CN107419220B

CN107419220B - Method for forming amorphous carbon/M metal layer on substrate

Info

Publication number: CN107419220B
Application number: CN201610347996.2A
Authority: CN
Inventors: 赖富德
Original assignee: National Kaohsiung First University of Science and Technology
Current assignee: National Kaohsiung First University of Science and Technology
Priority date: 2016-05-23
Filing date: 2016-05-23
Publication date: 2020-05-19
Anticipated expiration: 2036-05-23
Also published as: CN107419220A

Abstract

The invention discloses a manufacturing method of forming a carbon-metal double layer and a carbon-metal-carbon triple layer on a substrate, which comprises the steps of applying a nickel sputtering process, bombarding a nickel target by plasma, and depositing a copper or nickel layer on the substrate; bombarding the carbon-containing reaction gas and the copper or nickel target by plasma to form a copper or nickel and carbon mixed layer on the nickel layer; applying a vacuum annealing process to form an (amorphous) phase carbon/copper or nickel layer/(amorphous) phase carbon/copper or nickel layer on the substrate. In another embodiment, the sputtering chamber is pre-coated with nickel, then the plasma bombards the copper or nickel target and the graphite target simultaneously or sequentially, and then the annealing is performed, and the (amorphous) phase carbon/copper or nickel layer/(amorphous) phase carbon triple layer is formed in the hydrogen-containing atmosphere.

Description

Method for forming amorphous carbon/M metal layer on substrate

Technical Field

The invention relates to a low-temperature manufacturing method of a carbon single component layer, or a carbon-copper double layer or a carbon-copper-carbon three layer, in particular to a method for forming a target product by bombarding copper, carbon-containing reaction gas or a copper target and a graphite target simultaneously or in a preset sequence on a substrate at the temperature of between room temperature and 400 ℃, and then annealing or not annealing at a preset temperature so as to be used by industrial industry.

Background

Perfect graphene refers to a thin film with a regular hexagonal lattice structure and a thickness of only a single carbon atom layer, wherein carbon atoms are covalently bonded to each other along a plane by sp2 hybrid domains. Graphene is known to have excellent carrier mobility (5000-10000 cm)²Vs), hardness (1050GPa), thermal conductivity (5000W/mk), and current carrying capacity (108A/cm)²) And an extremely large reaction surface-to-volume ratio (2630 m)²In terms of/g). The graphene has various advantages, so that the graphene becomes an excellent material with both substitution and integration in the application range of next generation biomedical, electronic and photoelectric components. Therefore, since 2004, it was found that graphene has not been actively developed in various fields, but almost every method of preparing graphene involves double layers or even more, hundreds to thousands of layers of graphene, and there is graphene in which a non-orthohexagonal lattice structure includes defects.

The more common preparation methods include mechanical exfoliation, thermal cracking of high temperature silicon carbide, and Chemical Vapor Deposition (CVD). The mechanical stripping method is used for obtaining graphene by destroying weak Vanderwal bonding between a high-orientation thermal cracking graphite layer and an interlayer. The method for preparing the graphene is fast and convenient, and more attractive, expensive process equipment is not needed, and the preparation can be carried out only by a small amount of cost of adhesive tapes, graphite sheets and the like. Further, the graphite master used for exfoliation is highly oriented thermally cracked graphite having high purity and excellent crystallinity, and thus, the obtained graphene hardly has any defects. Unfortunately, the resulting graphite flakes incorporate non-uniform graphite flakes ranging from single-layer, double-layer, and even several-layer, and thus are not conducive to introduction into the standard processes of the semiconductor industry.

Chemical Vapor Deposition (CVD) is currently the most common method for preparing graphene, and is currently the most suitable method for integrating with the standard processes of the semiconductor industry today, while obtaining large-area and high-quality graphene. Therefore, the method is a quite popular technology for preparing graphene at present. To reduce reactive gases such as methane (CH)₄) Etc. the conventional technique uses cobalt, nickel, copper, etc. transition metal elements as catalysts to reduce the cracking temperature, especially copper. For example, in 2011, a research team, which is introduced by the central research institute of applied sciences, china, and the sun-Yuan Su, directly grows graphene with a chip scale size on an insulating substrate. They were first SiO₂Depositing a copper film with the thickness of about 300nm on a Si substrate in a sputtering way, then putting the substrate into a CVD cavity, raising the temperature of the cavity to 900 ℃, and then introducing methane gas; carbon atoms cracked from methane are deposited on the surface of copper, and at the same time, the carbon atoms deposited on the surface of copper gradually diffuse into the interlayer between the copper thin film and the substrate through the Grain boundary (Grain boundary) of the copper thin film, further nucleate and form graphene. The method can save the step of substrate transfer, directly grow the graphene on the target substrate, and simultaneously, can reduce the probability of film damage possibly caused in the transfer process because the transfer step is saved, thereby improving the yield of production. The cracking temperature of the hydrocarbon gas of the carbon source gas must be maintained at a high temperature of about 900 ℃. This may still be an obstacle for future graphene introduction into assembly processes.

The above process must be further applied with a copper metal removal process. Namely, the copper or nickel is removed by wet etching using a solution such as hydrochloric acid or nitric acid. After complete etching, the graphene can float in the etching solution, and then the graphene is fished out of the etching solution by different substrates, so that subsequent various instrument analyses can be performed. In the process of film transfer, in order to ensure the integrity of graphene, before metal etching, a layer of organic polymer is coated on the surface of graphene to serve as an etching protection film. Most of the organic polymer layer is a long-chain hydrocarbon non-crystalline substance, once the substance contacts the surface of the graphene, the substance cannot be thoroughly cleaned, and the organic polymer remaining on the surface of the graphene shields the contact of the graphene and the environment, so that the sensitivity of the graphene to environmental changes is reduced, and the application of the graphene in the aspect of sensors is limited.

The graphene referred to above generally refers to graphene in which carbon atoms are arranged in a single layer or several layers or even tens of atomic layers. However, when the number of carbon atoms is several hundreds to several tens of thousands, graphene is not generally used, and it is industrially very useful, but it is still necessary to optimize the preparation at a low temperature. The above-mentioned processes are all prepared at high temp. of above 750 deg.C.

Disclosure of Invention

In order to solve the problem that the conventional technology needs high temperature, the invention provides a low-temperature manufacturing method for preparing a carbon/copper double layer on a substrate and a carbon/copper layer/carbon triple layer on the substrate at low temperature, also comprises a preparation method of a carbon single-component layer, and also comprises a preparation method of graphene.

It is an object of the present invention to provide a low temperature manufacturing of a (amorphous) crystalline carbon layer.

It is another object of the present invention to provide a method for low temperature manufacturing of (amorphous) phase carbon/copper layer or nickel layer/micro oxidized (amorphous) phase carbon.

It is a further object of the present invention to provide a method for low temperature manufacturing of (amorphous) phase carbon/copper layer or nickel layer/(amorphous phase carbon).

The technical solution of the invention is as follows:

the invention discloses a low-temperature manufacturing method for forming a carbon/copper layer or a nickel layer on a substrate, wherein, the first embodiment comprises the steps of applying a copper or nickel sputtering process, bombarding a copper or nickel target by plasma, and depositing the copper or nickel layer on the substrate; bombarding the carbon-containing reaction gas and the copper or nickel target by plasma to form a copper-carbon mixed layer on the copper or nickel layer; an annealing process is applied in a vacuum furnace to form an (amorphous) phase carbon/copper layer or a nickel layer/micro-oxidized (amorphous) phase carbon on the substrate. When the annealing is carried out in a hydrogen-containing atmosphere, an (amorphous) phase carbon/copper layer or nickel layer/(amorphous phase carbon structure) is obtained.

In a variation of the first embodiment, the sputtering is performed while the chamber is heated to a predetermined temperature. The preset temperature refers to that the cavity is sputtered at the temperature below 400 ℃, and after sputtering is finished, annealing at 250-1100 ℃ is carried out or annealing is not carried out. If the annealing is carried out in a vacuum annealing furnace, the copper layer/micro-oxidation crystalline phase carbon and the substrate are further etched and removed, and then the lower crystalline phase carbon structure layer can be obtained.

The other technical scheme of the invention is as follows:

in a second preferred embodiment, a copper or nickel target and a graphite target are simultaneously bombarded with a plasma in a sputtering chamber to form a copper/carbon or nickel/carbon hybrid layer on a substrate. An annealing process is applied in a vacuum furnace to form an (amorphous) phase carbon/copper layer or a nickel layer/micro-oxidized (amorphous) phase carbon on the substrate. Annealing in a hydrogen-containing atmosphere results in an (amorphous) phase carbon/copper layer or nickel layer/(amorphous phase carbon structure).

In a variation of the second embodiment, the sputtering is performed while the chamber is heated to a predetermined temperature. Sputtering the cavity at a temperature below 400 ℃, and then annealing at 250-1100 ℃ or not annealing. If the annealing is carried out in a vacuum annealing furnace, the copper layer/micro-oxidation crystalline phase carbon and the substrate are further etched and removed, and then the lower crystalline phase carbon structure layer can be obtained.

The invention also adopts the technical scheme that:

in a third preferred embodiment, a copper or nickel target, a graphite target, a copper or nickel target, is sequentially bombarded with a plasma in a sputtering chamber to form a copper or nickel/carbon/copper or nickel layer on a substrate. An annealing process is applied in a vacuum furnace to form an (amorphous) phase carbon/copper layer or a nickel layer/micro-oxidized (amorphous) phase carbon on the substrate. When the annealing is carried out in a hydrogen-containing atmosphere, an (amorphous) phase carbon/copper layer or nickel layer/(amorphous phase carbon structure) is obtained. In a variation of the third preferred embodiment, the sputtering is performed while the chamber is heated to a predetermined temperature. The preset temperature refers to that the cavity is sputtered at the temperature below 400 ℃, and after sputtering is finished, annealing at 250-1100 ℃ is carried out or annealing is not carried out. If the annealing is carried out in a vacuum annealing furnace, the copper layer/micro-oxidation crystalline phase carbon and the substrate are further etched and removed, and then the lower crystalline phase carbon structure layer can be obtained.

The methods of the second and third preferred embodiments are advantageous for controlling the number of layers of crystallized carbon, for example, obtaining graphene one to several carbon atom layers thick.

The invention also aims at the terminal continuous application of different structure layers, for example, when sputtering is finished at normal temperature and annealing is not carried out, the invention is provided for the LED industry (continuous application E) or used as an electrode plate of a super capacitor. The single-layer structure of the crystalline phase carbon single layer or the single-layer structure of the amorphous phase carbon or the single-layer structure of the crystalline phase carbon/copper/crystalline phase carbon or the amorphous phase carbon/copper/amorphous phase carbon three-layer structure can be applied to electrode plates or soft plate substrates of super capacitors, heat dissipation substrates and ultrathin and ultralight body armor. And the crystal phase carbon/copper or nickel or amorphous phase carbon/copper or nickel double-layer structure can be applied to an electrode plate of a super capacitor or a cathode plate of a lithium battery.

The invention has the characteristics and advantages that:

1. the cavity can be directly applied to the LED industry or an electrode plate of a super capacitor by sputtering the copper-carbon or nickel-carbon mixed layer at normal temperature.

2. The cavity is sputtered with a mixed layer of copper carbon or nickel carbon at normal temperature, and medium-high temperature low (high) vacuum annealing is carried out to obtain a single-layer structure of crystalline phase carbon, a double-layer structure of crystalline phase carbon/copper or nickel (or a micro-oxidation crystalline phase carbon three-layer structure thereon), and medium-high temperature annealing is carried out in a hydrogen-containing atmosphere to obtain a three-layer structure of crystalline phase carbon/copper or nickel/crystalline phase carbon. The single-layer structure can be applied to electrode plates of a super capacitor, soft plate substrates, heat dissipation substrates and ultrathin and ultralight body armor. The double-layer structure can be applied to a plate electrode of a super capacitor and a cathode plate of a lithium battery. Low temperature annealing can similarly result in single, double or triple layer structures, except that the aforementioned crystalline phase carbon is replaced by amorphous phase carbon.

3. The sputtering is not limited to be carried out at normal temperature, and the sputtering can also be carried out in a cavity heated to a preset temperature (the structure containing the crystalline phase carbon/copper can be obtained at medium and low temperature not exceeding 400 ℃), and the annealing is preferably carried out at medium or high temperature, so that the quality is better.

The concept of the present invention not exceeding 400 ℃ can also be applied to electron gun evaporation (heating only copper or nickel blocks and graphite) in which the substrate can be not heated (or kept at a low temperature).

Drawings

The invention is illustrated and explained only by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which:

fig. 1A is a schematic flow chart of a pretreatment process of a silicon substrate.

FIG. 1B is a schematic view of a flow chart of a pretreatment process for a glass substrate and a quartz substrate.

Fig. 1C is a schematic flow chart of depositing an oxide layer on a silicon substrate.

FIG. 2A is a flow chart of a sputtering process for forming a single component layer of (amorphous) phase carbon structure or a two component layer of (amorphous) phase carbon/copper, a three component layer of (amorphous) phase carbon/copper or nickel/(amorphous) phase carbon by plasma bombardment of a single target and a carbon-containing reaction gas according to a first preferred embodiment of the present invention.

Fig. 2B is a flow chart of a sputtering process of a single-component layer of (non) crystalline phase carbon structure or a (non) phase carbon/copper or nickel (non) binary layer, or a (non) phase carbon/copper or nickel/(non) crystalline phase carbon ternary layer when the temperature of the chamber is raised according to a second preferred embodiment of the present invention, which is a variation of the first preferred embodiment.

FIG. 3A is a flow chart of a sputtering process for forming a single-component layer of (non-) crystalline carbon structure or a two-component layer of (non-) crystalline carbon/copper or nickel, or a three-component layer of (non-) crystalline carbon/copper or nickel/(non-) crystalline carbon by plasma bombardment of a single target and a graphite target according to a third preferred embodiment of the present invention.

Fig. 3B is a flow chart of a sputtering process of a (non) crystalline phase carbon structure single component layer or a (non) crystalline phase carbon/copper or nickel two component layer, or a (non) crystalline phase carbon/copper or nickel/(non) crystalline phase carbon three component layer when the temperature of the chamber is raised according to a fourth preferred embodiment of the present invention.

FIG. 4A is a flow chart of a sputtering process for forming a single-component layer of (non) crystalline phase carbon structure or a two-component layer of (non) crystalline phase carbon/copper or nickel, or a three-component layer of (non) crystalline phase carbon/copper or nickel/crystalline phase carbon by bombarding a single target and a graphite target in a predetermined order according to a fifth preferred embodiment of the present invention.

Fig. 4B is a schematic diagram of a process for sputtering a (amorphous) phase carbon structure single-component layer or a (amorphous) phase carbon/copper or nickel two-component layer or a (amorphous) phase carbon/copper or nickel/(amorphous) phase carbon three-component layer when the temperature of the chamber is raised according to a variation of the fifth preferred embodiment of the present invention.

Description of the symbols

VCH: this shows that the product is crystalline carbon and annealed at a high temperature during the vacuum furnace.

VAL: this shows that the product was amorphous carbon and annealed at a low temperature during the vacuum annealing.

RCH: the annealing is carried out in a reducing atmosphere of hydrogen, the product is crystalline phase carbon, and the annealing is carried out at medium and high temperatures.

RAL: this shows that the annealing was performed in a reducing atmosphere of hydrogen gas, and the product was amorphous carbon and was annealed at a low temperature.

B: and applying the negative plate of the continuous lithium battery.

E: and the LED industrial application is continued.

F: and connecting the soft board substrate, the heat dissipation substrate and the ultrathin and ultralight bullet-proof vest.

S: and connecting the super capacitor electrode plate for application.

Detailed Description

The following examples disclose a method for producing a single-component layer of (amorphous) crystalline carbon, a two-component layer of (amorphous) crystalline carbon/copper or nickel and a three-component layer of (amorphous) crystalline carbon/copper layer/(amorphous) crystalline carbon at low temperatures. The crystalline carbon (crystal carbon) refers to carbon atoms in a regular arrangement, and the amorphous carbon refers to amorphous carbon.

The substrate of the invention can be a silicon substrate, a glass substrate, a quartz substrate, a PET substrate, wherein the PET film is a high temperature resistant (up to 350 ℃) polyester film. Glass substrates are also substrates that can withstand high temperatures (up to 550 ℃).

The silicon substrate pre-cleaning is shown in fig. 1A. As shown in step 100, the silicon substrate is soaked in a mixture of sulfuric acid, hydrogen peroxide, and deionized water (d.i. water) for several minutes, and simultaneously cleaned with an ultrasonic oscillator for 5-15 minutes. The strip is removed and washed with d.i. as shown in step 110. Next, as shown in step 120, the silicon substrate is soaked in diluted hydrofluoric acid (e.g., 0.1% HF) as a buffer for about 10-40 seconds. Then, as shown in step 130, the test piece is taken out and washed clean with d.i.water. Then, as shown in step 140, the test piece is purged with nitrogen gas, thereby completing the process. When the substrate is a glass substrate or a quartz substrate, the cleaning step is slightly different as shown in fig. 1B. In step 105, the substrate is soaked in acetone and cleaned with an ultrasonic oscillator for 5-15 minutes, and then cleaned with d.i. water in step 110. Next, as shown in step 115, soaking in isopropanol and washing for 5-15 min with an ultrasonic oscillator; then, as shown in step 130, the test strip is taken out and washed clean with d.i.water. In step 140, the test piece is purged with nitrogen gas.

According to a preferred embodiment of the present invention, if the substrate is a silicon substrate, an oxide layer with a thickness of about 100nm or more must be deposited in the subsequent deposition process to prevent the copper, nickel, iron or cobalt and silicon from directly generating metal silicide during annealing. The nickel or cobalt or copper on the substrate helps to control the number of layers of graphene more precisely, as shown in fig. 1C. Nickel or cobalt or iron on the substrate also helps the carbon layer accelerate the catalyst to the crystalline phase carbon. The crystalline phase carbon layer referred to herein may be graphite or graphene, which refers to graphene having a number of crystalline layers ranging from several to tens of atomic layers.

Nickel and copper both have the characteristic of accelerating the conversion of the carbon layer into crystalline carbon. Therefore, in the following embodiments, M appearing in fig. 2A, 2B, 3A, 3B, 4A, 4B of the flow chart represents one of nickel or copper. In the sputtering process, the copper target has no ferromagnetism, does not influence the magnetic field, and is beneficial to controlling the position of the plasma. Since the nickel target is made of a ferromagnetic material, the influence of the nickel target must be considered in the magnetron device at the rear end of the target. The nickel layer is relatively advantageous for controlling the number of atomic layers of crystalline phase carbon compared to copper and nickel, because nickel has a lower solubility for carbon. Therefore, to control carbon to a lower atomic layer number, nickel is preferred. If the number of carbon atom layers is not limited, a copper target is preferred.

Referring to FIG. 2A, a first preferred embodiment of the present invention is shown in the flow chart of the sputtering process for forming a single component layer of (non) crystalline phase carbon structure or a two component layer of (non) phase carbon/copper or nickel, a three component layer of (non) phase carbon/copper or nickel/(non) crystalline phase carbon by plasma bombardment of a single target of copper or nickel and a carbon-containing reaction gas. According to a preferred embodiment of the present invention, the sputtering process is performed in a sputtering chamber. First, as shown in step 210, the pre-cleaned substrate is placed on the anode, and the cathode is pre-positioned with a copper or nickel target in the chamber. Next, as shown in step 220, the reactive magnetron sputtering chamber is evacuated to 1E-6 torr. It is particularly noted that if the substrate is a PET substrate, a glass substrate, whether or not coated with a nickel or iron or cobalt layer, they are not suitable for annealing at temperatures above 350 ℃ and 550 ℃, respectively, to avoid substrate disintegration.

Then, referring to step 230, target cleaning is performed. Shielding a test piece preset on the anode, introducing inert gas such as argon with the flow rate of about 50sccm into a magnetron sputtering chamber with the pressure of 7mTorr, applying bias voltage to the argon to form plasma with the power of 230-260 watts, and cleaning a copper or nickel target for about 10-30 minutes, preferably about 15-25 minutes.

The mask is then opened and a layer of copper or nickel is sputtered, as shown in step 240. Controlling the pressure of the cavity in the magnetron sputtering cavity to be 3mTorr and applying bias voltage: an inert gas, such as argon, is introduced at a flow rate of about 30sccm to plasma the argon for a pre-plating time of about 3-12 minutes, more preferably about 10 minutes. The corresponding power is about 140-160 watts in the example. So that the thickness of the copper or nickel layer is controlled between 5 nm and 300 nm.

Then, referring to step 250, reactive magnetron sputtering is performed. That is, the introduced gas contains a reaction gas of carbon in addition to an inert gas such as argon gas to form plasma, so as to plate a copper-carbon mixed layer with a predetermined thickness on the copper layer. In a preferred embodiment, the carbon-containing reactant gas is acetylene (C)₂H₂) Ethane (C)₂H₆) Propane (C)₃H₈) And the like. The more preferred reactant gas is acetylene. The parameter conditions were as follows: argon at a flow rate of about 30sccm and acetylene at a flow rate of 1-3 sccm. The power was 150 watts. The chamber pressure was 3 mTorr. The pre-plating time is about 30-120 minutes.

Subsequently, the vacuum of the sputtering chamber is released. At this time, there are several options, one of which is (1) taking the substrate out of the sputtering chamber in step 270, and the structure on the substrate from bottom to top is a mixed layer of copper or nickel layer/copper carbon or nickel carbon. The product can be applied in succession to the substrate of a light-emitting diode (LED), denoted here and hereafter by "E", or to the electrode plates of a supercapacitor, denoted "S" in the figure. (2) The substrate enters a vacuum annealing furnace for annealing, step 258.

The substrate/copper or nickel layer/copper carbon or nickel carbon according to the invention can be optionally annealed in a vacuum furnace or in a reducing atmosphere containing hydrogen, depending on the subsequent applicability of the final product. For convenience of illustration of the annealing temperature and its intended structure shown in the flow chart, the steps below sputtering the copper or nickel-carbon mixed layer will be indicated by (xxx), the first letter "V" in the small brackets represents vacuum furnace annealing, the first letter "R" represents annealing in a reducing atmosphere containing hydrogen, the second letter "a" represents an amorphous phase, the second letter "C" represents a crystalline phase, the third letter "H" represents medium and high temperatures, e.g., annealing at 250-1100 ℃, and the third letter "L" represents low temperature annealing at 50-249 ℃. For example, the (VCH) step means high temperature annealing in which the product is crystalline carbon, and the (VAL) step means low temperature annealing in which the product is amorphous carbon. The (RCH) step means intermediate/high temperature annealing performed in a reducing atmosphere of hydrogen gas, the product being crystalline phase carbon, and the (RAL) step means low temperature annealing performed in a reducing atmosphere of hydrogen gas, the product being amorphous phase carbon. The annealing in the vacuum annealing furnace means that the vacuum degree is 1E-1torr to 1E-2torr, and at the moment, the small amount of oxygen in the vacuum furnace can lead the surface layer after annealing to form oxidized crystalline carbon (medium and high temperature annealing) or oxidized amorphous carbon (low temperature annealing). This layer of oxidised crystalline carbon is of poor quality, whereas at higher vacuum, e.g. above 1E-3, the oxidised (non-) crystalline carbon will convert to slightly oxidised (non-) crystalline carbon. In the following description, unless otherwise specified, "single layer", "double layer" and "three layers" merely describe the material layers, that is, the constituent layers, and do not mean the atomic-scale layers. For example, an amorphous carbon monolayer, a crystalline carbon monolayer, may be several atomic layers to tens of thousands of atomic layers, unlike a defined monolayer in which single atomic layer carbon is known as graphene.

And annealing in a vacuum furnace, wherein the product on the substrate after annealing is a crystalline phase carbon/copper or nickel or an amorphous phase carbon/copper or nickel double-layer structure (under low vacuum degree). This is because copper or nickel has little solubility in carbon, and therefore, when the above-mentioned vacuum furnace annealing is performed, carbon in the copper-carbon or nickel-carbon mixed layer diffuses upward and downward, and the upward-diffused carbon layer further combines with the micro-oxygen in the vacuum furnace to form CO or CO in a gas phase₂And is entrained by the gas flow, as described above, e.g. with a vacuum of 10^-1torr-10^- ²torr. If the degree of vacuum is increased, e.g. 10^-3Above torr, the carbon layer diffused upward will be slightly oxidized, i.e. three-layer structure of crystalline phase carbon/copper layer or nickel layer/slightly oxidized crystalline phase carbon. The degree of oxidation depends on the degree of vacuum. Vacuum annealing ensures the quality of the (amorphous) phase carbon adjacent to the substrate. In contrast, when annealed in a reducing atmosphere containing hydrogen, the product on the annealed substrate will be a three-layer structure of crystalline carbon/copper or nickel/crystalline carbon, or amorphous carbon/copper or nickel/amorphous carbon, depending on the annealing temperature and time. This is because when the annealing is performed under hydrogen or ammonia gas, the carbon layer on the uppermost layer can be protected from oxidation during the annealing by the annealing atmosphere.

Depending on the end-use application, the uppermost copper or nickel layer may be removed or retained by wet etching. When the amorphous carbon/copper or nickel bilayer and the crystalline carbon/copper or nickel bilayer are selected to be removed by wet etching, the preferred embodiment is to remove the copper or nickel layer with ferric nitrate, as shown in step 280. In wet etching to remove the copper or nickel layer, the amorphous carbon/copper or nickel bilayer structure and the crystalline carbon/copper or nickel may be stripped, leaving only amorphous carbon or crystalline carbon, preferred applications include: the heat dissipation substrate is continuously applied to soft board substrates, heat dissipation substrates and ultrathin and ultralight body armor. Denoted herein and hereinafter by "F". Another preferred successive application is as an electrode plate of a supercapacitor denoted by "S".

In addition, the final product of the RCH step is a crystalline phase carbon/copper or nickel/crystalline phase carbon or RAL step, the final product is a three-layer structure of amorphous phase carbon/copper or nickel/amorphous phase carbon, and the three-layer structure and the substrate are easily separated in a physical film pulling mode because the bonding of the crystalline phase carbon or amorphous phase carbon of the bottom layer and the substrate is poor. When the final product is a three-layer structure of crystalline carbon/copper or nickel/crystalline carbon, or amorphous carbon/copper or nickel/amorphous carbon, it is preferably applied sequentially as F and S.

In addition, when the above-mentioned (VAL) step or (VCH) step is not performed by the above-mentioned wet etching, the obtained amorphous carbon/copper or nickel double layer structure and crystalline carbon/copper or nickel double layer structure preferably include S (in succession to the supercapacitor electrode plate) and a cathode in succession to the lithium battery, hereinafter denoted by B, wherein the above-mentioned amorphous carbon is heated to form crystalline carbon during the manufacturing process of the cathode of the lithium battery.

The first preferred embodiment of the present invention described above can be further modified to the second preferred embodiment. In a second preferred embodiment, before sputtering the copper-carbon mixed layer, the chamber is heated to a first predetermined annealing temperature, and then the copper-carbon or nickel-carbon mixed layer is sputtered, and the temperature is maintained until a crystalline phase carbon/copper or nickel layer, an amorphous phase carbon/copper or nickel layer, a crystalline phase carbon/copper or nickel layer/crystalline phase carbon, or an amorphous phase carbon/copper or nickel layer/amorphous phase carbon of the target structure is formed.

Please refer to the flow chart in fig. 2B. Steps 210-240 are as described above, and then the chamber is heated to the first predetermined temperature before the step of sputtering copper carbon or nickel carbon. As in step 245. Next, step 251 is performed at a first predetermined temperature, wherein the copper or nickel target and the carbon-containing reaction gas are bombarded by plasma, the mixed copper-carbon or nickel-carbon layer on the copper or nickel layer also forms a crystalline phase carbon/copper layer on the substrate when the first predetermined temperature is 250 to 400 ℃, and the mixed copper-carbon or nickel-carbon layer on the copper layer also forms an amorphous phase carbon/copper layer on the substrate when the first predetermined temperature is a low temperature of 50 to 250 ℃. The flow rate, chamber pressure, and power of the carbon-containing reactant gas are as described in the first preferred embodiment.

The substrate with the amorphous carbon/copper or nickel layer may be removed and subsequently applied as S or B as shown in step 262. on the other hand, the substrate removed in step 262 may be removed and subjected to wet etching as shown in step 280 to remove the copper or nickel plate and the substrate, and then subsequently applied as S or E or F.

When sputtering is performed at a predetermined temperature of 250-400 ℃, the substrate is formed with a crystalline phase carbon/copper or nickel layer, and then moved to a vacuum annealing furnace for intermediate or high temperature annealing to form a structure with better crystalline phase quality, as shown in step 260, and wet etching is performed to remove the copper or nickel layer and the substrate according to the purpose of subsequent applications, as shown in step 280. When sputtering is performed at a predetermined temperature of 250-400 c, a crystalline carbon/copper or nickel layer is formed on the substrate and can be directly removed, as shown in step 275.

On the other hand, after the chamber is heated to the first predetermined temperature, the copper or nickel target and the carbon-containing reaction gas may be bombarded simultaneously by plasma in an atmosphere containing hydrogen to form crystalline carbon/copper or nickel/crystalline carbon (the preheating temperature of the chamber is 250-400 ℃) or amorphous carbon/copper or nickel/amorphous carbon (the preheating temperature of the chamber is 50-249 ℃) on the substrate, as shown in step 255.

Then, on the substrate: after the crystalline carbon/copper or nickel/crystalline carbon is formed, the substrate is transferred to an annealing furnace under hydrogen containing atmosphere for annealing at medium or high temperature as described above to improve the quality of the crystalline carbon, as shown in step 265. The sputtering is performed in a relatively low temperature chamber (50-249 deg.C), and the three-layer structure of amorphous carbon/copper or nickel/amorphous carbon on the substrate can also be directly taken out, as shown in step 263.

In order to precisely control the weight percentage (wt%) of copper, nickel, or carbon in the copper, nickel, or carbon mixed layer to precisely obtain the number of amorphous carbon layers or crystalline carbon layers, the flow of the third preferred embodiment is shown in fig. 3A. Wherein, the cathode target is a double target (copper or nickel target and graphite target). Step 210-step 220 are as the previous embodiments, and then, when going to step 232, the shielding above the substrate is covered first, the target cleaning is performed for several minutes, then, when going to step 242, the copper or nickel target and the graphite target are bombarded simultaneously for several minutes, and when the speed is stable, the sputtering of the copper or nickel-carbon mixed layer with the predetermined thickness on the substrate is started.

Next, after the vacuum step, there are several options, including (1) removing the substrate and applying subsequent applications including the S or E option. (2) The substrate is transferred to an annealing furnace, step 258 for a VCH step or a VAL step; or an annealing furnace in a hydrogen-containing atmosphere, as shown in step 259, to perform the RCM step or the RAL step. Alternatively, after the VCH step or VAL step, the copper or nickel layer (and substrate) may be further removed by wet etching, as previously described, depending on the end application, to form a single layer structure of crystalline carbon or amorphous carbon, or to leave the copper or nickel layer as a crystalline carbon/copper or nickel or amorphous carbon/copper or nickel double layer structure, i.e., not to etch the copper or nickel layer, as shown in step 280.

The variation of the third preferred embodiment is the fourth preferred embodiment, please refer to fig. 3B. Steps 210-232 are as described above, followed by heating the chamber to a predetermined temperature, step 245. That is, sputtering of copper or nickel and graphite by plasma bombardment is performed at a medium temperature of 250-400 ℃ or a low temperature of 50-249 ℃, and a crystalline phase carbon/copper or nickel or amorphous phase carbon/copper or nickel bilayer is formed on the substrate at the medium temperature of 250-400 ℃ or the low temperature of 50-249 ℃, respectively, as shown in step 252.

Then, when the sputtering is performed at a predetermined temperature of 250-400 ℃, the substrate formed with the crystalline phase carbon/copper or nickel layer is moved to a vacuum annealing furnace and then annealed at a medium or high temperature to form a structure body with better quality of crystalline phase carbon, as shown in step 260, and then wet etching is performed to remove the copper or nickel layer and the substrate according to the application purpose, as shown in step 280. When the sputtering is performed at a predetermined temperature of 250-400 c, the crystalline phase carbon/copper or nickel layer is formed on the substrate, or directly removed, as shown in step 275.

On the other hand, after the chamber is heated to the first predetermined temperature, the copper or nickel target and the graphite target may be bombarded simultaneously by plasma under the atmosphere containing hydrogen to form crystalline phase carbon/copper or nickel/crystalline phase carbon (the preheating temperature of the chamber is 250-400 ℃) or amorphous phase carbon/copper or nickel/amorphous phase carbon (the preheating temperature of the chamber is 50-249 ℃) on the substrate, as shown in step 256.

Then, on the substrate: after the crystalline phase carbon/copper or nickel/crystalline phase carbon is formed, the substrate is transferred to a vacuum annealing furnace in a hydrogen-containing atmosphere to anneal at the medium or high temperature for a predetermined time to improve the quality of the crystalline phase carbon, as shown in step 265, the substrate is removed, as shown in step 276, and a three-layer structure of crystalline phase carbon/copper or nickel/crystalline phase carbon is formed on the substrate. The sputtering is performed in a relatively low temperature (50-249 deg.C) chamber, and a three-layer structure of amorphous carbon/copper or nickel/amorphous carbon on the substrate is formed on the substrate, or directly taken out, as shown in step 263.

Another variation of the present invention is the fifth preferred embodiment as shown in the flow chart of fig. 4A. The same as the third preferred embodiment is the copper or nickel and graphite dual target, except that the sputtering of the copper or nickel and graphite dual target of the third preferred embodiment is performed simultaneously to form the mixed layer, and the fifth preferred embodiment is performed in a predetermined order. I.e. copper or nickel targets, graphite targets, copper targets. The sputtered product was copper/carbon/copper.

When in the annealing furnace without hydrogen, as shown in step 258, the VCH step or VAL step is optionally performed to obtain a crystalline phase carbon/copper or nickel or amorphous phase carbon/copper or nickel bilayer structure, respectively. The copper or nickel layer (and the substrate) is removed by wet etching to obtain a single layer structure of crystalline carbon or amorphous carbon (step 280). Without etching but removing the substrate, a crystalline phase carbon/copper or nickel (after VCH step) or an amorphous phase carbon/copper or nickel bilayer structure (after VAL step) is formed. Alternatively, a hydrogen-containing atmosphere annealing furnace, such as 259, may be followed by RCH or RAL to obtain a crystalline carbon/copper or nickel/crystalline carbon or amorphous carbon/copper or nickel/amorphous carbon triple layer structure.

Variation of the fifth preferred embodiment: the sixth preferred embodiment. Steps 210 to 245 are as described in the fourth preferred embodiment. Bombarding a copper or nickel target, a graphite target and a copper or nickel target in sequence at a preset cavity temperature. When the sputtering is performed at a predetermined temperature of 250 to 400 ℃, there will be a two-layer structure of crystalline carbon/copper or nickel layer on the substrate, although the target material is bombarded with copper or nickel targets, graphite targets, copper or nickel targets, as shown in step 253. And then moved to the annealing furnace for

subsequent steps

260, 262, 280 or 275, as previously described.

Alternatively, after the chamber is heated to the first predetermined temperature, the copper or nickel target, the graphite target, or the copper or nickel target may be sequentially bombarded with plasma in an atmosphere containing hydrogen to form a crystalline carbon/copper or nickel/crystalline carbon or amorphous carbon/copper or nickel/amorphous carbon triple layer structure on the substrate, as shown in step 254. Then, the substrate is moved to an annealing furnace under a hydrogen-containing atmosphere and then annealed at a medium or high temperature, as shown in step 265, to form a crystalline phase carbon/copper or nickel/crystalline phase carbon three-layer structure with better crystalline phase quality. In addition, when the sequential plasma bombardment of the copper or nickel target, the graphite target, and the copper or nickel target in the hydrogen-containing atmosphere is performed in a lower temperature chamber at 50 to 249 ℃, the resulting amorphous carbon/copper or nickel/amorphous carbon triple layer structure, see step 254, can also be directly removed, as shown in step 263, and then used sequentially, as shown in S or B.

The final products of the third to sixth preferred embodiments described above are very widely used, and as described in the first preferred embodiment, include: when the sputtering is finished at normal temperature and annealing is not carried out any more, the electrode plate is provided for the continuous application (E) of the LED industry or used as an electrode plate (S) which is continuously applied to a super capacitor. The single-layer structure of the crystal phase carbon single layer or the single-layer structure of the amorphous phase carbon, or the single-layer structure of the phase carbon/copper or the nickel/crystal phase carbon, or the amorphous phase carbon/copper or the nickel/amorphous phase carbon three-layer structure can be applied to the electrode plate of a super capacitor, such as a connection application S or a soft plate substrate, a heat dissipation substrate, and ultra-thin and ultra-light body armor, such as a connection application F. The crystalline phase carbon/copper or nickel or amorphous phase carbon/copper or nickel double layer structure can be applied to an electrode plate of a super capacitor (successive application S) or a cathode plate of a lithium battery such as successive application B.

According to the first to sixth preferred embodiments, when the number of carbon layers is suitably controlled, graphene excellent in electrical conductivity and thermal conductivity can be obtained. In the third preferred embodiment, the fifth preferred embodiment and the variation thereof, the number of carbon layers can be more easily controlled by the double-target sputtering compared with the single target and the carbon-containing reaction gas of the first preferred embodiment and the variation thereof. Whether dual target sputtering is simultaneous or sequential.

In the above examples, the vacuum furnace annealing was mainly performed without intentionally introducing a reducing gas. The hydrogen-containing atmosphere annealing furnace is a general annealing furnace, and hydrogen is introduced. Of course, the present invention is not limited thereto, and the hydrogen-containing atmosphere annealing furnace may be applied to a vacuum furnace, but a reducing gas such as hydrogen or nitrogen is intentionally used to (purge) the micro oxygen inside the furnace body.

In addition, annealing in the scope of the claims, unless otherwise specified, refers to annealing in a hydrogen-containing atmosphere, both at low vacuum levels, e.g., 1E-1torr to 1E-2 torr. As mentioned above, under high vacuum above 1E-3torr, the substrate/(non-) crystalline carbon metal layer has micro-oxidized (non-) crystalline carbon thereon, i.e., substrate/(non-) crystalline carbon/copper layer or nickel layer/micro-oxidized (non-) crystalline carbon.

The invention has the following advantages: 1. the cavity can be directly applied to the electrode plate of the LED industry or the super capacitor by sputtering the copper-carbon or nickel-carbon mixed layer at normal temperature.

2. The cavity is sputtered with a mixed layer of copper carbon or nickel carbon at normal temperature, and medium-high temperature low (high) vacuum annealing is carried out to obtain a crystalline phase carbon single layer structure, a crystalline phase carbon/copper or nickel double layer structure (or a micro-oxidation crystalline phase carbon three layer structure thereon), and medium-high temperature annealing in a hydrogen-containing atmosphere can obtain a crystalline phase carbon/copper or nickel/crystalline phase carbon three layer structure. The single-layer structure can be applied to electrode plates of a super capacitor, soft plate substrates, heat dissipation substrates and ultrathin and ultralight body armor. The double-layer structure can be applied to a plate electrode of a super capacitor and a cathode plate of a lithium battery. Low temperature annealing can similarly result in single, double or triple layer structures, except that the aforementioned crystalline phase carbon is replaced by amorphous phase carbon.

4. The concept of the present invention not exceeding 400 ℃ can also be applied to electron gun evaporation (heating only copper or nickel blocks and graphite) in which the substrate can be not heated (or kept at a low temperature).

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention.

Claims

1. A method for forming an amorphous carbon/M metal layer on a substrate, the method comprising:

providing a substrate;

applying an M metal sputtering process to plasma bombard an M metal target to deposit an M metal layer on the substrate, wherein the M metal is selected from one of copper and nickel;

bombarding a carbon-containing reaction gas and an M metal target by using plasma to form a mixed layer of M metal and carbon on the M metal layer;

and carrying out an annealing process at an annealing temperature of 50-250 ℃ to form an amorphous carbon/M metal layer on the substrate.

2. The method of claim 1, wherein the step of bombarding the carbon-containing reactant gas and the M metal target with a plasma comprises sputtering in a hydrogen-containing atmosphere and annealing in a hydrogen-containing atmosphere to form amorphous carbon/M metal layer/amorphous carbon on the substrate.

3. The method of claim 1, wherein the step of bombarding the carbon-containing reactant gas and the M metal target with a plasma comprises sputtering in a sputtering chamber maintained at a temperature of 250 ℃ to 400 ℃ in a hydrogen-containing atmosphere to form amorphous carbon/M metal layer/amorphous carbon on the substrate.

4. A low-temperature manufacturing method for forming an amorphous carbon/M metal layer on a substrate is characterized by comprising the following steps:

providing a substrate;

applying a sputtering process to bombard the M metal target and the graphite target simultaneously by plasma so as to deposit a mixed layer of M metal and carbon on the substrate, wherein the M metal is selected from one of copper and nickel;