Method for preventing metal copper corrosion, structure for preventing metal copper corrosion

Abstract

The present application provides a method for preventing corrosion of metallic copper and a structure for preventing corrosion of metallic copper, which belong to the technical field of metal corrosion prevention. The method for preventing corrosion of metallic copper includes forming a graphene layer having a thickness of at least two atomic layers on the surface of a copper substrate. By forming a graphene layer having a thickness of at least two atomic layers on the surface of the copper substrate, the method for preventing corrosion of metallic copper according to the present application weakens charge transfer between the corrosive substance and the copper substrate, making it less likely that the copper substrate will react electrochemically with the graphene layer on the surface, thereby improving the corrosion prevention performance of the copper substrate.

Description

[Technical Field]

[0001] The present application relates to the technical field of metal corrosion prevention, and specifically to a method for preventing metal copper corrosion and a structure for preventing metal copper corrosion.

[0002] Cross-reference to related applications This application claims priority based on a Chinese application bearing application number 2023103159451 and entitled "Method for preventing corrosion of metal copper, structure for preventing corrosion of metal copper," filed with the State Intellectual Property Office of the People's Republic of China on March 28, 2023, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] Copper is a widely used non-ferrous metal material with excellent electrical and thermal conductivity and ductility, a relatively low melting point, and ease of smelting, making it suitable for large-scale, low-cost industrial production and processing. It is therefore widely used in the electrical, light, machinery, construction, and defense industries. Oxygen corrosion of copper poses a major problem in copper use. When copper is exposed to air for a long period of time, oxygen gas and water vapor in the air react with copper to form copper oxide, which can significantly impair the quality of copper products and directly impair their normal function. Currently, copper corrosion prevention methods often involve plating with other metals, organic protective layers, or oxide protective layers. However, these methods suffer from drawbacks such as poor electrical and thermal conductivity, being relatively thick, poor light transmittance, and incomplete protection. Because copper is widely used, copper oxidation and corrosion results in hundreds of millions of yen lost each year. Therefore, the development of new protective layer materials that are low-cost, high-quality, ultra-thin, and have better corrosion protection is of great practical value and economic and environmental significance. Summary of the Invention

[0004] The present application provides a method for preventing corrosion of metallic copper and a structure for preventing corrosion of metallic copper, which can improve at least the corrosion prevention performance of metallic copper.

[0005] Some embodiments of the present application provide a method for preventing metallic copper corrosion, comprising forming a graphene layer at least two atomic layers thick on a surface of a copper substrate.

[0006] In the above technical solutions, the method for preventing corrosion of metal copper according to some embodiments of the present application forms a graphene layer with a thickness of at least two atomic layers on the surface of the copper substrate, thereby weakening the charge transfer between the corrosive substance and the copper substrate, making it difficult for the copper substrate to undergo an electrochemical reaction with the graphene layer on the surface, and improving the corrosion prevention performance of the copper substrate.

[0007] In some optional embodiments of the present application, the thickness of the graphene formed on the surface of the copper substrate is 2 to 10 atomic layers.

[0008] In some alternative embodiments of the present application, the copper substrate is single crystal copper.

[0009] In the above alternative embodiment of the present application, if the copper substrate is single crystal copper, the corrosion prevention performance is better.

[0010] In some optional embodiments of the present application, a method for obtaining single-crystal copper includes the steps of placing polycrystalline copper on a substrate, placing the substrate in a CVD (Chemical Vapor Deposition) furnace, and heating the polycrystalline copper to 1000°C to 1080°C in an atmosphere containing an inert gas and hydrogen gas, where the flow rate of the inert gas is 100 sccm to 1000 sccm and the flow rate of the hydrogen gas is 1 sccm to 50 sccm, to perform a single-crystallization process on the polycrystalline copper.

[0011] In some alternative embodiments of the present application, a method for forming at least two layers of graphene on a surface of a copper substrate includes: The method includes the steps of forming graphene having a thickness of one atomic layer on the surface of a copper substrate to obtain a first graphene layer, forming graphene having a thickness of one atomic layer on the surface of a copper carrier to obtain a second graphene layer, transferring at least one second graphene layer onto the surface of the first graphene layer, and performing a graphene bonding treatment at 300°C to 500°C in an atmosphere containing an inert gas and hydrogen gas.

[0012] Optionally, in the graphene bonding process, the flow rate of the inert gas is between 100 sccm and 1000 sccm, and the flow rate of the hydrogen gas is between 5 sccm and 100 sccm.

[0013] Optionally, the temperature at which the graphene bonding process is carried out is 300°C, 320°C, 350°C, 380°C, 400°C, 420°C, 450°C, 480°C or 500°C.

[0014] Optionally, the duration of the graphene bonding treatment is at least 6 hours.

[0015] Optionally, the graphene bonding treatment time is between 6 hours and 24 hours.

[0016] In the above alternative embodiment, the method for preventing corrosion of metal copper includes forming graphene with a thickness of one atomic layer on the surface of a copper substrate to obtain a first graphene layer, forming graphene with a thickness of one atomic layer on the surface of a copper carrier to obtain a second graphene layer, and then transferring the prepared second graphene layer to the surface of the first graphene layer on the copper substrate and performing a graphene bonding treatment to obtain a double-layer graphene layer. In this manner, the first graphene layer can be more firmly bonded to the surface of the copper substrate, reducing interfacial diffusion, and the second graphene layer has a shielding effect, resulting in less charge transfer and being nearly neutral, thereby suppressing the occurrence of electrochemical reactions and improving the corrosion protection performance of the copper substrate.

[0017] In some optional embodiments of the present application, when at least one second graphene layer is transferred onto the surface of the first graphene layer, one second graphene layer is transferred at a time, and a graphene bonding process is performed after each transfer of one second graphene layer.

[0018] In some alternative embodiments of the present application, a method for forming a first graphene layer or a second graphene layer having a thickness of one atomic layer on a surface of a copper substrate or a copper carrier includes: The method includes a step of growing and forming a first graphene layer or a second graphene layer having a thickness of one atomic layer on at least a part of the surface of a copper substrate or a copper carrier by chemical vapor deposition at 1000°C to 1080°C in an atmosphere containing methane, hydrogen gas, and an inert gas.

[0019] Optionally, the flow rate of methane is 0.005 sccm to 0.05 sccm, the flow rate of the inert gas is 100 sccm to 1000 sccm, and the flow rate ratio of methane to hydrogen gas is 1:200 to 1:1500.

[0020] In some alternative embodiments of the present application, a method for transferring at least one second graphene layer onto a surface of a first graphene layer includes: Before the transfer, the method includes the steps of first forming a resin layer on the surface of the second graphene layer, then etching the graphene other than the second graphene layer, and then etching the copper carrier located on the back surface of the second graphene layer to obtain the second graphene layer attached to the surface of the resin layer, and then placing the second graphene layer attached to the surface of the resin layer on the surface of the first graphene layer to perform a graphene bonding process.

[0021] In the above alternative embodiment, the resin layer acts as a carrier for the second graphene layer after it is detached from the copper carrier, thereby allowing the second graphene layer to be transferred to the surface of the first graphene layer while maintaining relatively good morphology.

[0022] In some alternative embodiments of the present application, the resin layer comprises polymethyl methacrylate or polypropylene carbonate.

[0023] In some optional embodiments of the present application, the step of forming a resin layer on the surface of the second graphene layer includes the steps of spin-coating a resin solution dissolved in a solvent onto the surface of the second graphene layer, and heating the resin solution at a heating temperature of 40°C to 160°C for 1 minute to 5 minutes.

[0024] In some alternative embodiments of the present application, the solvent comprises anisole.

[0025] In some optional embodiments of the present application, when the main component of the resin layer is polymethyl methacrylate, the mass fraction of polymethyl methacrylate in the resin solution is 3 wt% to 13 wt%, and the heating temperature is 80°C to 160°C; alternatively, when the main component of the resin layer is polypropylene carbonate, the mass fraction of polypropylene carbonate in the resin solution is 6 wt% to 18 wt%, and the heating temperature is 40°C to 70°C.

[0026] In some alternative embodiments of the present application, O2 plasma, O3 plasma, argon gas plasma, or hydrogen gas plasma is used to etch graphene other than the second graphene layer.

[0027] In some alternative embodiments of the present application, the copper carrier located on the back surface of the second graphene layer is etched using a 0.05 mol / L to 0.5 mol / L (NH4)2S2O8 solution and FeCl3 solution. In some alternative embodiments of the present application, the method for forming at least two layers of graphene on the surface of a copper substrate includes: The method includes a step of growing and forming a graphene layer having a thickness of a plurality of atomic layers on at least a part of the surface of a copper substrate by chemical vapor deposition at 1000°C to 1080°C in an atmosphere containing methane, hydrogen gas, and an inert gas.

[0028] Optionally, the flow rate of methane is 0.005 sccm to 0.1 sccm, the flow rate of the inert gas is 100 sccm to 1000 sccm, and the flow rate ratio of methane to hydrogen gas is 1:10 to 1:150.

[0029] In the above-mentioned alternative embodiment of the present application, the method for preventing corrosion of metal copper includes directly growing graphene on at least a portion of a copper substrate by chemical vapor deposition, and controlling the flow rates of methane and hydrogen gases to control the thickness of the graphene layer. Because the graphene layer has a multi-layer graphene stacked structure, the density of defects directly accessible to the copper surface is significantly reduced, and the graphene layer can block various oxidation routes and improve the corrosion protection performance of the copper substrate.

[0030] Some other embodiments of the present application provide a metallic copper corrosion-inhibiting structure, which is prepared by the metallic copper corrosion-inhibiting method described above.

[0031] In the above embodiment, the graphene layer having a thickness of at least two atomic layers can weaken the charge transfer between the corrosive substance and the copper substrate, making it difficult for the copper substrate to undergo electrochemical reaction with the graphene layer on the surface, thereby improving the corrosion resistance of the copper substrate.

[0032] Some other embodiments of the present application provide a metal copper corrosion prevention structure, which includes a copper substrate and a graphene layer provided on at least a portion of the surface of the copper substrate, the graphene layer having a thickness of at least two atomic layers.

[0033] In the above embodiment, the graphene layer having a thickness of at least two atomic layers weakens the charge transfer between the corrosive substance and the copper substrate, making it difficult for the copper substrate to undergo an electrochemical reaction with the graphene layer on the surface, thereby improving the corrosion resistance of the copper substrate.

[0034] In order to more clearly explain the technical solutions of the embodiments of the present application, the drawings used in the embodiments will be briefly described below. The drawings described are only for illustrating some embodiments of the present application and are not intended to limit the scope. Those skilled in the art can obtain other related drawings based on these drawings without using inventive abilities. [Brief explanation of the drawings]

[0035] [Figure 1] 1 is a comparative graph showing the change over time in the corroded area at 200° C. of the metal copper corrosion prevention structures according to Example 1 and Comparative Example 1. [Figure 2] 1 shows SEM photographs of the copper corrosion prevention structures according to Examples 1 to 3 and Comparative Example 1 after being corroded in oxygen gas at 230 Pa and at 600° C. for 1 second. [Figure 3] 1 shows SEM photographs of the copper corrosion prevention structures according to Examples 1 to 3 and Comparative Example 1 after they were corroded in oxygen gas at 230 Pa and at 600° C. for 10 minutes. [Figure 4] 1 is a comparative photograph showing the corrosion prevention effect of the metal copper corrosion prevention structures of Example 1 and Comparative Example 1 after being heated at a high temperature of 250° C. for 6 hours. [Figure 5] 1 shows comparative photographs of the corrosion prevention effects of the metal copper corrosion prevention structures of Examples 1 and 2 and Comparative Example 1 after heating at a high temperature of 250° C. for 0 hours, 0.5 hours, 10 hours, and 15 hours. DETAILED DESCRIPTION OF THE INVENTION

[0036] Copper is a widely used non-ferrous metal material with excellent electrical and thermal conductivity, ductility, a relatively low melting point, and ease of smelting, making it suitable for large-scale, low-cost industrial production and processing. Therefore, it is widely used in the electrical, light, machinery, construction, and defense industries. Oxygen corrosion of copper is a major problem in copper's use. When copper is exposed to air for a long period of time, oxygen and water vapor in the air react with copper to form copper oxide, significantly degrading the quality of copper products and ultimately directly impairing their normal function. Currently, copper corrosion prevention methods, such as plating with other metals, organic protective layers, and oxide protective layers, have drawbacks, including relatively poor electrical and thermal conductivity, relatively thick coatings, poor optical transparency, and incomplete protection. Because of copper's widespread use, copper oxidation and corrosion causes losses of hundreds of millions of yen each year.

[0037] However, the inventors discovered that in the method of using graphene to protect copper from corrosion, interfacial diffusion occurs due to the weak bond at the graphene-copper interface, and because graphene is more inert than copper, it acts as a cathode in electrochemical reactions, rapidly reducing the graphene's corrosion protection ability at the exposed graphene-copper interface. While there are currently many methods to solve this problem, all of these methods rely on the alignment of the graphene and copper crystal lattice directions or the flatness of the copper surface, making them complicated and unsuitable for diverse industrial applications.

[0038] In light of the above, the inventors have conducted research and developed a method for preventing corrosion of copper metal to improve its corrosion protection. This method involves forming a graphene layer at least two atomic layers thick on the surface of a copper substrate, weakening the charge transfer between corrosive substances and the copper substrate and making it less likely for the copper substrate to electrochemically react with the graphene layer on the surface. This blocks the following four routes to corrosion protection failure: (1) defects generated during graphene growth, (2) interfacial diffusion due to weak bonds between graphene and copper, (3) electrochemical reactions between graphene and copper, and (4) penetration of corrosive molecules. Furthermore, this method can prevent further copper corrosion and maintain good corrosion protection performance even when defects exist or arise during the work process.

[0039] The present application will be described in detail below with reference to examples. As will be appreciated by those skilled in the art, the following examples are merely illustrative of the present application and are not intended to limit the scope of the present application. In the examples, specific conditions are not specified, and the experiments can be carried out under conventional conditions or under conditions recommended by the manufacturer. For reagents or equipment whose manufacturers are not specified, conventional commercially available products can be used.

[0040] Hereinafter, methods for preventing corrosion of metallic copper and structures for preventing corrosion of metallic copper according to some embodiments of the present application will be described in detail.

[0041] The method for preventing metallic copper corrosion according to some embodiments of the present application forms a graphene layer at least two atomic layers thick on the surface of a copper substrate.

[0042] Optionally, the thickness of the graphene layer formed on the surface of the copper substrate is 2 to 10 atomic layers thick.

[0043] For example, the thickness of the graphene layer formed on the surface of the copper substrate may be 2 atomic layers, 3 atomic layers, 4 atomic layers, 5 atomic layers, 6 atomic layers, 7 atomic layers, 8 atomic layers, 9 atomic layers, or 10 atomic layers.

[0044] Optionally, the thickness of the graphene layer formed on the surface of the copper substrate is 2 to 4 atomic layers thick.

[0045] Optionally, the copper substrate is single crystal copper.

[0046] When the copper substrate is single crystal copper, the corrosion prevention performance is better.

[0047] The method for converting polycrystalline copper into a single crystal includes the steps of placing the polycrystalline copper on a substrate, placing it in a CVD furnace, and heating it to 1000°C to 1080°C in an atmosphere containing an inert gas and hydrogen gas to perform a copper single crystallization process.

[0048] For example, the temperature for the copper single crystallization process is 1000°C, 1010°C, 1020°C, 1030°C, 1040°C, 1050°C, 1060°C, 1070°C or 1080°C.

[0049] Optionally, in the copper single crystallization process, the flow rate of the inert gas is 100 sccm to 1000 sccm, and the flow rate of the hydrogen gas is 1 sccm to 50 sccm.

[0050] The inert gas used in the copper single crystallization process includes one or more of helium gas, argon gas, xenon gas, and nitrogen gas.

[0051] For example, in a copper single crystallization process, the flow rate of the inert gas may be 100 sccm, 200 sccm, 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, 900 sccm, or 1000 sccm, and the flow rate of the hydrogen gas may be 1 sccm, 2 sccm, 5 sccm, 8 sccm, 10 sccm, 20 sccm, 30 sccm, 40 sccm, or 50 sccm.

[0052] Optionally, the time for the copper single crystallization treatment is 10 minutes to 300 minutes.

[0053] For example, the duration of the copper single crystallization treatment may be 10 minutes, 20 minutes, 50 minutes, 80 minutes, 100 minutes, 120 minutes, 150 minutes, 180 minutes, 200 minutes, 220 minutes, 250 minutes, 280 minutes or 300 minutes.

[0054] In some embodiments of the present application, a method for forming at least two layers of graphene on a surface of a copper substrate includes the steps of forming graphene having a thickness of one atomic layer on a surface of a copper substrate to obtain a first graphene layer, forming graphene having a thickness of one atomic layer on a surface of a copper carrier to obtain a second graphene layer, and transferring at least one second graphene layer onto the surface of the first graphene layer, and performing a graphene bonding treatment at 300°C to 500°C in an atmosphere containing an inert gas and a hydrogen gas.

[0055] By way of example, the temperature of the graphene bonding process can be 300°C, 320°C, 350°C, 380°C, 400°C, 420°C, 450°C, 480°C or 500°C.

[0056] Optionally, in the graphene bonding process, the flow rate of the inert gas is between 100 sccm and 1000 sccm, and the flow rate of the hydrogen gas is between 5 sccm and 100 sccm.

[0057] In the graphene bonding process, the inert gas includes any one or more of helium gas, argon gas, xenon gas, and nitrogen gas.

[0058] As an example, in the graphene bonding process, the flow rate of the inert gas can be 100 sccm, 200 sccm, 300 sccm, 400 sccm, 500 sccm, 600 sccm, 700 sccm, 800 sccm, 900 sccm, or 1000 sccm, and the flow rate of the hydrogen gas can be 1 sccm, 2 sccm, 5 sccm, 8 sccm, 10 sccm, 20 sccm, 30 sccm, 40 sccm, 50 sccm, 60 sccm, 70 sccm, 80 sccm, 90 sccm, or 100 sccm.

[0059] Optionally, the duration of the graphene bonding treatment is at least 6 hours.

[0060] By way of example, the duration of the graphene bonding treatment may be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours.

[0061] Optionally, the graphene bonding treatment time is between 6 hours and 24 hours.

[0062] In the present embodiment, graphene with a thickness of one atomic layer is formed on the surface of a copper substrate to obtain a first graphene layer, graphene with a thickness of one atomic layer is formed on the surface of a copper carrier to obtain a second graphene layer, and the prepared second graphene layer is then transferred to the surface of the first graphene layer on the copper substrate and subjected to a graphene bonding treatment to obtain a double-layer graphene layer. In this manner, the first graphene layer can be more firmly bonded to the surface of the copper substrate, reducing interfacial diffusion, and the second graphene layer has a shielding effect, resulting in less charge transfer and being nearly neutral, thereby suppressing the occurrence of electrochemical reactions and improving the corrosion protection performance of the copper substrate.

[0063] Optionally, when at least one second graphene layer is transferred onto the surface of the first graphene layer, one second graphene layer is transferred at a time, and a graphene bonding process is performed after each transfer of one second graphene layer.

[0064] A method for transferring at least one second graphene layer onto the surface of a first graphene layer includes the steps of: first forming a resin layer on the surface of the second graphene layer before the transfer; then etching graphene other than that of the second graphene layer; and then etching the copper carrier on the back surface (other side) of the second graphene layer to obtain the second graphene layer attached to the surface of the resin layer; and then placing the second graphene layer attached to the surface of the resin layer on the surface of the first graphene layer to perform a graphene bonding process.

[0065] The resin layer includes polymethyl methacrylate or polypropylene carbonate.

[0066] The resin layer is formed on the surface of the second graphene layer by spin-coating a resin solution dissolved in a solvent onto the surface of the second graphene layer, and heating at 40° C. to 160° C. for 1 to 5 minutes.

[0067] The solvent contains anisole. When the main component of the resin layer is polymethyl methacrylate, the mass fraction of polymethyl methacrylate in the resin solution is 3 wt% to 13 wt%, and the heating temperature is 80°C to 160°C. When the main component of the resin layer is polypropylene carbonate, the mass fraction of polypropylene carbonate in the resin solution is 6 wt% to 18 wt%, and the heating temperature is 40°C to 70°C.

[0068] Optionally, O2 plasma, O3 plasma, argon gas plasma, or hydrogen gas plasma is used to etch the graphene other than the second graphene layer.

[0069] Optionally, etch the copper carrier on the backside of the second graphene layer using 0.05 mol / L to 0.5 mol / L (NH4)2S2O8 solution and FeCl3 solution.

[0070] Optionally, the step of etching the copper carrier on the backside of the second graphene layer is performed in a water bath, and the water bath is first dried at 60°C to 90°C before the graphene bonding process.

[0071] The resin layer acts as a carrier for the second graphene layer after it is detached from the copper carrier, allowing the second graphene layer to be transferred to the surface of the first graphene layer while maintaining relatively good morphology.

[0072] A method for forming a first graphene layer or a second graphene layer having a thickness of one atomic layer on a surface of a copper substrate or a copper carrier includes the steps of growing and forming the first graphene layer or the second graphene layer having a thickness of one atomic layer on at least a part of the surface of the copper substrate or the copper carrier by chemical vapor deposition at 1000°C to 1080°C in an atmosphere containing methane, hydrogen gas, and an inert gas, and then introducing methane and hydrogen gases successively and allowing the resultant to cool naturally at atmospheric pressure.

[0073] Optionally, the flow rate of methane is between 0.005 sccm and 0.05 sccm, the flow rate of the inert gas is between 100 sccm and 1000 sccm, and the ratio of the flow rates of methane and hydrogen gas is between 1:200 and 1:1500.

[0074] By way of example, the flow rate of methane may be 0.005 sccm, 0.008 sccm, 0.01 sccm, 0.02 sccm, 0.03 sccm, 0.04 sccm or 0.05 sccm, and the flow rate ratio of methane to hydrogen gas may be 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1100, 1:1200, 1:1300, 1:1400 or 1:1500.

[0075] Optionally, the growth time is between 10 minutes and 30 minutes.

[0076] By way of example, the growth time may be 10 minutes, 12 minutes, 15 minutes, 18 minutes, 20 minutes, 22 minutes, 25 minutes, 28 minutes or 30 minutes.

[0077] In some embodiments of the present application, a method for forming at least two layers of graphene on a surface of a copper substrate includes growing a graphene layer having a thickness of multiple atomic layers on at least a portion of the surface of the copper substrate by chemical vapor deposition at 1000°C to 1080°C in an atmosphere containing methane, hydrogen gas, and an inert gas, and then introducing methane and hydrogen gases sequentially and allowing the substrate to cool naturally at atmospheric pressure.

[0078] Optionally, the flow rate of methane is 0.005 sccm to 0.1 sccm, the flow rate of the inert gas is 100 sccm to 1000 sccm, and the ratio of the flow rates of methane and hydrogen gas is 1:10 to 1:150.

[0079] By way of example, the flow rate of methane may be 0.005 sccm, 0.008 sccm, 0.01 sccm, 0.02 sccm, 0.03 sccm, 0.04 sccm, 0.05 sccm, 0.06 sccm, 0.07 sccm, 0.08 sccm, 0.09 sccm, 0.1 sccm, and the flow rate ratio of methane to hydrogen gas may be 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, or 1:150.

[0080] Optionally, the growth time is between 10 minutes and 300 minutes.

[0081] By way of example, the growth time may be 10 minutes, 20 minutes, 50 minutes, 80 minutes, 100 minutes, 120 minutes, 150 minutes, 180 minutes, 200 minutes, 220 minutes, 250 minutes, 280 minutes or 300 minutes.

[0082] In the method for preventing corrosion of metal copper according to the embodiments of the present application, a graphene layer having a thickness of at least two atomic layers is formed on the surface of a copper substrate, thereby weakening the charge transfer between the corrosive substance and the copper substrate, making it difficult for the copper substrate to undergo an electrochemical reaction with the graphene layer on the surface, thereby improving the corrosion prevention performance of the copper substrate.

[0083] Some other embodiments of the present application further provide a metallic copper corrosion-inhibiting structure, which is prepared by the metallic copper corrosion-inhibiting method described above.

[0084] The graphene layer, which is at least two atomic layers thick, weakens the charge transfer between the corrosive substance and the copper substrate, making it less likely for the copper substrate to react electrochemically with the graphene layer on its surface, thereby improving the corrosion protection performance of the copper substrate.

[0085] The metallic copper corrosion prevention structure includes a copper substrate and a graphene layer provided on at least a portion of the surface of the copper substrate, the graphene layer having a thickness of at least two atomic layers.

[0086] The method for preventing corrosion of metallic copper and the structure for preventing corrosion of metallic copper according to the present invention will be described in more detail below using examples.

[0087] Example 1 The embodiment of the present application provides a method for preventing metallic copper corrosion, which includes the following steps:

[0088] Step S1: Copper was subjected to single crystallization treatment. A rolled copper foil with a thickness of 25 μm was placed on a quartz substrate and placed in a CVD furnace, heated to 1040°C in an atmosphere of 500 sccm Ar and 10 sccm H2, and kept at 1040°C for 120 minutes to convert the polycrystalline copper foil into a single crystal.

[0089] Step S2: A graphene layer having a thickness of one atomic layer was formed on the surface of each of the copper carrier and the copper substrate. At least two 25 μm-thick single-crystallized rolled copper foils were placed on quartz substrates and placed in a CVD furnace. Growth was carried out for 20 minutes on at least a portion of the surface of the single-crystallized rolled copper foil at 1040°C in an atmosphere of 0.01 sccm CH, 10 sccm H, and 500 sccm Ar to form a graphene layer with a thickness of one atomic layer. Methane and hydrogen gas were then introduced, and the foil was allowed to cool naturally at atmospheric pressure.

[0090] Step S3: Bonding of graphene layers was performed. An 8 wt% solution of polymethyl methacrylate in anisole was spin-coated onto the surface of the graphene layer on the front side of the copper carrier and heated at 120°C for 2 minutes to obtain a polymethyl methacrylate layer. The graphene on the back side of the copper carrier was then completely etched using O2 plasma, and the copper carrier was then etched in a water bath using a 0.1 mol / L (NH4)2S2O8 solution to obtain a graphene layer attached to the surface of the polymethyl methacrylate layer. The graphene layer attached to the surface of the polymethyl methacrylate layer was then placed flat on the surface of the graphene layer on the surface of the copper substrate (with the two graphene layers in direct contact when placed), and the substrate was removed from the water bath, dried at 80°C, and annealed at 400°C for 10 hours in an atmosphere of 300 sccm Ar and 20 sccm H2 to remove the polymethyl methacrylate layer and bond the two graphene layers to obtain a bilayer graphene layer.

[0091] Example 2 The present application provides a method for preventing copper corrosion. In Example 1, after bonding two graphene layers to obtain a bilayer graphene layer, the graphene layer attached to the surface of the polymethyl methacrylate layer was then placed flat on the surface of the bilayer graphene layer on the surface of a copper substrate (with the graphene layers in direct contact with each other), removed from the water bath, dried at 80°C, and annealed at 400°C for 10 hours in an atmosphere of 300 sccm Ar and 20 sccm H2 to remove the polymethyl methacrylate layer and bond the two graphene layers to obtain a trilayer graphene layer.

[0092] Example 3 The present application provides a method for preventing copper corrosion. In Example 2, two graphene layers were bonded to form a three-layer graphene layer. The graphene layer attached to the surface of the polymethyl methacrylate layer was then placed flat on the surface of the three-layer graphene layer on the surface of a copper substrate (with the graphene layers in direct contact with each other). The substrate was then removed from the water bath, dried at 80°C, and annealed at 400°C for 10 hours in an atmosphere of 300 sccm Ar and 20 sccm H2. This removed the polymethyl methacrylate layer and bonded the two graphene layers to form a four-layer graphene layer.

[0093] Example 4 The embodiment of the present application provides a method for preventing metallic copper corrosion, which includes the following steps:

[0094] Step S1: Copper was subjected to single crystallization treatment. A rolled copper foil with a thickness of 25 μm was placed on a quartz substrate and placed in a CVD furnace, heated to 1040°C in an atmosphere of 500 sccm Ar and 10 sccm H2, and kept at 1040°C for 120 minutes to convert the polycrystalline copper foil into a single crystal.

[0095] Step S2: A graphene layer having a thickness of one atomic layer was formed on the surface of the copper carrier and the copper substrate. A 25 μm-thick single-crystallized rolled copper foil was placed on a quartz substrate and placed in a CVD furnace. First, growth was carried out on at least a portion of the surface of the single-crystallized rolled copper foil for 10 minutes at 1040°C in an atmosphere of 0.01 sccm CH4, 20 sccm H2, and 500 sccm Ar, and then growth was carried out on at least a portion of the surface of the single-crystallized rolled copper foil for 30 minutes at 1040°C in an atmosphere of 0.05 sccm CH4, 50 sccm H2, and 500 sccm Ar to form a graphene layer with a thickness of two atomic layers. Methane and hydrogen gas were then introduced, and the foil was allowed to cool naturally at atmospheric pressure, resulting in a bilayer graphene layer.

[0096] Comparative Example 1 The comparative example of this application provides a method for preventing metallic copper corrosion. The method for preventing metallic copper corrosion includes the following steps:

[0097] Step S1: Copper was subjected to single crystallization treatment. A rolled copper foil with a thickness of 25 μm was placed on a quartz substrate and placed in a CVD furnace, heated to 1040°C in an atmosphere of 500 sccm Ar and 10 sccm H2, and kept at 1040°C for 120 minutes to convert the polycrystalline copper foil into a single crystal.

[0098] Step S2: A graphene layer having a thickness of one atomic layer was formed on the surface of the copper carrier and the copper substrate. A 25 μm-thick single-crystallized rolled copper foil was placed on a quartz substrate and placed in a CVD furnace. Growth was carried out for 20 minutes at 1040°C in an atmosphere of 0.01 sccm CH, 10 sccm H, and 500 sccm Ar on at least a portion of the surface of the single-crystallized rolled copper foil to form a graphene layer with a thickness of one atomic layer. Methane and hydrogen gas were then introduced, and the foil was allowed to cool naturally at atmospheric pressure, yielding a single-layer graphene layer.

[0099] Test Example 1 Using a Kelvin probe force microscope and a nano-angle resolved photoelectron spectrometer, the surface potential and nano-angle resolved photoelectron spectrum of the graphene layers according to Example 1 and Comparative Example 1 were measured, respectively, and the results are shown in Table 1.

[0100] [Table 1] Table 1. Surface potential and downward shift of Dirac point of graphene layer according to Example 1 and Comparative Example 1

[0101] As can be seen from Table 1, the Kelvin probe force microscope measurements showed that the surface potential of the bilayer graphene layer in Example 1 was approximately 135 mV higher than that of the monolayer graphene layer in Comparative Example 1, indicating a relatively large number of electrons doped into the bilayer graphene layer. Nano-angle-resolved photoemission spectroscopy (NAPS) showed that the monolayer graphene layer in Cu was electron-doped, raising the Fermi level by approximately 0.15 eV. In contrast, in the bilayer graphene layer, the shifted electrons raised the Fermi level by approximately 0.2 eV, and electrons were primarily doped in the bottom layer, leaving the top layer nearly electrically neutral. First-principles calculations of differential charge density waves also confirmed that the bottom layer of the bilayer graphene layer was significantly bonded to Cu, while the top layer was nearly electrically neutral. This large Fermi level shift and unique electron distribution strengthened the bond between the bottom graphene and Cu, suppressing interfacial diffusion. In addition, due to the screening effect, the upper graphene layer is barely doped, and the density of active electrons on the surface of the upper graphene layer is significantly reduced. 2- It is even more difficult to reduce it to O 2- The diffusion of carbon atoms is also restricted vertically, reducing the cell reaction on the exposed Cu surface. This approach blocks four routes of failure for the graphene coating, namely, preventing the intrusion of corrosive molecules, inhibiting electrochemical reactions, reducing the density of intrinsic defects, and blocking interfacial diffusion. The synergistic effect of these four factors gives the multi-layer graphene layer excellent corrosion protection.

[0102] Test Example 2 The copper surface after oxidation was observed using an optical microscope, and brightness was used as a criterion for distinguishing between oxidized and unoxidized regions. The areas of the oxidized and unoxidized regions were statistically calculated. A comparative graph of the change over time in the corrosion area at 200°C for the metallic copper corrosion prevention structures of Example 1 and Comparative Example 1 is shown in Figure 1.

[0103] As can be seen from Figure 1, in the case of the double graphene layer, the copper oxidation rate was still maintained at 5% or less after 1000 hours at 200°C, and the oxidation rate when protected by the double graphene layer was five orders of magnitude lower than that of the single graphene layer.

[0104] Test Example 3 In-situ observation of the oxidation process was carried out using an in-situ environmental scanning electron microscope. SEM photographs of the copper corrosion prevention structures of Examples 1 to 3 and Comparative Example 1 after being corroded in oxygen gas at 230 Pa and 600°C for 1 second and 10 minutes are shown in Figures 2 and 3.

[0105] As can be seen from Figures 2 and 3, the two-layer graphene layer, the three-layer graphene layer, and the four-layer graphene layer can all protect the copper surface relatively well, whereas in the case of the single-layer graphene layer, it was completely destroyed within 1 second, and the form of copper oxide was observed.

[0106] Test Example 4 FIG. 4 shows a photograph comparing the corrosion prevention effects of the metallic copper corrosion prevention structures of Example 1 and Comparative Example 1 after heating at a high temperature of 250° C. for 6 hours, as observed with the naked eye.

[0107] As can be seen from FIG. 4, the area covered by the single-layer graphene layer turns black and dark, meaning that the surface is covered with copper oxide, while the area covered by the double-layer graphene layer still maintains the original luster of copper.

[0108] Test Example 5 The copper surface after oxidation was observed using an optical microscope, and comparative photographs of the corrosion prevention effects of the metal copper corrosion prevention structures of Examples 1 and 2 and Comparative Example 1 after heating at a high temperature of 250°C for 0 hours, 0.5 hours, 10 hours, and 15 hours are shown in Figure 5.

[0109] As can be seen from Figure 5, in the case of a single-layer graphene layer, after 0.5 hours of high-temperature oxidation, it is completely covered with copper oxide (a1 to a4 in Figure 5), while bilayer and trilayer graphene layers can protect the copper surface structure relatively well for 15 hours (b1 to b4 and c1 to c4 in Figure 5). Furthermore, for single defects (defects indicated by arrows in b1 to b4 and c1 to c4 in Figure 5), bilayer and trilayer graphene layers have almost the same ability to block the lateral propagation, and one advantage of trilayer graphene is that it can suppress the generation of new defects.

[0110] As described above, the method and structure for preventing corrosion of metallic copper according to the embodiments of the present application can protect a copper substrate for more than 5 years under conditions of room temperature and general humidity, and can protect copper for more than 1000 hours at 200° C. or for more than 6 hours at 250° C. Furthermore, the method for preventing corrosion of metallic copper according to the embodiments of the present application has excellent corrosion prevention effect without any particular requirements on the plane index, flatness of copper, or the interlayer twist angle of bilayer graphene.

[0111] The above are only specific examples of the present application and are not intended to limit the present application. Those skilled in the art may have various modifications and variations to the present application. As long as they do not deviate from the spirit and principles of the present application, any modifications, equivalent replacements, improvements, etc., fall within the scope of protection of the present application.

[0112] Industrial Availability Some embodiments of the present application provide a method for preventing corrosion of metallic copper. The method includes forming a graphene layer at least two atomic layers thick on the surface of a copper substrate. Some other embodiments of the present application provide a structure for preventing corrosion of metallic copper. The structure for preventing corrosion of metallic copper includes a copper substrate and a graphene layer provided on at least a portion of the surface of the copper substrate, the graphene layer having a thickness of at least two atomic layers. In the method for preventing corrosion of metallic copper and the structure for preventing corrosion of metallic copper according to the embodiments of the present application, by forming a graphene layer at least two atomic layers thick on the surface of the copper substrate, charge transfer between a corrosive substance and the copper substrate is weakened, making it less likely that the copper substrate will electrochemically react with the graphene layer on the surface, thereby improving the corrosion protection performance of the copper substrate.

[0113] Furthermore, the method and structure for preventing corrosion of metallic copper according to the present application can be implemented and used in various industrial applications, for example, in industries that use copper for production processing.

Claims

1. forming a graphene layer having a thickness of at least two atomic layers on the surface of a copper substrate. A method for preventing corrosion of metallic copper.

2. The thickness of the graphene layer formed on the surface of the copper substrate is 2 to 10 atomic layers.

2. The method for preventing corrosion of metallic copper according to claim 1.

3. The copper substrate is single crystal copper.

3. The method for preventing corrosion of metallic copper according to claim 1 or 2.

4. The method for obtaining the single crystal copper comprises: The polycrystalline copper is placed on a substrate, and the substrate is placed in a CVD furnace, and the substrate is heated to 1000°C to 1080°C in an atmosphere containing an inert gas and a hydrogen gas to perform a single crystallization treatment on the polycrystalline copper; The flow rate of the inert gas is 100 sccm to 1000 sccm, and the flow rate of the hydrogen gas is 1 sccm to 50 sccm.

4. The method for preventing corrosion of metallic copper according to claim 3.

5. The method for forming at least two graphene layers on the surface of the copper substrate includes the steps of: forming a graphene layer having a thickness of one atomic layer on the surface of the copper substrate to obtain a first graphene layer; forming a graphene layer having a thickness of one atomic layer on the surface of a copper carrier to obtain a second graphene layer; and transferring at least one of the second graphene layers onto the surface of the first graphene layer, and performing a graphene bonding treatment at 300°C to 500°C in an atmosphere containing an inert gas and a hydrogen gas; Optionally, in the graphene bonding process, a flow rate of the inert gas is 100 sccm to 1000 sccm, and a flow rate of the hydrogen gas is 5 sccm to 100 sccm; Optionally, the temperature at which the graphene bonding treatment is performed is 300°C, 320°C, 350°C, 380°C, 400°C, 420°C, 450°C, 480°C, or 500°C; Optionally, the graphene bonding treatment is for a period of at least 6 hours; Optionally, the graphene bonding treatment time is between 6 hours and 24 hours.

5. The method for preventing corrosion of metallic copper according to claim 1.

6. When transferring at least one second graphene layer onto the surface of the first graphene layer, one second graphene layer is transferred at a time, and the graphene bonding process is performed after each transfer of one second graphene layer.

6. The method for preventing corrosion of metallic copper according to claim 5.

7. the method for forming the graphene layer having a thickness of one atomic layer on the surface of the copper substrate to obtain the first graphene layer includes a step of growing the first graphene layer having a thickness of one atomic layer on at least a part of the surface of the copper substrate by chemical vapor deposition at 1000° C. to 1080° C. in an atmosphere containing methane, hydrogen gas, and an inert gas; or the method for forming the graphene layer having a thickness of one atomic layer on the surface of the copper carrier to obtain the second graphene layer includes a step of growing the second graphene layer having a thickness of one atomic layer on at least a part of the surface of the copper carrier by chemical vapor deposition at 1000° C. to 1080° C. in an atmosphere containing methane, hydrogen gas, and an inert gas; The flow rate of methane is 0.005 sccm to 0.05 sccm, the flow rate of the inert gas is 100 sccm to 1000 sccm, and the ratio of the flow rates of methane and hydrogen gas is 1:200 to 1:1500.

6. The method for preventing corrosion of metallic copper according to claim 5.

8. The method of transferring at least one second graphene layer onto a surface of the first graphene layer comprises: Before the transfer, a resin layer is first formed on the surface of the second graphene layer, graphene other than the second graphene layer is etched, and the copper carrier located on the back surface of the second graphene layer is etched to obtain the second graphene layer attached to the surface of the resin layer. The second graphene layer attached to the surface of the resin layer is then placed on the surface of the first graphene layer, and the graphene bonding treatment is performed. The method for preventing corrosion of metallic copper according to any one of claims 5 to 7.

9. The resin layer includes polymethyl methacrylate or polypropylene carbonate.

9. The method for preventing corrosion of metallic copper according to claim 8.

10. The step of forming the resin layer on the surface of the second graphene layer includes the steps of spin-coating a resin solution dissolved in a solvent on the surface of the second graphene layer and heating the resin solution at a heating temperature of 40° C. to 160° C. for 1 minute to 5 minutes.

10. The method for preventing corrosion of metallic copper according to claim 8 or 9.

11. The solvent includes anisole.

11. The method for preventing corrosion of metallic copper according to claim 10.

12. When the main component of the resin layer is polymethyl methacrylate, the mass fraction of polymethyl methacrylate in the resin solution is 3 wt % to 13 wt %, and the heating temperature is 80°C to 160°C; or when the main component of the resin layer is polypropylene carbonate, the mass fraction of polypropylene carbonate in the resin solution is 6 wt % to 18 wt %, and the heating temperature is 40°C to 70°C.

12. The method for preventing corrosion of metallic copper according to claim 10 or 11.

13. O ２ Plasma, O ３ and etching the graphene other than the second graphene layer using plasma, argon gas plasma, or hydrogen gas plasma. The method for preventing corrosion of metallic copper according to any one of claims 8 to 12.

14. 0.05 mol / L to 0.5 mol / L (NH ４ ) ２ S ２ O ８ solution and FeCl ３ Etching the copper carrier located on the backside of the second graphene layer using a solution. The method for preventing corrosion of metallic copper according to any one of claims 8 to 13.

15. The method for forming at least two graphene layers on the surface of the copper substrate includes the steps of: growing a graphene layer having a thickness of a plurality of atomic layers on at least a portion of the surface of the copper substrate by chemical vapor deposition at 1000°C to 1080°C in an atmosphere containing methane, hydrogen gas, and an inert gas; The flow rate of methane is 0.005 sccm to 0.1 sccm, the flow rate of the inert gas is 100 sccm to 1000 sccm, and the ratio of the flow rates of methane and hydrogen gas is 1:10 to 1:

150.

5. The method for preventing corrosion of metallic copper according to claim 1.

16. A copper corrosion inhibitor prepared by the method for inhibiting metallic copper corrosion according to any one of claims 1 to 15. Features a metal copper corrosion prevention structure.

17. The present invention comprises a copper substrate and a graphene layer provided on at least a portion of the surface of the copper substrate, the graphene layer having a thickness of at least two atomic layers. A metal copper corrosion prevention structure characterized by:

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