TWI787598B - Method of manufacturing ordered arrangement of graphene-carbon nano tube of metal substrate and composite coatings for carbon deposit - Google Patents

Abstract

The invention discloses a method of manufacturing ordered arrangement of graphene-carbon nano tube of metal substrate and composite coatings for carbon deposit, which deposits sputtering target and penetrating fluid into evacuated penetrating oven in order to make the penetrating fluid penetrates the sputtering target in the evacuated penetrating oven, and places the penetrated sputtering target into evacuated magnetic control sputtering target machine and controls cooling water of the evacuated magnetic control sputtering target machine, namely, operates evacuated magnetic control sputtering process on the metal substrate, utilizes the characteristic of metal organic salt of the penetrating fluid that can remain non-magnetic under 150℃ before decomposition, decomposes nano metal organic salt particles in high temperature zone after being sputtering and depositing on the metal substrate as catalyst of carbon so the carbon that came from the sputtering target can form carbon structural layer on concave / convex rough portion of the metal substrate. Accordingly, the invention reflects the beneficial effects of being easy and time saving on manufacture.

Description

Fabrication method of ordered arrangement of graphene carbon nanotubes on metal substrate and carbon deposition composite coating

The present invention relates to a manufacturing method for the ordered arrangement of graphene carbon nanotubes on a metal substrate and a carbon deposition composite coating, in particular to a method that is simpler and more convenient to manufacture, and can save man-hours. Those who have more practical and functional characteristics in its overall implementation and use.

Press, with the vigorous development of high technology, the volume of electronic components tends to be miniaturized, and the density per unit area is getting higher and higher, and its performance is continuously enhanced. Under these factors, the product quality of electronic components The demand is increasing almost every year.

Among them, as far as the metal substrates of common electronic components are concerned, during the production process, the metal substrates are mainly cleaned with chemicals [such as: strong acid, strong alkali] in the erosion tank to remove oil and rust. And after the neutralization tank and the cleaning tank are washed to remove the agent, And through a number of chemical tanks, the surface of the aluminum foil is processed by chemical erosion and corrosion to form a surface with a large number of concave holes, and then after neutralization and cleaning, strong acid and electrochemical action to form an oxidation tank with a voltage-resistant oxide layer, and finally through cleaning The neutralization tank and the drying tank are used to complete the manufacturing procedure of the metal base material.

However, although the above metal substrate manufacturing method can achieve the expected effect of making the metal substrate, it is also found in the actual implementation process that the metal substrate needs to go through a number of different grooves for production. The number of different steps not only makes the steps extremely complicated and inconvenient, but also consumes more man-hours for production, so that there is still room for improvement in the overall implementation of the operation.

The reason is that, in view of this, the inventor has been adhering to years of rich experience in design, development and actual production in this related industry, and then researched and improved it to provide a composite coating of ordered arrangement of graphene carbon nanotubes and carbon deposition on a metal substrate Manufacturing methods, in order to achieve the purpose of better practical value.

The main purpose of the present invention is to provide a manufacturing method for the ordered arrangement of graphene carbon nanotubes on metal substrates and carbon deposition composite coating, which is mainly easier and more convenient to manufacture, and can save more man-hours. And in its overall implementation and use, it has more practical and functional characteristics.

The main purpose and effect of the method for manufacturing the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating of the present invention are achieved by the following specific technical means: Its main system includes the following steps: A. Graphite sputtering target material: making graphite into magnetron sputtering target material of various geometric shapes; B. Penetrating liquid: dissolving organic metal salt in organic solvent to make it reach Saturate the solubility, and make the permeate; C. Infiltration: Put the sputtering target and the permeate into the vacuum infiltration furnace together, let the permeate penetrate into the sputtering target under the vacuum environment in the vacuum infiltration furnace Middle; D. Metal substrate: The metal substrate is formed with concave-convex roughness on the double-sided surface; E. Sputtering: The sputtering target material penetrated by the penetrating liquid is placed in a vacuum magnetron sputtering target machine , by controlling the cooling water in the vacuum magnetron sputtering target machine, the vacuum magnetron sputtering operation can be performed on the metal substrate treated in step D, and the organometallic salt of the penetrant is used before it is decomposed below 150°C It still remains non-magnetic, and after being sputtered, the metal particles of nano-organic metal salt are decomposed in the high temperature region and deposited on the metal substrate, as a catalyst for carbon, so that the carbon from the sputtering target is quickly Bond with each other to form an ordered carbon structure, that is, an ordered two-dimensional or three-dimensional carbon structure layer can be formed on the concave-convex rough part of the metal substrate.

A preferred embodiment of the manufacturing method of the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating of the present invention, wherein the graphite content of the sputtering target is ≧99.95%, and the porosity is 15%. ~30%.

The ordered arrangement and carbon deposition complex of graphene carbon nanotubes on the metal substrate of the present invention A preferred embodiment of the manufacturing method of composite coating, wherein, the vacuum infiltration furnace is provided with a furnace body, the furnace body is used for setting the sputtering target material, and the permeating liquid is made to submerge the sputtering target material in the furnace body, and then The furnace body is equipped with a vacuum valve connected to the air pressure control device. The high vacuum pump of the air pressure control device can be used to vacuumize the interior of the furnace body, and a vacuum gauge is installed on the furnace body. The furnace can be observed through the vacuum gauge. The air pressure inside the body.

In the preferred embodiment of the manufacturing method for the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating of the present invention, the furnace body of the vacuum infiltration furnace is connected with a permeate recovery tank, through the infiltration The liquid recovery tank recovers the used permeate for repeated recycling.

A preferred embodiment of the manufacturing method of the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating of the present invention, wherein the metal substrate is a high-purity aluminum foil with an aluminum content≧99.7%, and a copper content Any kind of 99.7% high-purity copper foil.

A preferred embodiment of the manufacturing method of the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating of the present invention, wherein the metal substrate is subjected to chemical rough plating, electrochemical corrosion, and spray coating on both sides. , Evaporation and sputtering forms a rough part on the surface.

The preferred embodiment of the manufacturing method of the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating of the present invention, wherein the vacuum magnetron sputtering target machine is a planar vacuum magnetron sputtering target machine, Either circular planar vacuum magnetron sputtering target machine or cylindrical magnetic vacuum magnetron sputtering target machine.

The ordered arrangement and carbon deposition complex of graphene carbon nanotubes on the metal substrate of the present invention A preferred embodiment of the method for manufacturing a composite coating, wherein the target surface of the sputtering target is maintained at a temperature below 150°C, and at the same time, the working temperature in the cavity of the vacuum magnetron sputtering target machine is at least 300°C, The vacuum degree is below 0.1Pa.

A preferred embodiment of the manufacturing method of the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating of the present invention, wherein the organometallic salt is any one of iron, cobalt, and nickel.

A preferred embodiment of the manufacturing method of the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating of the present invention, wherein the carbon structure layer formed on the concave-convex rough part of the metal substrate is Carbon nanotubes, graphene, or a combination of both.

1: Sputtering target

2: Penetrant

3: Vacuum infiltration furnace

31: furnace body

311: vacuum valve

312: Vacuum gauge

32: Air pressure control device

33: Permeate recovery tank

4: Vacuum magnetron sputtering target machine

5: Metal substrate

51: carbon structure layer

Figure 1: Schematic diagram of the production process of the present invention

Figure 2: Schematic diagram of the structure of the vacuum infiltration furnace of the present invention

Figure 3: Schematic diagram of the application of the present invention to a planar vacuum magnetron sputtering target machine

Figure 4: Schematic diagram of the application of the present invention to a circular planar vacuum magnetron sputtering target machine

Figure 5: Schematic diagram of the application of the present invention to a cylindrical magnetic vacuum magnetron sputtering target machine

Figure 6: Schematic diagram of the vacuum magnetron sputtering operation state of the present invention in an enhanced non-balanced closed magnetic field

Figure 7: Schematic diagram of the vacuum magnetron sputtering operation state of the present invention in a large multi-target non-balanced closed magnetic field

Figure 8: Another schematic diagram of the vacuum magnetron sputtering operation state of the present invention

Figure 9: Another schematic diagram of the vacuum magnetron sputtering operation state of the present invention

Figure 10: Schematic diagram of the forming state of the present invention

Figure 11: Schematic diagram of another forming state of the present invention

Figure 12: Another schematic diagram of the forming state of the present invention

In order to have a more complete and clear disclosure of the technical content used in the present invention, the purpose of the invention and the effects achieved, it will be described in detail below, and please refer to the disclosed drawings and figure numbers: first, please refer to As shown in the schematic diagram of the production process of the first figure of the present invention, the present invention mainly includes the following steps: A. Graphite sputtering target material: high-purity graphite with graphite content≧99.95% is made into magnetron sputtering targets of various geometric shapes material, and control the porosity of the sputtering target to 15%~30%; B. Penetrant: dissolve organic metal salts [such as: iron, cobalt, nickel, etc.] in organic solvents to make them reach saturated solubility , and make the permeate; C. permeate: Please refer to the second figure for the structure diagram of the vacuum infiltration furnace of the present invention As shown in the figure, the sputtering target (1) and the penetrant (2) are put into a vacuum infiltration furnace (3) together, and the vacuum infiltration furnace (3) is provided with a furnace body (31), and the furnace body (31 ) for setting the sputtering target (1), and make the permeate (2) submerge the sputtering target (1) in the furnace body (31), and set a vacuum valve in the furnace body (31) (311) is connected with the air pressure control device (32), and the high vacuum pump of the air pressure control device (32) can be used to vacuumize the interior of the furnace body (31), and a vacuum gauge is provided on the furnace body (31) (312), so that the pressure value inside the body of furnace (31) can be observed through the vacuum gauge (312), so that the penetrating liquid (2) can penetrate into the sputtering under the vacuum environment in the body of furnace (31) In the target (1), the furnace body (31) is also connected with a permeate recovery tank (33), so that the permeate that can be recycled through the permeate recovery tank (33) can be recycled for repeated use; D. Metal substrate: Metal substrates such as high-purity aluminum foil with an aluminum content ≥ 99.7% or high-purity copper foil with a copper content of 99.7% are chemically rough-plated or electrochemically etched or sprayed or sputtered on both sides to form Concave-convex roughness is formed on the surface of the metal substrate; E. Sputtering: Put the sputtering target (1) that has been infiltrated by the penetrant (2) into a vacuum magnetron sputtering target machine (4), and the vacuum The magnetron sputtering target machine (4) can be a planar vacuum magnetron sputtering target machine (please refer to the third figure together as shown in the schematic diagram of the use state of the present invention applied to a planar vacuum magnetron sputtering target machine], circular Planar vacuum magnetron sputtering target machine (please refer to the fourth figure together with the schematic diagram of the use state of the present invention applied to the circular plane vacuum magnetron sputtering target machine), cylindrical magnetic vacuum magnetron sputtering target machine [ Please refer to the fifth figure again and the present invention is applied to any one of the schematic diagram of the use state of the cylindrical magnetic vacuum magnetron sputtering target machine] to control the cooling water in the vacuum magnetron sputtering target machine (4), so that The target surface of the sputtering target (1) is kept at most below 150°C, while the vacuum magnetron sputtering The working temperature in the cavity of the target machine (4) is at least 300°C and the vacuum degree is below 0.1Pa, and then the vacuum magnetron sputtering operation can be performed on the metal substrate (5) processed in step D [please also Refer to the sixth figure, the schematic diagram of the vacuum magnetron sputtering operation state of the present invention in the enhanced unbalanced closed magnetic field, the seventh figure, the schematic diagram of the vacuum magnetron sputtering operation state of the present invention in the large multi-target non-balanced closed magnetic field, and the eighth figure Another schematic diagram of the vacuum magnetron sputtering operation state of the invention and the schematic diagram of another vacuum magnetron sputtering operation state of the present invention shown in Figure 9], using the organometallic salt of the penetrant (2) [such as: iron , cobalt, nickel, etc.] remains non-magnetic before being decomposed below 150°C, and after being sputtered to a high temperature area, metal particles of nano-organic metal salts such as iron, cobalt, and nickel are decomposed and deposited on the metal substrate On (5), as a carbon catalyst, the carbon atoms or carbon clusters from the sputtering target (1) in an endless supply are quickly bonded to each other to form an ordered carbon structure, so that the metal An ordered two-dimensional or three-dimensional carbon structure layer (51) of carbon nanotubes or graphene or a combination of both is formed on the concave-convex rough part of the entire or partial surface of the substrate (5) [the tenth figure of the present invention The schematic diagram of the forming state of the present invention, the schematic diagram of another forming state of the present invention in the eleventh figure and the schematic diagram of another forming state of the present invention in the twelfth figure], and use the vacuum magnetron sputtering target machine (4) to maintain the work The conditions are to control the length or sheet diameter of the carbon structure layer (51) formed on the metal substrate (5).

In this way, the metal substrate (5) can be applied to capacitor electrode foils, supercapacitor electrode foils, lithium battery electrodes, heat dissipation films, EMI heat dissipation films, and the like.

By the above, the description of the use and implementation of the present invention shows that compared with the prior art means, the present invention is mainly simpler and more convenient to manufacture, and more capable of It saves manufacturing man-hours and adds more practical and functional characteristics in its overall implementation and use.

However, the aforementioned embodiments or drawings do not limit the product structure or usage of the present invention, and any appropriate changes or modifications by those with ordinary knowledge in the technical field shall be considered as not departing from the patent scope of the present invention.

To sum up, the embodiment of the present invention can indeed achieve the expected use effect, and the specific structure disclosed by it has not only never been seen in similar products, nor has it been disclosed before the application, and it has fully complied with the provisions of the Patent Law In accordance with the requirements, it is very convenient to file an application for a patent for invention in accordance with the law, and sincerely ask for the review and approval of the patent.

Claims (9)

A manufacturing method for the ordered arrangement of graphene carbon nanotubes on a metal substrate and carbon deposition composite coating, which mainly includes the following steps: A. Graphite sputtering target material: making graphite into magnetrons of various geometric shapes Sputtering target; B. Penetration solution: dissolve the organic metal salt in the organic solvent to make it reach saturation solubility, and make the permeation solution; C. Penetration: put the sputtering target material and the permeation solution together Vacuum infiltration furnace, allowing the penetrant to infiltrate into the sputtering target material under the vacuum environment in the vacuum infiltration furnace, and the vacuum infiltration furnace is provided with a furnace body for setting the sputtering target material, and making the sputtering target material The permeate submerges the sputtering target in the furnace body, and a vacuum valve is provided in the furnace body to connect with the air pressure control device. The high vacuum pump of the air pressure control device can be used to evacuate the inside of the furnace body, and in the furnace body The furnace body is equipped with a vacuum gauge, and the air pressure value inside the furnace body is observed through the vacuum gauge; D. metal substrate: the metal substrate is formed with concave and convex rough parts on the double-sided surface; E. sputtering: the penetrating liquid is passed through After infiltration, the sputtering target material is put into the vacuum magnetron sputtering target machine, and the cooling water in the vacuum magnetron sputtering target machine can be controlled to perform vacuum magnetron sputtering on the metal substrate processed through step D. In the plating operation, the organometallic salt of the penetrating solution remains non-magnetic until it decomposes below 150°C. After being sputtered, the metal particles of nano-organic metal salt are decomposed in the high temperature area and deposited on the metal substrate. , as a carbon catalyst, making The carbon from the sputtering target can be quickly bonded to each other to form an ordered carbon structure, that is, an ordered two-dimensional or three-dimensional carbon structure layer can be formed on the concave-convex rough part of the metal substrate. The manufacturing method of ordered arrangement of graphene carbon nanotubes on metal substrate and carbon deposition composite coating as described in Claim 1, wherein, the graphite content of the sputtering target is ≧99.95%, and the porosity is 15%~ 30%. The manufacturing method of ordered arrangement of graphene carbon nanotubes on metal substrate and carbon deposition composite coating as described in Claim 1, wherein, the furnace body of the vacuum infiltration furnace is connected with a permeate recovery tank, through which the permeate The recovery tank recovers the used permeate for repeated use. The manufacturing method of ordered arrangement and carbon deposition composite coating of graphene carbon nanotubes on metal substrate as described in Claim 1, wherein the metal substrate is high-purity aluminum foil with aluminum content ≧99.7% and copper content 99.7% % of high-purity copper foil of any kind. The manufacturing method of ordered arrangement of graphene carbon nanotubes and carbon deposition composite coating of metal substrate as described in claim 1 or 4, wherein, the metal substrate is subjected to chemical rough plating, electrochemical corrosion, Any method of spraying or sputtering forms unevenness and roughness on the surface. The manufacturing method of ordered arrangement and carbon deposition composite coating of graphene carbon nanotubes on metal substrate as described in Claim 1, wherein, the vacuum magnetron sputtering target machine is a planar vacuum magnetron sputtering target machine, circular Any one of the planar vacuum magnetron sputtering target machine and the cylindrical magnetic vacuum magnetron sputtering target machine. The manufacturing method of ordered arrangement of graphene carbon nanotubes on metal substrate and carbon deposition composite coating as described in Claim 1, wherein the target surface of the sputtering target is maintained at a temperature below 150°C, and at the same time the The working temperature in the cavity of the vacuum magnetron sputtering target machine is at least 300°C and the vacuum degree is below 0.1Pa. The manufacturing method of ordered arrangement of graphene carbon nanotubes on metal substrate and carbon deposition composite coating as described in Claim 1, wherein the organometallic salt is any one of iron, cobalt, and nickel. The manufacturing method of the ordered arrangement of graphene carbon nanotubes on the metal substrate and the carbon deposition composite coating as described in claim 1, wherein the carbon structure layer formed on the concave-convex rough part of the metal substrate is carbon Any one or a combination of nanotubes and graphene.

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