CN113981410A - Antioxidant super-hydrophobic copper film and preparation method thereof - Google Patents
Antioxidant super-hydrophobic copper film and preparation method thereof Download PDFInfo
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- CN113981410A CN113981410A CN202111250495.XA CN202111250495A CN113981410A CN 113981410 A CN113981410 A CN 113981410A CN 202111250495 A CN202111250495 A CN 202111250495A CN 113981410 A CN113981410 A CN 113981410A
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- 239000010949 copper Substances 0.000 title claims abstract description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 65
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 39
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 72
- 239000000758 substrate Substances 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000000151 deposition Methods 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 230000008021 deposition Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 62
- 239000002994 raw material Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000010408 film Substances 0.000 claims description 38
- 229910052786 argon Inorganic materials 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000005530 etching Methods 0.000 claims description 17
- 239000005416 organic matter Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000007769 metal material Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical group CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 claims 1
- 230000003064 anti-oxidating effect Effects 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 abstract description 9
- 239000010439 graphite Substances 0.000 abstract description 9
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- JBAKCAZIROEXGK-LNKPDPKZSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O JBAKCAZIROEXGK-LNKPDPKZSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C23C16/22—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
-
- 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
- C23C16/52—Controlling or regulating the coating process
Abstract
The invention discloses an antioxidant super-hydrophobic copper film, which takes a copper nanocluster generated after an organic metal precursor is decomposed as a catalyst to catalyze a liquid organic precursor to be decomposed into graphite carbon, the graphite carbon is enriched on the surface of the copper nanocluster to form copper @ carbon core-shell structure grains (Cu @ C), and countless copper @ carbon grains are accumulated on the surface of a substrate to form the antioxidant super-hydrophobic copper film. The invention also discloses a preparation method of the antioxidant super-hydrophobic copper film. According to the antioxidant super-hydrophobic copper film and the preparation method thereof, the antioxidant copper-carbon film is formed on the surface of the substrate by using a chemical vapor deposition method, and the super-hydrophobic characteristic is obtained by using a rough nano-structure surface formed by deposition, so that the whole method is simple, the control is convenient, and the repeatability is good.
Description
Technical Field
The invention belongs to the technical field of corrosion-resistant materials, and particularly relates to an antioxidant super-hydrophobic copper film and a preparation method thereof.
Background
Metallic materials, which are the most widely and important basic materials in use today, have become one of the important signs for measuring the technological level of materials in a country. Because copper has excellent heat conduction and electric conductivity, and has higher ductility and lower cost, the copper plays an important role in various industries, such as: the coil of the transformer, the electrolytic copper electrode in the lithium battery and the wire and cable in the power grid. However, since copper is active and is easily corroded by water vapor, oxygen and other corrosive gases in the air, the heat and electricity conducting properties of copper are seriously deteriorated, the service life of related equipment is greatly shortened, even irreversible damage is generated, and huge economic loss is brought.
The corrosion of copper mainly follows an electrochemical corrosion mechanism, and factors influencing the corrosion are oxygen, water vapor, carbon dioxide, sulfur dioxide, sulfate ions and ammonium ions. The reaction steps can be generally expressed as:
Cu+2NH3→Cu(NH3)2 ++e-；Cu(NH3)2 ++H2O→Cu2O+2H++4NH3
with NH3And evaporation of water, Cu2+、SO4 2-And H+Gradually form Cu with increasing concentration of4(SO4)(OH)6And Cu3(SO4)(OH)4When the concentration is over-saturated, a precipitate is separated out, which causes corrosion.
Meanwhile, in the atmospheric environment, a water film of 10nm to 1mm is usually generated on the copper surface according to the difference of humidity in the air, and when the humidity in the atmosphere is low, the metal surface is only formed by films of a few water molecule layers (<10nm), so that the electrochemical corrosion condition cannot be achieved, and the corrosion rate is extremely low. When the relative humidity in the atmosphere is less than 100 percent but higher than the critical relative humidity of the sample surface during adsorption and deliquescence, a continuous electrolyte liquid film with the thickness of dozens to hundreds of water molecules (10 nm-1 mu m) can be formed on the metal surface, electrochemical corrosion occurs, and the corrosion rate is remarkably accelerated. When the environment is rainy or snowy and heavy fog weather, water drops directly settle on the surface of the metal to form a thicker (1 mu m-1 mm) water film layer, and electrochemical corrosion occurs.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an antioxidant super-hydrophobic copper film with antioxidant super-hydrophobic characteristics formed on a target substrate by using organic metal copper and liquid organic matters as precursors and using a chemical vapor deposition method, and a preparation method thereof.
The technical scheme for solving the technical problems comprises the following steps:
the oxidation-resistant super-hydrophobic copper film is a copper-carbon film formed by uniformly stacking a formed copper @ carbon core-shell structure on a substrate, wherein a graphitized carbon layer wraps copper nanoclusters, and the surface appearance of the copper-carbon film is in a nano-peak shape.
Another technical solution for solving the above technical problems of the present invention is:
the preparation method for preparing the antioxidant super-hydrophobic copper film adopts a chemical vapor deposition method, and comprises the following steps:
cleaning the substrate, namely putting the cut substrate into an ultrasonic cleaning machine for ultrasonic cleaning; and removing impurities on the surface of the substrate by adopting an ultrasonic cleaning mode, thereby ensuring the cleanness of the growth environment of the copper-carbon film.
Etching the substrate, namely placing the substrate into etching liquid to etch the surface of the substrate; the substrate is etched by using the etching liquid, so that the roughness of the substrate can be increased, more nucleation sites can be formed, and the deposition rate of the copper-carbon film can be increased.
Preparing a precursor, namely weighing 2-4 g of organic metal precursor and 20ml of liquid organic matter precursor respectively for later use; the organic metal precursor is used as a copper source, and the liquid organic matter precursor is used as a carbon source.
Loading, namely placing the etched substrate into a reaction zone of a tubular furnace, respectively loading the precursors into a raw material tank, sealing a valve of the raw material tank and connecting the raw material tank with the tubular furnace; the sealing property of the reaction environment is ensured, and the problem in the reaction process is avoided.
Introducing hydrogen, introducing the hydrogen into the tubular furnace, replacing air in the tubular furnace, and enabling the pressure in the tubular furnace to reach 1000-9000 Pa; the hydrogen participates in the reaction at the same time and is used as protective gas, so that the reaction product is not oxidized, the stable condition of the environment in the tube furnace is ensured, and the deposition operation is suitable.
Introducing argon, introducing argon into the raw material tank, completely filling the raw material tank with the argon, isolating air and enabling the pressure in the raw material tank to be the same as that in the tubular furnace; the argon is used as inert gas, so that the precursor is ensured not to react in the raw material tank after being gasified, and simultaneously, the argon is also used as power gas carrying the precursor.
Heating the reaction zone, namely heating the tubular furnace to ensure that the reaction zone in the tubular furnace is at a reaction temperature; heating the raw material tank to gasify the organic metal precursor and the liquid organic matter precursor; the tube furnace is allowed to react with the environment in the feed tank.
Depositing, opening a valve of the raw material tank, introducing the precursor into the reaction zone through argon gas for deposition, and depositing the deposited product on the surface of the substrate; the organic metal precursor is decomposed to generate copper nanoclusters, the liquid organic precursor is decomposed to form carbon nanoclusters (graphite carbon) under the catalytic action of the copper nanoclusters, the carbon nanoclusters are enriched on the surface of the copper nanoclusters to wrap the copper nanoclusters so as to form grains (Cu @ C) with a carbon @ copper core-shell structure, and then innumerable carbon @ copper core grains are accumulated on the surface of a substrate.
And (4) preserving heat, after the deposition is finished, quickly closing the argon and a raw material tank valve, controlling the concentration of hydrogen in the reaction zone of the tubular furnace, and reducing the temperature of the reaction zone of the tubular furnace to room temperature to obtain the antioxidant super-hydrophobic copper film. In the cooling process, the concentration of hydrogen in the tube furnace is ensured, and the generated product can be ensured not to have oxidation reaction, so that the obtained antioxidant super-hydrophobic copper film is ensured to have the characteristics of oxidation resistance and super-hydrophobicity.
The invention has the following beneficial effects: the Cu @ C film is produced and formed by a chemical vapor deposition method, so that an antioxidant copper-carbon film is formed on the surface of a substrate, and the super-hydrophobic characteristic is obtained by utilizing a rough nano-structure surface formed by deposition.
Drawings
Fig. 1 is a microscope display diagram showing the structure of a product obtained in example 1 of the present invention, wherein fig. 1(a) is an SEM image of the product, and fig. 1(b) is a TEM image of the product.
FIG. 2 shows XRD test results of the product obtained in example 1 of the present invention. Fig. 2(a) is an XRD pattern of the product as prepared, and fig. 2(b) is an XRD pattern of the product after being left in the air for 100 days.
FIG. 3 is an AFM three-dimensional image of the product obtained in example 1 of the present invention.
FIG. 4 shows the wetting angle test results of the product obtained in example 1 of the present invention with water as it is formed;
FIG. 5 shows the results of the wetting angle test with water after the product obtained in example 1 of the present invention is left for 100 days;
Detailed Description
The oxidation-resistant super-hydrophobic copper film is a copper-carbon film formed by uniformly accumulating a copper @ carbon core-shell structure formed by wrapping copper nanoclusters outside a graphitized carbon layer on a substrate, the surface appearance of the copper-carbon film is in a nano-peak shape, the copper nanoclusters are generated by decomposing an organic metal precursor, and a liquid organic matter precursor is decomposed under the catalytic action of the copper nanoclustersThe carbon nanocluster (graphitic carbon) is enriched on the surface of the copper nanocluster to wrap the copper nanocluster so as to form carbon @ copper core-shell structure crystal grains (Cu @ C), and then countless carbon @ copper core crystal grains are accumulated on the surface of a substrate so as to form the antioxidant super-hydrophobic copper film. In the present invention, the substrate may employ a metal or nonmetal, for example: quartz, corundum, stainless steel, aluminum alloy, Si3N4，GaN，TiN，SrTiO3And SrLaAlO4And the like. The organometallic copper can be, for example, Cu (hfac) (vtms), [ Cu (dppm) (NO3)]2 or Cu (I) based material such as Cu (acac)2, Cu (tfac)2, or Cu (II) based material such as Cu (acac) 2. The liquid organic matter precursor is a hydrocarbon with a lower decomposition temperature, specifically acetone, ethanol, ethylene glycol or n-propanol, and the decomposition temperature is lower than that of the organic metal precursor, specifically, the volatilization temperature of the selected organic metal precursor is 80-250 ℃, and the volatilization temperature of the selected liquid organic matter is 30-150 ℃.
Specifically, the present invention will be described in detail with reference to the following examples.
Example 1:
the preparation method of the antioxidant superhydrophobic copper film in embodiment 1 of the invention adopts a gas phase deposition method, and comprises the following steps:
cleaning the substrate, namely putting the cut substrate into an ultrasonic cleaning machine for ultrasonic cleaning; in this example, SiO was used2As a substrate, the substrate was cut into a 10 × 5mm rectangular shape, followed by ultrasonic cleaning with isopropyl alcohol for 10 minutes.
Etching the substrate, namely placing the substrate into etching liquid to etch the surface of the substrate; the selection of the etching liquid is selected according to the substrate material. In this example, HF solution (HF: H) was used2O＝1:4) etching SiO2Substrate for 5 min.
Preparing a precursor, namely weighing 2-4 g of organic metal precursor and 20ml of liquid organic matter precursor respectively for later use; in this example, 3g of Cu (acac) was weighed2As an organic metal precursor, 20mL of ethanol was measured as a liquid organic precursor.
Loading, namely placing the etched substrate into a reaction zone of a tubular furnace, respectively loading the precursors into a raw material tank, sealing a valve of the raw material tank and connecting the raw material tank with the tubular furnace; forming the environment of the reaction equipment.
Introducing hydrogen, introducing the hydrogen with the flow rate of 200sccm into the tubular furnace, replacing air in the tubular furnace, and enabling the pressure in the tubular furnace to reach 1000 Pa; so that the pressure in the tube furnace meets the reaction conditions.
Introducing argon, and respectively introducing argon with the flow of 50sccm into the raw material tank, so that the raw material tank is completely filled with the argon, the air is isolated, and the pressure in the raw material tank is the same as the pressure in the tubular furnace; the consistent pressure ensures that the situation of gas backflow cannot occur when the valve of the raw material tank is opened.
Heating the reaction zone, namely heating the tubular furnace to ensure that the reaction zone in the tubular furnace is at a reaction temperature of 400 ℃;
heating the raw material tank, namely heating the raw material tank loaded with the organic metal precursor to 200 ℃, heating the raw material tank loaded with the liquid organic matter precursor to 50 ℃ so as to gasify the organic metal precursor and the liquid organic matter precursor; thereby enabling the precursor to be carried with argon.
Depositing, opening a valve of the raw material tank, introducing the precursor into the reaction zone through argon gas for deposition, and depositing the deposited product on the surface of the substrate; in the reaction zone, a decomposition reaction is carried out firstly, under the condition of high temperature, the organic metal precursor is decomposed to generate a copper atom cluster, then the liquid organic precursor is also subjected to a decomposition reaction under the catalysis of the copper atom cluster to generate graphite carbon, the graphite carbon is adsorbed to the periphery of the copper atom cluster to form spherical Cu @ C crystal grains, and then the Cu @ C crystal grains are deposited on the substrate and stacked on the substrate, wherein the deposition time is 30min in the embodiment.
And (4) preserving heat, after the deposition is finished, quickly closing the argon and a raw material tank valve, controlling the concentration of hydrogen in the reaction zone of the tubular furnace, and reducing the temperature of the reaction zone of the tubular furnace to room temperature to obtain the antioxidant super-hydrophobic copper film. In the heat preservation process, the concentration of the hydrogen in the tube furnace is only required to be ensured, so that the pressure can be reduced to 50Pa, and the pressure can be satisfied.
As can be seen from FIG. 1, the surface of the oxidation-resistant super-hydrophobic copper thin film is formed by stacking spherical Cu @ C grains, a rough nano-structure surface formed on the surface of the oxidation-resistant super-hydrophobic copper thin film can be attached with super-hydrophobic characteristics, and meanwhile, as can be seen from a TEM image, the thickness of the carbon film is about 4 nm. As can be seen from fig. 3, a nano-peak structure is formed on the surface of the copper-carbon thin film. As shown in fig. 2, fig. 4 and fig. 5, it can be determined that the oxidation-resistant super-hydrophobic copper thin film has strong oxidation resistance and super-hydrophobic property after being placed in the air for 100 days.
Example 2:
the preparation method of the antioxidant super-hydrophobic copper film in embodiment 2 of the invention adopts a gas phase deposition method, and comprises the following steps:
cleaning the substrate, namely putting the cut substrate into an ultrasonic cleaning machine for ultrasonic cleaning; in this example, corundum was used as a substrate, and the substrate was cut into a 5X 5mm rectangular shape, followed by ultrasonic cleaning with propanol for 20 minutes.
Etching the substrate, namely placing the substrate into etching liquid to etch the surface of the substrate; the selection of the etching liquid is selected according to the substrate material. In this example, HF solution (HF: H) was used2O ═ 1:4) the corundum substrate was etched for 7 min.
Preparing a precursor, namely weighing 2-4 g of organic metal precursor and 20ml of liquid organic matter precursor respectively for later use; in this example, 2g of Cu (hfac) (vtms) was weighed out as an organometallic precursor, and 20mL of methanol was weighed out as a liquid organic precursor.
Loading, namely placing the etched substrate into a reaction zone of a tubular furnace, respectively loading the precursors into a raw material tank, sealing a valve of the raw material tank and connecting the raw material tank with the tubular furnace; forming the environment of the reaction equipment.
Introducing hydrogen, introducing the hydrogen with the flow rate of 600sccm into the tubular furnace, replacing air in the tubular furnace, and enabling the pressure in the tubular furnace to reach 5000 Pa; so that the pressure in the tube furnace meets the reaction conditions.
Introducing argon, and respectively introducing argon with the flow of 70sccm into the raw material tank, so that the raw material tank is completely filled with the argon, the air is isolated, and the pressure in the raw material tank is the same as the pressure in the tubular furnace; the consistent pressure ensures that the situation of gas backflow cannot occur when the valve of the raw material tank is opened.
Heating the reaction zone, namely heating the tubular furnace to ensure that the reaction zone in the tubular furnace is at a reaction temperature of 500 ℃;
heating the raw material tank to 250 ℃ and 40 ℃ to the raw material tank loaded with the organic metal precursor so as to gasify the organic metal precursor and the liquid organic precursor; thereby enabling the precursor to be carried with argon.
Depositing, opening a valve of the raw material tank, introducing the precursor into the reaction zone through argon gas for deposition, and depositing the deposited product on the surface of the substrate; in the reaction zone, a decomposition reaction is carried out firstly, under the condition of high temperature, the organic metal precursor is decomposed to generate a copper atom cluster, then the liquid organic precursor is also subjected to a decomposition reaction under the catalysis of the copper atom cluster to generate graphite carbon, the graphite carbon is adsorbed to the periphery of the copper atom cluster to form spherical Cu @ C crystal grains, and then the Cu @ C crystal grains are deposited on the substrate and stacked on the substrate, wherein the deposition time is 45min in the embodiment.
And (4) preserving heat, after the deposition is finished, quickly closing the argon and a raw material tank valve, controlling the concentration of hydrogen in the reaction zone of the tubular furnace, and reducing the temperature of the reaction zone of the tubular furnace to room temperature to obtain the antioxidant super-hydrophobic copper film. In the heat preservation process, the concentration of the hydrogen in the tube furnace is only required to be ensured, so that the pressure can be reduced to 50Pa, and the pressure can be satisfied.
Example 3:
the preparation method of the antioxidant superhydrophobic copper film in embodiment 3 of the invention adopts a gas phase deposition method, and comprises the following steps:
cleaning the substrate, namely putting the cut substrate into an ultrasonic cleaning machine for ultrasonic cleaning; in this example, stainless steel was used as a substrate, and the substrate was cut into a 5 × 5mm rectangular shape, followed by ultrasonic cleaning with ethanol for 30 minutes.
Etching the substrate, namely placing the substrate into etching liquid to etch the surface of the substrate; the selection of the etching liquid is selected according to the substrate material. In this example, HCl solution (HCl: H) was used2O ═ 1:10) the stainless steel substrate was etched for 10 min.
Preparing a precursor, namely weighing 2-4 g of organic metal precursor and 20ml of liquid organic matter precursor respectively for later use; in this example, 4g of Cu (tfac) was weighed2As the organic metal precursor, 20mL of ethylene glycol was measured as a liquid organic precursor.
Loading, namely placing the etched substrate into a reaction zone of a tubular furnace, respectively loading the precursors into a raw material tank, sealing a valve of the raw material tank and connecting the raw material tank with the tubular furnace; forming the environment of the reaction equipment.
Introducing hydrogen, introducing the hydrogen with the flow rate of 1000sccm into the tubular furnace, replacing air in the tubular furnace, and enabling the pressure in the tubular furnace to reach 9000 Pa; so that the pressure in the tube furnace meets the reaction conditions.
Introducing argon, and introducing argon with the flow of 100sccm into the raw material tank respectively, so that the raw material tank is completely filled with the argon, the air is isolated, and the pressure in the raw material tank is the same as the pressure in the tubular furnace; the consistent pressure ensures that the situation of gas backflow cannot occur when the valve of the raw material tank is opened.
Heating the reaction zone, namely heating the tubular furnace to ensure that the reaction zone in the tubular furnace is at a reaction temperature of 600 ℃;
heating the raw material tank, namely heating the raw material tank loaded with the organic metal precursor to 120 ℃, heating the raw material tank loaded with the liquid organic matter precursor to 150 ℃ so as to gasify the organic metal precursor and the liquid organic matter precursor; thereby enabling the precursor to be carried with argon.
Depositing, opening a valve of the raw material tank, introducing the precursor into the reaction zone through argon gas for deposition, and depositing the deposited product on the surface of the substrate; in the reaction zone, a decomposition reaction is carried out firstly, under the condition of high temperature, the organic metal precursor is decomposed to generate a copper atom cluster, then the liquid organic precursor is also subjected to a decomposition reaction under the catalysis of the copper atom cluster to generate graphite carbon, the graphite carbon is adsorbed to the periphery of the copper atom cluster to form spherical Cu @ C crystal grains, and then the Cu @ C crystal grains are deposited on the substrate and stacked on the substrate, wherein the deposition time is 60min in the embodiment.
And (4) preserving heat, after the deposition is finished, quickly closing the argon and a raw material tank valve, controlling the concentration of hydrogen in the reaction zone of the tubular furnace, and reducing the temperature of the reaction zone of the tubular furnace to room temperature to obtain the antioxidant super-hydrophobic copper film. In the heat preservation process, the concentration of the hydrogen in the tube furnace is only required to be ensured, so that the pressure can be reduced to 50Pa, and the pressure can be satisfied.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. An anti-oxidation super-hydrophobic copper film is characterized in that: the oxidation-resistant super-hydrophobic copper film is a copper carbon film formed by uniformly stacking a formed copper @ carbon core-shell structure on a substrate, wherein a graphitized carbon layer wraps a copper nano cluster, and the surface appearance of the copper carbon film is in a nano peak shape.
2. The preparation method of the oxidation-resistant super-hydrophobic copper film as claimed in claim 1, which is characterized by adopting a chemical vapor deposition method, and comprises the following steps:
cleaning the substrate, namely putting the cut substrate into an ultrasonic cleaning machine for ultrasonic cleaning;
etching the substrate, namely placing the substrate into etching liquid to etch the surface of the substrate;
preparing a precursor, namely weighing 2-4 g of organic metal precursor and 20ml of liquid organic matter precursor respectively for later use;
loading, namely placing the etched substrate into a reaction zone of a tubular furnace, respectively loading the precursors into a raw material tank, sealing a valve of the raw material tank and connecting the raw material tank with the tubular furnace;
introducing hydrogen, introducing the hydrogen into the tubular furnace, replacing air in the tubular furnace, and enabling the pressure in the tubular furnace to reach 1000-9000 Pa;
introducing argon, introducing argon into the raw material tank, completely filling the raw material tank with the argon, isolating air and enabling the pressure in the raw material tank to be the same as that in the tubular furnace;
heating the reaction zone, namely heating the tubular furnace to ensure that the reaction zone in the tubular furnace is at a reaction temperature;
heating the raw material tank to gasify the organic metal precursor and the liquid organic matter precursor;
depositing, opening a valve of the raw material tank, introducing the precursor into the reaction zone through argon gas for deposition, and depositing the deposited product on the surface of the substrate;
and (4) preserving heat, after the deposition is finished, quickly closing the argon and a raw material tank valve, controlling the hydrogen concentration in the reaction zone of the tubular furnace, and reducing the temperature of the reaction zone of the tubular furnace to room temperature to obtain the antioxidant super-hydrophobic copper film.
3. The preparation method of the oxidation-resistant super-hydrophobic copper film according to claim 2, characterized in that: the substrate comprises a sheet made of a metal material or a non-metal material, and the rectangular sheet is cut into a size of 5-10 mm multiplied by 5 mm.
4. The preparation method of the oxidation-resistant super-hydrophobic copper film according to claim 2, characterized in that: the cleaning liquid filled in the ultrasonic cleaning machine is isopropyl ketone, acetone or ethanol; the scaleThe etching solution is HF solution, HCl solution, H2SO4Solutions or NaOH solutions.
5. The preparation method of the oxidation-resistant super-hydrophobic copper film according to claim 2, characterized in that: the organic metal precursor is Cu (I) or Cu (II) organic metal copper; the liquid organic matter precursor is a hydrocarbon with low decomposition temperature, and comprises acetone, ethanol, ethylene glycol or n-propanol.
6. The preparation method of the oxidation-resistant super-hydrophobic copper film according to any one of claims 2 to 5, characterized in that: the ultrasonic cleaning time is 10-30 min, and the etching time is 5-10 min.
7. The method for preparing the antioxidant superhydrophobic copper thin film according to claim 6, wherein: the volatilization temperature of the organic metal precursor is 80-250 ℃; the volatilization temperature of the liquid organic matter is 30-150 ℃; the reaction temperature is 400-600 ℃.
8. The method for preparing the antioxidant superhydrophobic copper thin film according to claim 6, wherein: and carrying out decomposition reaction in the reaction zone, wherein the deposition time is 30-60 min.
9. The method for preparing the antioxidant superhydrophobic copper thin film according to claim 6, wherein: the flow rate of the introduced hydrogen is 200-1000 sccm; the flow of the introduced argon is 50-150 sccm.
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