CN115466954A - 金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法 - Google Patents
金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 110
- 239000010432 diamond Substances 0.000 title claims abstract description 110
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 55
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000007747 plating Methods 0.000 claims abstract description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000007669 thermal treatment Methods 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 230000003746 surface roughness Effects 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 4
- 238000007735 ion beam assisted deposition Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 238000007517 polishing process Methods 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 abstract description 4
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
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- 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
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- 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
- C23C16/44—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 method of coating
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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Abstract
一种金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法，属于复合材料制备领域。首先对金刚石基底进行预处理，之后在金刚石表面镀覆催化层，接着采用直流喷射等离子体电弧炉对镀有催化层的金刚石进行快速热处理得到金刚石/石墨烯材料，然后镀覆或涂覆生长碳纳米管的催化剂，最后采用化学气相沉积法在石墨烯表面生长垂直碳纳米管，最终获得金刚石/石墨烯/碳纳米管全碳基复合材料。本发明复合材料制备方法工艺成熟，通过石墨烯作为中间过渡层以共价键分别连接金刚石和垂直阵列碳纳米管，具有稳定的键合方式，兼具优异的热学性能和独特的电学性能，实现了高稳定性、高性能全碳基复合功能材料的制备，有望满足未来功率电子器件的设计和应用。
Description
技术领域
本发明涉及复合材料制备技术领域，尤其涉及一种金刚石、石墨烯和碳纳米管组成的全碳基复合材料的制备方法。
背景技术
碳具有石墨、金刚石、富勒烯、碳纳米管、石墨烯等多种同素异形体。金刚石是自然界中导热性能最好的材料，常温下的热导率能达到2200W·m-1·K-1，是铜的5倍，同时金刚石的电学特性包括大的禁带宽度(5.5eV)、高的载流子迁移率(空穴:3800cm2·V-1·s-1，电子:4500cm2·V-1·s-1)，在半导体功率器件中有着巨大的潜能。碳纳米管可以看做是石墨烯片层卷曲而成，因此碳纳米管和石墨烯分别作为一维、二维碳材料，在热导率和电子迁移率方面都可具有极高的数值。石墨烯在室温下的载流子迁移率约为15000cm2·V-1·s-1，单层石墨烯的导热系数可高达5300W·m-1·K-1，而碳纳米管基于其特殊卷曲结构，沿着长度方向的热交换性能很高，因此合适取向的碳纳米管可以结合良好导热性能的材料如金刚石，通过调控载流子运输行为实现全碳基复合材料制备并应用于功率电子器件。
但金刚石中碳原子为sp3杂化，垂直于金刚石表面生成碳纳米管阵列相当于将sp3键合直接转化为sp2键合，理论上难以实现，所以一般在金刚石上生成垂直排布的碳纳米管都需要在金刚石表面添加催化剂作为碳纳米管的形核位点。但上述方法存在一定的问题，比如催化剂的种类、大小和用量都对碳纳米管的直径、结晶度有显著影响，不易调控碳纳米管形貌，并且不同催化剂可能会影响金刚石基底与碳纳米管之间的结合强度。已知石墨烯与碳纳米管都为碳原子sp2杂化纳米结构，并且以石墨烯和垂直碳纳米管构建共价键合稳定三维结构技术成熟。而金刚石表面原位催化生成的石墨烯与金刚石具有良好的晶体结构匹配性，快速热处理后得到的金刚石/石墨烯结构质量高、稳定性好且电学性能优异。因此通过石墨烯在金刚石和垂直碳纳米管之间作为过渡层，由共价键连接三种材料进而制备出结构稳定、具有良好导热性能和独特电学性能的金刚石/石墨烯/碳纳米管全碳基复合材料。
发明内容
本发明提供一种金刚石、石墨烯和碳纳米管全碳基复合材料的制备方法。该材料结合金刚石、石墨烯和碳纳米管在导热传输和电学上的优异性能，以石墨烯作为过渡层以共价键连接金刚石和垂直取向碳纳米管，实现金刚石、石墨烯和碳纳米管三种材料结构上的稳定键合，在功率电子器件领域具有良好的应用前景。
如上所述金刚石、石墨烯和碳纳米管全碳基复合材料的制备方法，具体实施步骤为：
(1)对金刚石基底进行抛光、酸洗和超声清洗；
(2)对步骤(1)得到的金刚石表面镀覆厚度为10-50nm的催化层；
(3)通过直流喷射等离子体电弧炉将步骤(2)中得到的表面含有催化层的金刚石在等离子体气氛下进行快速热处理生成石墨烯；
(4)将步骤(3)热处理后表面含有金属或合金催化层的金刚石放置于稀酸溶液直至催化层完全溶解，清洗后得到金刚石/石墨烯材料；
(5)在步骤(4)得到的金刚石/石墨烯材料上镀覆或涂覆生长碳纳米管的催化剂；
(6)采用化学气相沉积方法在步骤(5)得到的金刚石/石墨烯材料中石墨烯表面生长垂直碳纳米管，得到所述金刚石/石墨烯/碳纳米管复合材料。
进一步地，步骤(1)所述金刚石基底可为人造或天然单晶、多晶金刚石中的一种。
进一步地，步骤(1)所述抛光过程为机械抛光，表面粗糙度小于1nm。
进一步地，步骤(1)所述酸洗和超声清洗过程为将抛光后的金刚石置于HNO3：H2SO4＝1:3混合酸溶液进行酸煮，冷却后使用丙酮、酒精、去离子水依次超声清洗，随后在氮气的氛围下烘干。
进一步地，步骤(2)所述催化层可为铁、钴、镍、铜、铬等过渡金属或含上述过渡金属一种及以上组分合金中的一种。
进一步地，步骤(2)所述催化层镀覆方法可为磁控溅射、电子束蒸发、离子束辅助沉积和原子层沉积中的一种。
进一步地，步骤(3)所述热处理等离子体气氛中氩气和氢气体积比为2:1，保温温度为700-900℃，热处理保温时长为0.5-2.5min，热处理升温速率大于50℃/s。
进一步地，步骤(4)所述稀酸溶液可为稀盐酸、稀硝酸中的一种。
进一步地，步骤(5)所述催化剂优先为铁、钴、镍、铜、铬等过渡金属中的一种或它们不同组分的合金中1种或2种以上混合物中的一种，对应的镀覆方法为磁控溅射、电子束蒸发、离子束辅助沉积和原子层沉积中的一种；也可为氯化铁、硝酸铁、氯化亚铁、二茂铁等含有一种或多种金属的盐类或有机化合物中的一种，对应的涂覆方法为旋涂，镀覆方法为气态输入。
进一步地，步骤(6)所述化学气相沉积法可为热解化学气相沉积、等离子体增强化学气相沉积中的一种。
本发明实施过程的关键在于：
1.本发明中为了满足生长石墨烯的金刚石样品足够平整，要求金刚石表面粗糙度小于1nm。
2.本发明中为得到缺陷少的高质量石墨烯，要求使用直流喷射等离子体电弧炉设备，保证含有催化层的金刚石的热处理过程中升降温速度足够快，保证金刚石和石墨烯共价键合的同时避免升降温过程对石墨烯结构产生损伤。
3.本发明在制备碳纳米管生长催化剂前需保证制备石墨烯的残余催化层去除干净，避免残余催化层对后续碳纳米管的生长造成影响。
本发明的优点在于：
本发明涉及一种金刚石、石墨烯和碳纳米管全碳基复合材料制备方法，通过石墨烯作为中间层通过共价键连接金刚石和碳纳米管，得到稳定且拥有良好热学性能和独特电学性能的复合材料。
本发明突出优势在于：
1.本发明采用的制备方法周期短，工艺技术成熟，采用的催化剂等为常见原料，成本低廉，可大规模生产应用。
2.本发明通过石墨烯作为过渡层以共价键连接金刚石和垂直碳纳米管两种碳基材料，得到键合稳定的全碳基复合结构。
3.金刚石、石墨烯、碳纳米管都具有良好的热导率和载流子迁移率，本发明得到的复合材料结合三种材料特性具有良好导热性能和独特电学性能，以满足功率电子器件的设计和应用。
具体实施方式
下面结合具体实施例对本发明的技术方案做进一步说明。
实施例1
1、对化学气相沉积(100)单晶金刚石进行抛光酸洗。首先将化学气相沉积(100)单晶金刚石进行机械抛光，其表面粗糙度值达到0.72nm，然后将抛光后的单晶金刚石在浓硝酸、浓硫酸比例为1:3的混合酸液中煮沸3h，冷却后使用丙酮、酒精、去离子水依次超声清洗15min。
2、采用磁控溅射法在步骤1得到的单晶金刚石表面镀一层厚度为40nm的Cu催化层。其中背底真空度为10-4Pa，射频功率为200W，镀制时间为20min。
3、使用直流喷射等离子体电弧炉将步骤2)中得到的表面镀Cu的单晶金刚石在氩气和氢气混合等离子体气氛下进行快速热处理。其中，氩气流量为6slm，氢气流量为3slm，磁场电流为3.5A，电弧电流为70A。热处理最高保温温度达800℃，热处理时间为1.5min，升降温速率达55℃/s，灭弧后样品在氩气氛围下随炉冷却至室温取出。
4、将步骤3快速热处理后得到的镀Cu单晶金刚石放置于体积分数为2％的稀硝酸中浸泡约3.5h，取出后放置于去离子水中将表面残余盐酸清洗干净，得到金刚石/石墨烯复合材料。
5、采用磁控溅射技术在步骤4得到的金刚石/石墨烯材料表面镀一层厚度为30nm的Fe催化层。其中背底真空度为5×10-4Pa，射频功率为200W，镀制时间为15min。
6、采用等离子体增强化学气相沉积技术，在步骤5所得含Fe催化层的金刚石/石墨烯材料石墨烯表面制备碳纳米管。首先将含Fe催化层的金刚石/石墨烯材料放入反应系统中，并抽真空至10-5Pa，然后加热基底到550℃，通入H2刻蚀，保持10min，开启系统的等离子源，功率选定在1200W，再调整基底到生长温度650℃，通入H2和CH4，CH4浓度为10％，生长时间30min。生长结束后将系统降温，取出样品，最终得到(100)单晶金刚石/石墨烯/碳纳米管全碳基复合材料。
实施例2
1、对高温高压(111)单晶金刚石进行抛光酸洗。首先将Ib型高温高压(111)单晶金刚石进行机械抛光，其表面粗糙度值达到0.69nm，然后将抛光后的单晶金刚石在浓硝酸、浓硫酸比例为1:3的混合酸液中煮沸3h，冷却后使用丙酮、酒精、去离子水依次超声清洗15min。
2、采用磁控溅射法在步骤1得到的单晶金刚石表面镀一层厚度为30nm的Ni催化层。其中背底真空度为10-4Pa，射频功率为200W，镀制时间为15min。
3、使用直流喷射等离子体电弧炉将步骤2中得到的表面镀Ni的单晶金刚石在氩气和氢气混合等离子体气氛下进行快速热处理。其中，氩气流量为6slm，氢气流量为3slm，磁场电流为3.5A，电弧电流为70A。热处理最高保温温度达750℃，热处理时间为2min，升降温速率达60℃/s，灭弧后样品在氩气氛围下随炉冷却至室温取出。
4、将步骤3快速热处理后得到的镀Ni单晶金刚石放置于体积分数为2％的稀盐酸中浸泡约4h，取出后放置于去离子水中将表面残余盐酸清洗干净，得到金刚石/石墨烯复合材料。
5、通过温和的超声处理将二茂铁(10wt.％)溶解在二甲苯中，在化学气相沉积过程生长碳纳米管过程中二茂铁与二甲苯混合物作为气源一起通入系统。
6、采用等离子体增强化学气相沉积技术，在步骤4所得的金刚石/石墨烯材料石墨烯表面制备碳纳米管。首先将金刚石/石墨烯材料放入反应系统中，并抽真空至10-4Pa，然后加热基底到600℃，通入H2刻蚀，保持15min，开启系统的等离子源，功率选定在1500W，再调整基底到生长温度700℃，通入二茂铁/二甲苯混合物，设定生长时间为45min。生长结束后将系统降温，取出样品，最终得到(111)单晶金刚石/石墨烯/碳纳米管全碳基复合材料。
实施例3
1、对化学气相沉积(111)多晶金刚石进行抛光酸洗。首先将化学气相沉积(111)多晶金刚石进行机械抛光，其表面粗糙度值达到0.82nm，然后将抛光后的多晶金刚石在浓硝酸、浓硫酸比例为1:3的混合酸液中煮沸3h，冷却后使用丙酮、酒精、去离子水依次超声清洗15min。
2、采用磁控溅射法在步骤1得到的多晶金刚石表面镀一层厚度为50nm的Ni催化层。其中背底真空度为5×10-4Pa，射频功率为200W，镀制时间为25min。
3、使用直流喷射等离子体电弧炉将步骤2中得到的表面镀Ni的多晶金刚石在氩气和氢气混合等离子体气氛下进行快速热处理。其中，氩气流量为6slm，氢气流量为3slm，磁场电流为3.5A，电弧电流为70A。热处理最高保温温度达850℃，热处理时间为2min，升降温速率达55℃/s，灭弧后样品在氩气氛围下随炉冷却至室温取出。
4、将步骤3快速热处理后得到的镀Ni多晶金刚石放置于体积分数为2％的稀硝酸中浸泡约4h，取出后放置于去离子水中将表面残余盐酸清洗干净，得到金刚石/石墨烯复合材料。
5、采用磁控溅射技术在步骤4得到的金刚石/石墨烯材料表面镀一层厚度为40nm的Fe催化层。其中背底真空度为5×10-4Pa，射频功率为200W，镀制时间为20min。
6、采用热解化学气相沉积技术，在步骤5所得含Fe催化层的金刚石/石墨烯材料制备碳纳米管。首先将含Fe催化层的金刚石/石墨烯材料放入反应系统中，并抽真空至10-5Pa，然后加热基底到700℃，通入H2刻蚀，保持20min，再调整基底到生长温度950℃，通入H2和C2H2，C2H2浓度为10％，生长时间25min。生长结束后将系统降温，取出样品，最终得到多晶金刚石/石墨烯/碳纳米管全碳基复合材料。
Claims (8)
1.一种金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法，其特征在于在金刚石表面镀覆催化层；随后采用直流喷射等离子体电弧炉对镀有催化层的金刚石进行快速热处理后去除催化层，得到共价键合的金刚石/石墨烯材料；然后镀覆或涂覆生长碳纳米管的催化剂；最后采用化学气相沉积法在石墨烯表面生长共价结合的垂直碳纳米管，得到结构稳定、性能良好的金刚石/石墨烯/碳纳米管全碳基复合材料；
具体制备步骤如下：
(1)对金刚石基底进行抛光、酸洗和超声清洗；
(2)对步骤(1)得到的金刚石表面镀覆厚度为10-50nm的催化层；
(3)通过直流喷射等离子体电弧炉将步骤(2)中得到的表面含有催化层的金刚石在等离子体气氛下进行快速热处理生成石墨烯；
(4)将步骤(3)热处理后表面含有金属或合金催化层的金刚石放置于稀酸溶液直至催化层完全溶解，清洗后得到金刚石/石墨烯材料；
(5)在步骤(4)得到的金刚石/石墨烯材料上镀覆或涂覆生长碳纳米管的催化剂；
(6)采用化学气相沉积方法在步骤(5)得到的金刚石/石墨烯材料中石墨烯表面生长垂直碳纳米管，得到所述金刚石/石墨烯/碳纳米管复合材料；
步骤(1)所述抛光过程为机械抛光，表面粗糙度小于1nm；
步骤(2)所述催化层为铁、钴、镍、铜、铬过渡金属或含上述过渡金属一种及以上组分合金中的一种。
2.如权利要求1所述金刚石/石墨烯/碳纳米管全碳基复合材料制备方法，其特征在于步骤(1)所述金刚石基底为人造或天然单晶、多晶金刚石中的一种。
3.如权利要求1所述金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法，其特征在于步骤(1)所述酸洗和超声清洗过程为将抛光后的金刚石置于HNO3：H2SO4＝1:3混合酸溶液进行酸煮，冷却后使用丙酮、酒精、去离子水依次超声清洗，随后在氮气的氛围下烘干。
4.如权利要求1所述金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法，其特征在于步骤(2)所述催化层镀覆方法为磁控溅射、电子束蒸发、离子束辅助沉积和原子层沉积中的一种。
5.如权利要求1所述金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法，其特征在于步骤(3)所述热处理等离子体气氛中氩气和氢气体积比为2:1，保温温度为700-900℃，热处理保温时长为0.5-2.5min，热处理升温速率大于50℃/s。
6.如权利要求1所述金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法，其特征在于步骤(4)所述稀酸溶液为稀盐酸、稀硝酸中的一种。
7.如权利要求1所述金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法，其特征在于步骤(5)所述催化剂为铁、钴、镍、铜、铬过渡金属中的一种或它们不同组分的合金中1种或2种以上混合物，对应的镀覆方法为磁控溅射、电子束蒸发、离子束辅助沉积和原子层沉积中的一种；或为氯化铁、硝酸铁、氯化亚铁、二茂铁含有一种或多种金属的盐类或有机化合物，对应的涂覆方法为旋涂，镀覆方法为气态输入。
8.如权利要求1所述金刚石/石墨烯/碳纳米管全碳基复合材料的制备方法，其特征在于步骤(6)所述化学气相沉积法为热解化学气相沉积、等离子体增强化学气相沉积中的一种。
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