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101481792A (zh) * 2008-01-08 2009-07-15 中国科学院物理研究所 一种硼掺杂金刚石超导材料的制备方法
KR20140072300A (ko) * 2012-11-30 2014-06-13 한국과학기술연구원 기체로부터의 입자 합성을 이용한 다이아몬드 파우더의 제조 방법 및 이에 의하여 제조된 다이아몬드 파우더
CN104164702A (zh) * 2014-08-08 2014-11-26 上海交通大学 一种硼掺杂超/精细金刚石单晶微粉的制备方法
CN106119807A (zh) * 2016-07-09 2016-11-16 大连理工大学 一种掺硼金刚石粉末的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101481792A (zh) * 2008-01-08 2009-07-15 中国科学院物理研究所 一种硼掺杂金刚石超导材料的制备方法
KR20140072300A (ko) * 2012-11-30 2014-06-13 한국과학기술연구원 기체로부터의 입자 합성을 이용한 다이아몬드 파우더의 제조 방법 및 이에 의하여 제조된 다이아몬드 파우더
CN104164702A (zh) * 2014-08-08 2014-11-26 上海交通大学 一种硼掺杂超/精细金刚石单晶微粉的制备方法
CN106119807A (zh) * 2016-07-09 2016-11-16 大连理工大学 一种掺硼金刚石粉末的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
REN, YIFANG: "A New Method for Producing Diamond Grains", ABRASIVES AND GRINDING, 30 April 1992 (1992-04-30), pages 45, XP009520926, ISSN: 1006-852X *
SHEN, XIAOTIAN ET AL.: "Preparation of CVD Microcrystalline Diamond Powders on Cu Substrates", DIAMOND & ABRASIVES ENGINEERING, vol. 36, no. 6, 31 December 2016 (2016-12-31), pages 20 - 24, XP009520927, ISSN: 1006-852X *

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