WO2022095747A1 - 一种金刚石表面改性的方法及应用 - Google Patents
一种金刚石表面改性的方法及应用 Download PDFInfo
- Publication number
- WO2022095747A1 WO2022095747A1 PCT/CN2021/126269 CN2021126269W WO2022095747A1 WO 2022095747 A1 WO2022095747 A1 WO 2022095747A1 CN 2021126269 W CN2021126269 W CN 2021126269W WO 2022095747 A1 WO2022095747 A1 WO 2022095747A1
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- WIPO (PCT)
- Prior art keywords
- diamond
- coating
- cleaning
- wetting angle
- fluorine
- Prior art date
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 187
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000004048 modification Effects 0.000 title claims abstract description 27
- 238000012986 modification Methods 0.000 title claims abstract description 27
- 238000004140 cleaning Methods 0.000 claims abstract description 153
- 238000000576 coating method Methods 0.000 claims abstract description 126
- 239000011248 coating agent Substances 0.000 claims abstract description 122
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- -1 fluorocarbon compound Chemical class 0.000 claims abstract description 20
- 230000007704 transition Effects 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 230000003287 optical effect Effects 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 55
- 238000009736 wetting Methods 0.000 claims description 50
- 229910052731 fluorine Inorganic materials 0.000 claims description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 45
- 239000011737 fluorine Substances 0.000 claims description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 238000000151 deposition Methods 0.000 claims description 38
- 230000008021 deposition Effects 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- 238000005229 chemical vapour deposition Methods 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000005553 drilling Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 230000003373 anti-fouling effect Effects 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- BLIQUJLAJXRXSG-UHFFFAOYSA-N 1-benzyl-3-(trifluoromethyl)pyrrolidin-1-ium-3-carboxylate Chemical compound C1C(C(=O)O)(C(F)(F)F)CCN1CC1=CC=CC=C1 BLIQUJLAJXRXSG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 238000004880 explosion Methods 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000127 oxygen difluoride Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 230000001568 sexual effect Effects 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000005520 cutting process Methods 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract description 3
- 239000012567 medical material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 28
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical class [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 14
- 239000003814 drug Substances 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 239000003513 alkali Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 5
- 230000003064 anti-oxidating effect Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
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- 239000011159 matrix material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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Images
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
- 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
- C23C16/50—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 using electric discharges
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- 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
-
- 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
-
- 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
Definitions
- the invention belongs to the technical field of diamond modification, and in particular relates to a method and application of diamond surface modification.
- Diamond has high hardness, good light transmittance and stable chemical properties. It can be widely used in jewelry, optical materials, machining materials, semiconductor materials, thermal conductive materials and other fields. Many people have carried out various researches on the application of diamond. For example, in the patent CN103436853B of Suzhou Jinyuan Nano Technology Co., Ltd. Shi Zhen et al, a diamond film is used as an imprint template. In patent CN101489928B, diamond powder is used for grinding and polishing. In the patent CN108362751A, Xu Qingbo of Wuhan University of Technology and others used diamond as an electrochemical biosensor. In the patent CN103269816B, diamond is used as a diamond composite sheet, a dresser and so on.
- the object of the present invention is to provide an improved method for diamond surface modification in order to overcome the deficiencies of the prior art, and to use fluorocarbon compounds and/or fluorosilicon compounds to modify the diamond surface, so that the application of the modified diamond The field has been greatly expanded.
- the technical scheme adopted in the present invention is:
- a method for diamond surface modification comprising a diamond surface cleaning process and a process of forming a coating on the diamond surface, the coating comprising a surface coating located on the outermost surface and an optional surface coating located on the surface coating and the diamond surface.
- the transition coating between the diamond surfaces, the top coating is formed of a fluorocarbon compound and/or a fluorosilicon compound, the transition coating has one or two or more layers, and each layer is selected from A combination of one or more of fluorocarbon, fluorosilicon, carbon, silicon, and silicon carbide is formed.
- the top coat layer is formed of fluorocarbon compounds and/or fluorosilicon compounds means that the top coat layer is mainly formed of fluorocarbon compounds and/or fluorosilicon compounds, and there may also be some Doping elements, for example, include one or more of O, H, and N, but are not limited thereto.
- each layer of the transition coating is formed by a combination of one or more selected from fluorocarbons, fluorosilicon compounds, carbon, silicon, and silicon carbide, which means that each layer of the transition coating is
- the layer is mainly formed of a combination of one or more selected from fluorocarbons, fluorosilicon compounds, carbon, silicon, and silicon carbide, and some doping elements may also exist in the transition coating, such as including O, H, One or more of N, but not limited thereto.
- the thickness, refractive index, wetting angle, oxidation resistance and friction coefficient of the coating can be adjusted.
- a solid foundation has been laid for applications in drilling and exploration, medical equipment, fluorine chemicals, electronic chemicals and other fields.
- the thickness of the coating is 1 nm-100 ⁇ m; the refractive index of the coating is 1.5-3.5, and the refractive index is tested with reference to GB/T 7962.1-2010; the wetting angle of the coating is 1 ⁇ 120°, the wetting angle is tested with reference to GB/T30447-2013; the oxidation resistance of the coating is 400-1200°C, and the oxidation resistance is tested with reference to GB/T 13303-1991; the coating The friction coefficient of the layer is 0.04 to 1.0, and the friction coefficient is tested with reference to GB/T 10006-1988.
- the thickness of the coating is 2 nm-90 ⁇ m, or 3 nm-70 ⁇ m, or 4 nm-50 ⁇ m; the wetting angle is 20-120°, or 50-120°, or 70-120°, or 80-120°, or 90-120°, or 100-120°; the oxidation resistance is 600-1200°C, or 800-1200°C.
- the coating may only be the topcoat formed directly on the diamond surface.
- the coating may comprise the topcoat at the outermost surface and a transition coating between the topcoat and the diamond surface.
- the transition coating can be a one-layer structure, the one-layer structure is mainly composed of one or more selected from the group consisting of fluorocarbons, fluorosilicon compounds, carbon, silicon, and silicon carbide or the transition coating is a two-layer structure, and each layer is mainly formed by a combination of one or more selected from fluorocarbons, fluorosilicon compounds, carbon, silicon, and silicon carbide, preferably , in the two-layer structure, one layer directly formed on the diamond surface is mainly formed of carbon, and the other layer is mainly formed of silicon carbide; or the transition coating is a multi-layer structure, and each layer is mainly composed of selected Formed from a combination of one or more of fluorocarbons, fluorosilicon compounds, carbon, silicon, silicon carbide, preferably, a layer of the multi-layer
- each layer of the coating layer is an amorphous, single crystal, polycrystalline layer or a liquid layer, and each layer of the coating layer further contains doping elements, and the The doping element is one or more of O, N and H.
- each layer of the coating is formed by a chemical vapor deposition method
- the working gas used in the chemical vapor deposition method is methane, hydrogen, carbon tetrafluoride, silicon tetrafluoride, silane , one or more of ethanol, acetone, nitrogen, argon, fluorine, ammonia, hydrogen fluoride, oxygen difluoride, xenon difluoride, nitrogen trifluoride, and the working gas that forms the surface coating
- At least fluorine source gas is contained, and the purity of each gas in the working gas is >99.9999%.
- the selected gases/liquids are ultra-high-purity electronic chemicals, and the impurity content of the liquid can be selected to be less than 1000ppm, preferably less than 1ppb, according to the requirements of working conditions and costs.
- the working temperature is room temperature-1000 °C
- the working pressure is 0.001Pa-100kPa
- the deposition power is 0.1W-100kW
- the energy source is plasma cyclotron resonance, DC glow discharge, microwave plasma discharge, magnetron sputtering, hot wire plasma, barrier dielectric discharge, DC arc one or more energy coupling, through the chemical vapor deposition method
- the thickness of the coating can be adjusted between 1nm-100 ⁇ m, the refractive index can be adjusted between 1.5 and 3.5, the wetting angle can be adjusted between 1 and 120°, and the oxidation resistance can be adjusted between 400 and 1200°C. Adjustable between, friction coefficient between 0.04 ⁇ 1.0 adjustable.
- the working temperature is 25-1000°C, or 50-900°C, or 100-900°C, or 150-900°C, or 200-900°C, or 300- 900°C;
- the working pressure is 1Pa ⁇ 100kPa, or 10Pa ⁇ 100kPa, or 100Pa ⁇ 100kPa, or 0.5 ⁇ 100kPa, or 0.5 ⁇ 80kPa, or 0.5 ⁇ 50kPa, or 0.5 ⁇ 30kPa, or 0.5-20kPa;
- the deposition power is 1-100kW, or 10-80kW, or 10-60kW, or 10-40kW.
- the diamond is natural diamond, synthetic diamond, polycrystalline diamond, single crystal diamond, diamond film, diamond synthesized by explosion method, powder diamond synthesized at high temperature and high pressure, modified diamond, doped diamond or Diamond-like carbon
- the diamond also contains a carbon material of sp3 structure to a certain extent, and the carbon material includes one of carbon fibers, graphite, carbon nanotubes, buckyballs, polycrystalline carbon, amorphous carbon, and carbon black.
- the diamond surface cleaning process includes the following steps:
- alkaline cleaning mix and prepare alkaline cleaning solution with ammonia, hydrogen peroxide and pure water in a volume ratio of 1:(0.1-10):(1-100), and ultrasonically clean for 1min-120min;
- Plasma cleaning place the alcohol-washed diamond in high-purity hydrogen with purity>99.9999%, high-purity argon with purity>99.9999%, and high-purity oxygen with purity>99.9999% in a volume ratio of 1: (0.01-100):(0.01-1) mixed gas, control the electron temperature (0.1-100) ⁇ 10 4K, electron density (0.1-100) ⁇ 10 11/cm 3, clean for 0.1min-120min, The fresh diamond face is exposed.
- each liquid raw material used is of pharmaceutical grade
- the impurity level can be selected to be below 1000ppm of impurity content according to the actual situation, or the impurity level can be selected to meet the requirements of the diamond cleaning process of the corresponding level. choose.
- the impurity content of each of the liquid raw materials is preferably less than 1 ppb.
- the mass concentration of the hydrochloric acid in the cleaning process, can be selected to be 0.01-37.5% according to the actual situation, the mass concentration of the hydrogen peroxide is 0.01-85%, and the mass concentration of the ammonia water is 0.01-100%, the mass concentration of the sulfuric acid is 0.01-105%, and the mass concentration of the isopropanol is 0.01-99.99%.
- the mass concentration of the hydrochloric acid is 5-37.5%, or 10-37%, or 20-37%, or 30-37%;
- the mass concentration is 5-80%, or 10-70%, or 20-60%, or 30-50%, or 30-40%;
- the mass concentration of the ammonia water is 1-29%, or 5 to 29%, or 10 to 29%, or 20 to 29%;
- the mass concentration of the sulfuric acid is 1 to 100%, or 20 to 100%, or 40 to 100%, or 60 to 100%. %, or 80 to 100%;
- the mass concentration of the isopropanol is 10 to 99.99%, or 30 to 99.99%, or 50 to 99.99%, or 70 to 99.99%, or 80 to 99.99% , or 90 to 99.99%.
- the mass concentration of the hydrochloric acid is 37%
- the mass concentration of the hydrogen peroxide is 35%
- the mass concentration of the ammonia water is 29%
- the mass concentration of the sulfuric acid is 96%
- the mass concentration of the isopropanol is The concentration is 99.99%.
- one or more of surfactants, wetting agents, coupling agents, defoaming agents, and dispersing agents are optionally added to each of the cleaning solutions to improve cleaning effects.
- the mixed gas may optionally include one or more of fluorine-containing gas, chlorine-containing gas, nitrogen-containing gas, and carbon-containing gas. Not limited to this.
- the surface of the diamond after acid washing, alkali washing, oxidative cleaning and alcohol washing is controlled to be less than 10 particles/mL, and the metal on the diamond surface is controlled to be less than 1 ppb.
- the diamond surface has no organic pollutants.
- the plasma cleaning energy source is one or a combination of glow plasma, microwave plasma, barrier dielectric discharge plasma, and DC discharge plasma.
- the discharge cleaning pressure is 0.01Pa-100kPa
- the discharge cleaning power is 0.1W-100kW
- the surface micro-damage layer is removed by cleaning
- the thickness of the diamond is removed by plasma is 0.2-0.8 ⁇ m.
- the discharge cleaning gas pressure is 0.1Pa ⁇ 90kPa, or 0.1Pa ⁇ 80kPa, or 0.1Pa ⁇ 60kPa, or 0.1Pa ⁇ 40kPa, or 0.1Pa ⁇ 20kPa;
- the power of the discharge cleaning is 1W-100kW, or 100W-80kW, or 1-70kW, or 1-50kW, or 3-30kW, or 3-20kW.
- step (a) in the diamond surface cleaning process the volume ratio of the hydrochloric acid, hydrogen peroxide, and pure water is 1:(0.1-5):(5-100), cleaning The time is 2min ⁇ 100min, the preferred cleaning time is 5min ⁇ 60min, and the more preferred cleaning time is 5min ⁇ 40min.
- step (b) the volume ratio of the ammonia water, hydrogen peroxide and pure water is 1:(0.1-5):(1-100), and the cleaning time is 2min ⁇ 100min, preferably the cleaning time is 5min ⁇ 60min, more preferably cleaning The time is 10min ⁇ 40min.
- step (c) the volume ratio of the sulfuric acid, hydrogen peroxide and pure water is 1:(0.1-10):(0-50), and the cleaning time is 10min ⁇ 100min, preferably, the volume ratio is 1:(0.1- 10): (0-20), the cleaning time is 15min-50min; more preferably, the volume ratio is 1:(0.1-5):(0-10).
- the cleaning time is 1min-100min; preferably 4min-60min; more preferably 10min-40min.
- the volume ratio of the hydrogen, argon, and oxygen is 1:(0.01-50):(0.05-1), and the electron temperature (0.5-50) ⁇ 10 4K and the electron density (0.5-50) are controlled. ) ⁇ 10 11/cm 3, cleaning 1min-100min;
- the volume ratio of described hydrogen, argon, oxygen is 1:(0.05-20):(0.05-1), control electron temperature (0.5-30 ) ⁇ 10 4K, electron density (0.5-30) ⁇ 10 11/cm , cleaning 4min-60min; more preferably, the volume ratio of the hydrogen, argon, and oxygen is 1:(0.05-10):( 0.05-1), control electron temperature (0.5-20) ⁇ 10 4K, electron density (0.5-20) ⁇ 10 11 /cm 3, clean 4min-50min; further preferably, the hydrogen, argon, oxygen The volume ratio is 1:(0.05-5):(0.05-1), the electron temperature (0.5-10) ⁇ 10 4K, the electron density (0.5-10) ⁇ 10 11/cm 3 are controlled, and the cleaning time
- Another technical solution adopted in the present invention is a surface-modified diamond, wherein the surface-modified diamond is obtained by the above-mentioned method for diamond surface modification.
- the above-mentioned surface-modified diamond is used in the fields of jewelry, optics, grinding and polishing, drilling, fluorine chemical, medicine, and electronic chemicals.
- the wavelength of light passing through the surface-modified diamond is controlled, and by adjusting the thickness of the coating to correspond to the integer wavelength + 1/4 of the wavelength, the corresponding
- the complementary color of the surface-modified diamond makes the surface-modified diamond correspondingly present different transparent colors.
- the thickness of the coating when it is light blue, the thickness of the coating is 0.16 ⁇ m; when it is light red, the thickness of the coating is 0.128 ⁇ m; When it is gray, the thickness of the coating is 5 ⁇ m, and the mass content of sp 2 structure carbon in the coating is less than 0.05%; when it is black, the thickness of the coating is more than 10 ⁇ m, and the sp 2 structure in the coating is The mass content of carbon is greater than 0.05%;
- the wetting angle of the surface of the surface-modified diamond to water is greater than or equal to 110°
- the wetting angle to oil is greater than or equal to 80°
- the surface is water and oil repellent, making the surface
- the modified diamond is no-clean and anti-fouling, and keeps the appearance of diamond jewelry shiny, wherein, the wetting angle is adjusted by adjusting the mass content of fluorine in the surface coating.
- the wetting angle begins to increase, and when the mass content of the fluorine is greater than 20%, the wetting angle reaches a limit value;
- the temperature resistance of the surface-modified diamond is greater than or equal to 1000°C, which is greater than 850°C that the diamond can burn daily, which can greatly improve the resistance of the surface-modified diamond in the high temperature state usually seen in fires.
- Safety wherein the oxidation resistance is adjusted by adjusting the mass content of the fluorosilicon compound in the top coat, the oxidation resistance increases as the mass content of the fluorosilicon compound increases, and when When the mass content of the fluorosilicon compound is greater than 20%, there is a clear anti-oxidation effect, and when the mass content of the fluorosilicon compound is greater than 80%, the anti-oxidation property is no longer improved.
- the temperature resistance of the surface-modified diamond is greater than 1000°C, and the surface-modified diamond is used as an optical window and lens, and can be used in high-power lasers and microwave windows.
- the conventional bearing power density it is increased by more than 50%, wherein the oxidation resistance is adjusted by adjusting the mass content of the fluorosilicon compound in the surface coating, and the oxidation resistance increases with the fluorosilicon The mass content of the compound increases, and when the mass content of the fluorosilicon compound is greater than 80%, the oxidation resistance is no longer improved;
- the wetting angle of the surface of the surface-modified diamond to water is greater than or equal to 110°, and the wetting angle to oil is greater than or equal to 80°.
- Anti-reflection, anti-reflection, anti-fouling and anti-fog coatings can increase solar energy utilization by 2-5% and reduce manual cleaning costs by more than 80%, wherein the wetting angle is adjusted by adjusting the fluorine in the surface coating. The difference in mass content is adjusted. When the mass content of fluorine is greater than 0.5%, the wetting angle begins to increase, and when the mass content of fluorine is greater than 20%, the wetting angle reaches a limit value.
- the size of the wetting angle of the coating is selected according to the surface tension of the selected solvent and the diamond particle size,
- the surface-modified diamond can be highly dispersed and freely suspended in the water-based or oil-based grinding and polishing liquid.
- the particle size range of the diamond is selected in the range of several nanometers to several micrometers. Only by adjusting the surface tension , to achieve the purpose of suspension, wherein, the adjustment of the wetting angle is adjusted by adjusting the mass content of fluorine in the surface coating.
- the wetting angle When the mass content of fluorine is greater than 0.5%, the wetting angle The angle begins to increase, and when the mass content of the fluorine is greater than 20%, the wetting angle reaches a limit value. No need to add dispersant and suspending agent. The difficulty of preparing the grinding liquid is reduced, the purity of the grinding liquid is improved, and the disposal cost of the grinding liquid waste is reduced. Mainly used in thinning and CMP polishing in the semiconductor industry.
- the chemical industry with fluorine as the core has strong corrosiveness, high toxicity and high permeability.
- the surface-modified diamond can fully satisfy the characteristics of corrosion resistance, low permeability and good thermal conductivity due to the existence of the coating. It is one of the necessary materials in the field of fluorine chemical industry.
- the surface-modified diamond surface When applied to the medical field, the surface-modified diamond surface is oil- and water-repellent, has good bioaffinity, high strength, does not cause rejection reaction, and has low toxicity, and can be applied to surgical instruments and implanted human tissue instruments superior.
- the surface-modified diamond When applied to the field of electronic chemicals, the surface-modified diamond has good chemical inertness, no metal and particle dissolution, and is a good material for ultra-high-purity electronic chemical equipment. Mainly used in the production process of ultra-high purity sulfuric acid, hydrochloric acid, nitric acid, ammonia water and hydrofluoric acid below 10ppt.
- the present invention has the following advantages compared with the prior art:
- the present invention improves the color, light transmittance, hydrophilic properties, anti-oxidation properties, etc. of the diamond surface by using fluorocarbon compounds and/or fluorosilicon compounds for modification and modification on the diamond surface, and expands the use of the modified diamond in jewelry.
- the application effect of jewelry can also be used as optical window materials, medical materials, abrasive materials and cutting materials. It greatly expands the application field and use effect of diamond. It has laid a foundation for diamonds to be used in a wider range of fields and with higher effects.
- Figure 1 is a scanning electron microscope image of the surface of diamond (before modification).
- the surface-modified diamond of the present invention adopts the surface-modified diamond of the present invention to improve mainly in:
- lower biological rejection means lower medical expenses, lower pain, and higher surgical success rate
- the method of the invention takes diamond as a matrix, and prepares a coating of several nanometers to several hundreds of micrometers by cleaning the matrix and plasma chemical vapor deposition, which can effectively improve parameters such as surface wetting angle, friction coefficient and oxidation resistance of diamond.
- Fig. 1 the electron microscope scanning diagram of the surface of a certain diamond (before modification), and after being modified by the method of the present invention, the electron microscope scanning diagram of the surface of the diamond shows: before and after the modification, the diamond surface morphology No significant changes.
- the process route of surface modified diamond is carried out according to the process of surface acid cleaning ⁇ surface alkali cleaning ⁇ surface oxidation treatment ⁇ isopropanol cleaning ⁇ plasma cleaning ⁇ plasma chemical vapor deposition coating. in:
- Isopropyl alcohol cleaning clean the organic matter on the diamond surface, and at the same time remove the water, etc., to avoid re-contamination of the surface caused by high temperature baking.
- Plasma cleaning is used to remove the contamination layer on the diamond surface, remove the surface micro-damage layer, and form a good nucleation and bonding point with hydrogen, oxygen, fluorine and other related corrosive plasma atmosphere gases. .
- Coating deposition use plasma chemical vapor deposition carbon, silicon, nitrogen, oxygen, fluorine, hydrogen composite layer. Deposit specific thicknesses, specific surface wetting angles, and oxidation-resistant coatings according to process requirements.
- This example provides a method for preparing a surface-modified diamond, including the steps of cleaning and forming a coating on the diamond, and specifically including the following steps:
- the purity of each gas used in step (6) is greater than 99.9999%.
- the refractive index of the deposited coating after step (6) was 2.4; the wetting angle of the coating was 110°; the oxidation resistance of the coating was 900° C.; the friction coefficient of the coating was 0.6.
- the surface-modified diamond is mainly used in the jewelry industry, so that the surface of the diamond jewelry has non-destructive and antifouling properties.
- This example provides a method for preparing a surface-modified diamond, including the steps of cleaning and forming a coating on the diamond, and specifically including the following steps:
- microwave plasma chemical vapor deposition working pressure is 15kPa
- deposition temperature 800°C
- deposition power 20kW
- the deposition time is 10min
- the thickness of the deposited coating is 2 ⁇ m;
- microwave plasma chemical vapor deposition working pressure is 15kPa
- deposition temperature 800°C
- deposition power 20kW
- deposition time 30 min
- the thickness of the deposited coating is 6 ⁇ m
- the surface-modified diamond is obtained.
- the purity of each gas used in step (6) is greater than 99.9999%.
- the refractive index of the deposited coating after step (6) was 2.4; the wetting angle of the coating was 110°; the oxidation resistance of the coating was 1000° C.; the friction coefficient of the coating was 0.6.
- the surface-modified diamond is mainly used in additive-free diamond powder grinding fluid, and has good dispersibility and suspension.
- This example provides a method for preparing a surface-modified diamond, including the steps of cleaning and forming a coating on the diamond, and specifically including the following steps:
- microwave plasma chemical vapor deposition working pressure is 2kPa
- deposition temperature 600 °C
- deposition power 10kW
- the deposition time is 5 min
- the thickness of the deposited coating is 0.2 ⁇ m
- the surface-modified diamond is obtained.
- the purity of each gas used in step (6) is greater than 99.9999%.
- the color of the deposited coating after step (6) is dark blue, the refractive index of the coating is 3.0; the wetting angle of the coating is 110°; the oxidation resistance of the coating is 850°C; The coefficient of friction is 1.0.
- the surface-modified diamond is mainly used in optical diamond lenses and solar cells.
- This example provides a method for preparing a surface-modified diamond, including the steps of cleaning and forming a coating on the diamond, and specifically including the following steps:
- microwave plasma chemical vapor deposition working pressure is 1kPa
- deposition temperature 400°C
- deposition power 40kW
- the deposition time is 55 min
- the thickness of the deposited coating is 20 ⁇ m
- the surface-modified diamond is obtained.
- the purity of each gas used in step (6) is greater than 99.9999%.
- the refractive index of the deposited coating after step (6) was 1.5; the wetting angle of the coating was 120°; the oxidation resistance of the coating was 1200° C.; the friction coefficient of the coating was 0.04.
- the surface-modified diamond is mainly used in drilling, fluorine chemical, medical equipment, and high-purity electronic chemicals industries.
- test method of refractive index is GB/T 7962.1-2010;
- the test method of wetting angle is GB/T 30447-2013;
- test method for anti-oxidation is GB/T 13303-1991;
- the test method of friction coefficient is GB/T 10006-1988.
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Abstract
Description
Claims (13)
- 一种金刚石表面改性的方法,包括金刚石表面清洗工序和在所述金刚石表面形成涂层的工序,其特征在于,所述涂层包括位于最表面的表涂层和位于所述表涂层与所述金刚石表面之间的过渡涂层,所述表涂层由氟碳化合物和氟硅化合物形成或所述表涂层由氟硅化合物形成,所述的过渡涂层有二层,该二层结构中的直接形成在所述金刚石表面的一层由碳形成,另一层由碳化硅形成。
- 根据权利要求1所述的金刚石表面改性的方法,其特征在于:所述涂层的厚度为1nm-100μm;所述涂层的折射率为1.5~3.5,所述折射率参照GB/T 7962.1-2010进行测试;所述涂层的润湿角为1~120°,所述润湿角参照GB/T 30447-2013进行测试;所述涂层的抗氧化性为400~1200℃,所述抗氧化性参照GB/T 13303-1991进行测试;所述涂层的摩擦系数为0.04~1.0,所述摩擦系数参照GB/T 10006-1988进行测试。
- 根据权利要求1所述的金刚石表面改性的方法,其特征在于:所述涂层的每一层分别通过化学气相沉积法形成,所述化学气相沉积法使用的工作气体为甲烷、氢气、四氟化碳、四氟化硅、硅烷、乙醇、丙酮、氮气、氩气、氟气、氨气、氟化氢、二氟化氧、二氟化氙、三氟化氮中的一种或几种,且形成所述表涂层的工作气体至少含有氟源气,所述工作气体中每一种气体的纯度>99.9999%。
- 根据权利要求3所述的金刚石表面改性的方法,其特征在于:所述化学气相沉积法中,工作温度为室温-1000℃,工作气压为0.001Pa-100kPa,沉积功率为0.1W-100kW;所述化学气相沉积法采用等离子体化学气相沉积工艺,选用的能源为等离子体回旋共振、直流辉光放电、微波等离子体放电、磁控溅射、热丝等离子体、阻挡介质放电、直流电弧中的一个或几个能源耦合,通过所述化学气相沉积法可使所述涂层的厚度在1nm-100μm之间可调、折射率在1.5~3.5之间可调、润湿角在1~120°之间可调、抗氧化性在400~1200℃之间可调、摩擦系数在0.04~1.0之间可调。
- 根据权利要求1所述的金刚石表面改性的方法,其特征在于:所述过渡涂层为不定形、单晶、多晶层或液态层,所述过渡涂层中还含有掺杂元素,所述掺杂元素为O、N、H中的一种或几种。
- 根据权利要求5所述的金刚石表面改性的方法,其特征在于:所述过渡涂层的元素组成为C、Si、F、O、N、H,且C:Si:F:O:N:H=1:(0.001~1):(0.001~1):(0.001~1):(0.001~1):(0.001~1)。
- 根据权利要求1所述的金刚石表面改性的方法,其特征在于:所述金刚石为自然 界金刚石、人造金刚石、聚晶金刚石、单晶金刚石、金刚石薄膜、爆炸法合成的金刚石、粉末金刚石、改性金刚石、掺杂金刚石或类金刚石,所述金刚石还含sp3结构的碳材料,所述碳材料为碳纤维、石墨、纳米碳管、巴基球、多晶碳、无定形碳、碳黑中的一种或几种。
- 根据权利要求1所述的金刚石表面改性的方法,其特征在于,所述金刚石表面清洗工序包括以下步骤:(a)酸洗:以盐酸、双氧水、纯水按体积比1:(0.1-10):(1-100)混合配制酸清洗液,超声清洗1min-120min;(b)碱洗:以氨水、双氧水、纯水按体积比1:(0.1-10):(1-100)混合配制碱清洗液,超声清洗1min-120min;(c)表面氧化清洗:以硫酸、双氧水、纯水按体积比1:(0.1-10):(0-100)混合配制氧化清洗液,超声清洗1min-120min;(d)醇洗:以超高纯异丙醇作为清洗液,超声清洗1min-120min;(e)等离子体清洗:将所述醇洗后的金刚石置于以纯度>99.9999%的高纯氢气、纯度>99.9999%的高纯氩气、纯度>99.9999%的高纯氧气按体积比1:(0.01-100):(0.01-1)混合的混合气体中,控制电子温度(0.1-100)×104K、电子密度(0.1-100)×10 11个/cm3,清洗0.1min-120min;所述清洗工序中使用的各液体原料为药品级别,杂质含量为1000ppm以下;所述盐酸的质量浓度为0.01~37.5%,所述双氧水的质量浓度为0.01~85%,所述氨水的质量浓度为0.01~100%,所述硫酸的质量浓度为0.01-105%,所述异丙醇的质量浓度为0.01~99.99%。
- 根据权利要求8所述的金刚石表面改性的方法,其特征在于,所述清洗工序中使用的各液体原料的杂质含量为1ppb以下;各所述清洗液中还可选的添加有表面活性剂、润湿剂、耦合剂、消泡剂、分散剂中的一种或几种,以提高清洗效果;所述等离子体清洗工序中使用的混合气体中还可选的包括含氟气体、含氯气体、含氮气体、含碳气体中的一种或几种。
- 一种表面改性金刚石,所述表面改性金刚石通过权利要求1~9中任一项权利要求所述的金刚石表面改性的方法制得。
- 权利要求10所述的表面改性金刚石在珠宝领域、光学领域、研磨抛光领域、钻探领域、氟化工领域、医药领域、电子化学品领域中的用途;应用于所述珠宝领域时,通过调节所述涂层的厚度,控制光线透过表面改性金刚 石的波长,通过调节所述涂层的厚度为对应整数波长+1/4该波长即可以出现对应的补色,使表面改性金刚石对应呈现出通透的不同颜色;和/或通过调节所述涂层的润湿角,使得表面改性金刚石的表面对水的润湿角大于等于110°,对油的润湿角大于等于80°,憎水憎油,使表面改性金刚石免洗防污,其中,所述润湿角是通过调整所述表涂层中氟的质量含量的不同进行调节的,当所述氟的质量含量大于0.5%时,所述润湿角开始增大,当所述氟的质量含量大于20%时,所述润湿角达到极限值;和/或通过调节所述涂层的抗氧化性,使表面改性金刚石耐温大于等于1000℃,提高表面改性金刚石的安全性,其中,所述抗氧化性是通过调整所述表涂层中氟硅化合物的质量含量进行调节的,所述抗氧化性随着所述氟硅化合物的质量含量提高而提升,且当所述氟硅化合物的质量含量大于80%时,所述抗氧化性不再提升;应用于所述光学领域时,通过调节所述涂层的抗氧化性,使表面改性金刚石耐温大于等于1000℃,使表面改性金刚石作为光学窗口或透镜,其中,所述抗氧化性是通过调整所述表涂层中氟硅化合物的质量含量进行调节的,所述抗氧化性随着所述氟硅化合物的质量含量提高而提升,且当所述氟硅化合物的质量含量大于80%时,所述抗氧化性不再提升;和/或通过调节所述涂层的厚度和润湿角,并使得表面改性金刚石的表面对水的润湿角大于等于110°,对油的润湿角大于等于80°,使表面改性金刚石用于太阳能行业中,其中,所述润湿角是通过调整所述表涂层中氟的质量含量的不同进行调节的,当所述氟的质量含量大于0.5%时,所述润湿角开始增大,当所述氟的质量含量大于20%时,所述润湿角达到极限值;应用于所述研磨抛光领域时,通过金刚石粒度的选择及所述涂层的润湿角的调整,其中,所述金刚石粒度选择数纳米~数微米之间,所述涂层的润湿角的大小根据选用的溶剂的表面张力和金刚石粒度进行选择的,以达到重力平衡,使表面改性金刚石在水基或油基研磨抛光液中分散,自由悬浮,其中,所述润湿角的调整是通过调整所述表涂层中氟的质量含量的不同进行调节的,当所述氟的质量含量大于0.5%时,所述润湿角开始增大,当所述氟的质量含量大于20%时,所述润湿角达到极限值;所述表面改性金刚石用于半导体行业的减薄及CMP抛光中。
- 根据权利要求11所述的用途,其特征在于:应用于所述钻探领域时,由于所述涂层的存在,在孕镶结构钻头中,所述涂层屏蔽金刚石与刀具基体钢材料的接触。
- 根据权利要求11所述的用途,其特征在于:应用于所述医药领域时,所述表 面改性金刚石用于手术器械或植入人体组织器械上。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115093227A (zh) * | 2022-06-23 | 2022-09-23 | 河南工业大学 | 一种以镀膜金刚石为原料制备聚晶金刚石的方法 |
CN115819118A (zh) * | 2022-11-25 | 2023-03-21 | 湖南柯盛新材料有限公司 | 抗氧化涂层和含有抗氧化涂层的石墨模具及其制备方法 |
CN116159722A (zh) * | 2022-09-27 | 2023-05-26 | 波盈流体技术(上海)有限公司 | 一种高硬度阀芯及其表面处理工艺 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112030145B (zh) * | 2020-11-05 | 2021-03-23 | 上海征世科技有限公司 | 一种金刚石表面改性的方法及应用 |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4063907A (en) * | 1975-07-28 | 1977-12-20 | General Electric Company | Modifying the surface of diamond particles |
CN103469205A (zh) * | 2013-08-01 | 2013-12-25 | 合肥永信等离子技术有限公司 | 一种荷叶类金刚石膜的镀膜工艺 |
CN104045081A (zh) * | 2013-03-11 | 2014-09-17 | 中国科学院宁波材料技术与工程研究所 | 一种金刚石复合体及其制备方法 |
CN104707996A (zh) * | 2013-12-11 | 2015-06-17 | 中国科学院宁波材料技术与工程研究所 | 一种金刚石复合体以及金刚石表面金属化方法 |
CN105312554A (zh) * | 2014-07-07 | 2016-02-10 | 张家港市超声电气有限公司 | 一种用等离子体对粉体材料表面改性的方法 |
CN108941541A (zh) * | 2018-07-25 | 2018-12-07 | 芜湖昌菱金刚石工具有限公司 | 一种金刚石表面形成高温稳定覆层的方法 |
CN111663113A (zh) * | 2020-05-11 | 2020-09-15 | 江苏净钻环保科技有限公司 | 一种含dlc表面修饰层的超高比表面积梯度掺硼金刚石电极及其制备方法与应用 |
CN112030133A (zh) * | 2020-11-06 | 2020-12-04 | 苏州香榭轩表面工程技术咨询有限公司 | 一种金刚石及其制备方法和应用 |
CN112030145A (zh) * | 2020-11-05 | 2020-12-04 | 苏州香榭轩表面工程技术咨询有限公司 | 一种金刚石表面改性的方法及应用 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5462784A (en) * | 1994-11-02 | 1995-10-31 | International Business Machines Corporation | Fluorinated diamond-like carbon protective coating for magnetic recording media devices |
CN102234785B (zh) * | 2010-04-30 | 2013-08-21 | 永恒科技有限公司 | 衬底涂层及其形成方法 |
TWI539164B (zh) * | 2013-11-22 | 2016-06-21 | 財團法人工業技術研究院 | 塗佈探針及其製作方法 |
CN106282935A (zh) * | 2015-05-15 | 2017-01-04 | 新科实业有限公司 | 具有类金刚石涂层的材料及其制备方法 |
CN206845103U (zh) * | 2017-01-19 | 2018-01-05 | 上海征世科技有限公司 | 聚晶金刚石钻头 |
CN107475667A (zh) * | 2017-08-16 | 2017-12-15 | 信利光电股份有限公司 | 一种高疏水类金刚石薄膜及其制备方法 |
CN107502860B (zh) * | 2017-08-16 | 2020-07-17 | 信利光电股份有限公司 | 一种高疏水多元掺杂类金刚石薄膜及其制备方法 |
CN111334776B (zh) * | 2018-12-18 | 2024-03-15 | 深圳先进技术研究院 | 疏水类金刚石复合涂层及其制备方法与疏水器件及其制备方法 |
-
2020
- 2020-11-05 CN CN202011219989.7A patent/CN112030145B/zh active Active
-
2021
- 2021-10-26 WO PCT/CN2021/126269 patent/WO2022095747A1/zh active Application Filing
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4063907A (en) * | 1975-07-28 | 1977-12-20 | General Electric Company | Modifying the surface of diamond particles |
CN104045081A (zh) * | 2013-03-11 | 2014-09-17 | 中国科学院宁波材料技术与工程研究所 | 一种金刚石复合体及其制备方法 |
CN103469205A (zh) * | 2013-08-01 | 2013-12-25 | 合肥永信等离子技术有限公司 | 一种荷叶类金刚石膜的镀膜工艺 |
CN104707996A (zh) * | 2013-12-11 | 2015-06-17 | 中国科学院宁波材料技术与工程研究所 | 一种金刚石复合体以及金刚石表面金属化方法 |
CN105312554A (zh) * | 2014-07-07 | 2016-02-10 | 张家港市超声电气有限公司 | 一种用等离子体对粉体材料表面改性的方法 |
CN108941541A (zh) * | 2018-07-25 | 2018-12-07 | 芜湖昌菱金刚石工具有限公司 | 一种金刚石表面形成高温稳定覆层的方法 |
CN111663113A (zh) * | 2020-05-11 | 2020-09-15 | 江苏净钻环保科技有限公司 | 一种含dlc表面修饰层的超高比表面积梯度掺硼金刚石电极及其制备方法与应用 |
CN112030145A (zh) * | 2020-11-05 | 2020-12-04 | 苏州香榭轩表面工程技术咨询有限公司 | 一种金刚石表面改性的方法及应用 |
CN112030133A (zh) * | 2020-11-06 | 2020-12-04 | 苏州香榭轩表面工程技术咨询有限公司 | 一种金刚石及其制备方法和应用 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115093227A (zh) * | 2022-06-23 | 2022-09-23 | 河南工业大学 | 一种以镀膜金刚石为原料制备聚晶金刚石的方法 |
CN116159722A (zh) * | 2022-09-27 | 2023-05-26 | 波盈流体技术(上海)有限公司 | 一种高硬度阀芯及其表面处理工艺 |
CN116159722B (zh) * | 2022-09-27 | 2023-12-08 | 波盈流体技术(上海)有限公司 | 一种高硬度阀芯及其表面处理工艺 |
CN115819118A (zh) * | 2022-11-25 | 2023-03-21 | 湖南柯盛新材料有限公司 | 抗氧化涂层和含有抗氧化涂层的石墨模具及其制备方法 |
CN115819118B (zh) * | 2022-11-25 | 2023-09-22 | 湖南柯盛新材料有限公司 | 抗氧化涂层和含有抗氧化涂层的石墨模具及其制备方法 |
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