CN107419220A - Carbon-metal double layer and method for forming carbon-metal-carbon triple layer on substrate - Google Patents

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

Manufacturing method of carbon, metal double layer and carbon, metal, carbon triple layer formed on substrate

technical field

The present invention relates to a low-temperature manufacturing method of carbon single-component layer, or carbon-copper double-layer or carbon-copper-carbon three-layer, especially relates to a substrate that is subjected to plasma bombardment of copper and carbon-containing reaction gas at a temperature below room temperature to 400°C. Or the copper target and the graphite target are bombarded at the same time or in a predetermined order, and then annealed at a predetermined temperature or not annealed to form the target product for industrial use.

Background technique

Perfect graphene refers to a thin film with a single carbon atomic layer thickness and a regular hexagonal lattice structure formed by carbon atoms covalently bonded to each other in sp2 mixed orbital domains along a plane. Graphene is known to have excellent carrier mobility (5000-10000cm ² /Vs), hardness (1050Gpa), thermal conductivity (5000W/mk), current carrying capacity (108A/cm ² ) and extremely large reaction surface- Volume ratio (2630m ² /g). The advantages in various aspects make graphene an excellent material with both replacement and integration in the application range of next-generation biomedicine, electronics, and optoelectronic components. Therefore, since the discovery of graphene in 2004, all walks of life have actively developed the preparation methods of graphene. However, among the various preparation methods, almost every method will be accompanied by double-layer or even more Graphene with hundreds to thousands of layers, in addition, there are also graphene containing defects in the non-regular hexagonal lattice structure.

Conventional and major preparation methods include mechanical exfoliation, high-temperature silicon carbide pyrolysis, and chemical vapor deposition (CVD) methods. The mechanical exfoliation method is used to obtain graphene by destroying the weak Van der Waals bond between the highly oriented pyrolysis graphite layer and the layer. The preparation of graphene by this method is not only fast and convenient, but more attractive is that it does not require expensive process equipment, and only needs a small amount of cost such as tape and graphite sheet to proceed. In addition, the graphite master sheet used for exfoliation is highly oriented pyrolytic graphite with high purity and excellent crystallinity, so the obtained graphene has almost no defects. It is a pity that what is finally obtained is uneven graphite fragments ranging from single-layer, double-layer to several-layer, so it is not conducive to the standard process of the semiconductor industry.

Chemical vapor deposition (Chemical vapor deposition, CVD) is currently the most common method used to prepare graphene. This method is also the most suitable method for integration with the standard process of today's semiconductor industry, and at the same time, it can obtain large area and high quality. of graphene. Therefore, it is a very popular technology for preparing graphene at present. In order to reduce the cracking temperature of reaction gases such as methane (CH ₄ ), conventional techniques use cobalt, nickel, copper, and other transition metal elements as catalysts to lower the cracking temperature, especially copper. For example, in 2011, a research team led by Ching-Yuan Su of the Applied Science Research Center of Academia Sinica, Taiwan, directly grew chip-sized graphene on an insulating substrate. They first deposited a layer of copper film with a thickness of about 300nm on the SiO ₂ /Si substrate by sputtering, then put the substrate into the CVD chamber, and raised the temperature of the chamber to 900°C before passing in methane gas; the carbon atoms from the cracking of methane will be deposited on the surface of copper, and at the same time, the carbon atoms deposited on the surface of copper will gradually diffuse to the interlayer between the copper film and the substrate through the grain boundary of the copper film, Further nucleates and forms graphene. This method can omit the step of substrate transfer, and directly grow graphene on the target substrate. At the same time, because of the omission of this transfer step, it can reduce the probability of film damage during the transfer process, thus improving production efficiency. yield. The cracking temperature of the hydrocarbon gas of the above-mentioned carbon source gas still needs to be maintained at a high temperature of about 900°C. This may still be an obstacle to the future graphene-introduced component process.

The above process must be followed by a copper metal removal process. That is, the copper or nickel is removed by wet etching using a solution such as hydrochloric acid or nitric acid. When fully etched, the graphene will float in the etching solution. At this time, use a different substrate to pick up the graphene from the etching solution, and then perform subsequent instrumental analysis. In the process of film transfer, in order to ensure the integrity of graphene, before etching the metal, a layer of organic polymer is coated on the surface of graphene as an etching protection film. This layer of organic macromolecules is mostly long-chain hydrocarbons without crystallization. Once this substance touches the surface of graphene, it cannot be completely removed. The organic macromolecules remaining on the surface of graphene will shield graphene and Environmental exposure reduces the sensitivity of graphene to environmental changes and limits the application of graphene in sensors.

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 layers of carbon atoms is hundreds to tens of thousands, it is generally not called graphene, and it has a very good follow-up application in industry, but the premise still needs to be the best preparation at low temperature. The above-mentioned processes are all prepared at high temperature, at least above 750°C.

Contents of the invention

In order to solve the problem that the conventional technology requires high temperature, the present invention will provide a low-temperature manufacturing method for preparing carbon/copper double layer on the substrate and carbon/copper layer/carbon three-layer formation on the substrate at low temperature, which also includes carbon single-component layering The preparation method also includes the preparation method of graphene.

The object of the present invention is to provide a method for producing (amorphous) crystalline carbon layers at low temperature.

Another object of the present invention is to provide a method for producing (amorphous) crystalline carbon/copper layer or nickel layer/slightly oxidized (amorphous) carbon at low temperature.

Another object of the present invention is to provide a method for producing (amorphous) crystalline carbon/copper layer or nickel layer/(amorphous) carbon at low temperature.

Technical solution of the present invention is:

The invention discloses a low-temperature manufacturing method for forming a carbon/copper layer or a nickel layer on a substrate, wherein, embodiment 1 includes applying a copper or nickel sputtering process, plasma bombarding a copper or nickel target to deposit copper or nickel Layer on the substrate; bombard the carbon-containing reaction gas and copper or nickel target with plasma to form a copper and carbon mixed layer on the copper or nickel layer; apply an annealing process in a vacuum furnace to form (amorphous) crystalline carbon/ Copper layer or nickel layer/slightly oxidized (amorphous) crystalline carbon on the substrate. When the annealing is carried out in an atmosphere containing hydrogen, a (amorphous) crystalline carbon/copper layer or a nickel layer/(amorphous) crystalline carbon structure is obtained.

A variation of the first embodiment is that the sputtering is performed when the temperature of the cavity is raised to a predetermined temperature. The predetermined temperature means that the cavity is sputtered at a temperature below 400° C., and after the sputtering is completed, annealing at 250° C. to 1100° C. or no annealing is performed. Wherein, if the annealing is carried out in a vacuum annealing furnace, after further etching to remove the copper layer/micro-oxidized crystalline carbon and the substrate, the lower crystalline carbon structure layer can be obtained.

Another technical solution of the present invention is:

In the second preferred embodiment, the copper or nickel target and the graphite target are simultaneously bombarded with plasma in the sputtering chamber to form a copper/carbon or nickel/carbon mixed layer on the substrate. An annealing process is performed in a vacuum furnace to form (amorphous) crystalline carbon/copper layer or nickel layer/slightly oxidized (amorphous) crystalline carbon on the substrate. When annealed in a hydrogen-containing atmosphere, a (amorphous) crystalline carbon/copper layer or a nickel layer/(amorphous) crystalline carbon structure is obtained.

A variation of the second embodiment is that the sputtering is performed when the temperature of the cavity is raised to a predetermined temperature. The cavity is sputtered at a temperature below 400°C. After the sputtering is completed, annealing at 250°C-1100°C or no annealing is performed. Wherein, if the annealing is carried out in a vacuum annealing furnace, after further etching to remove the copper layer/micro-oxidized crystalline carbon and the substrate, the lower crystalline carbon structure layer can be obtained.

Another technical scheme of the present invention is:

In a third preferred embodiment, a plasma sequentially bombards a copper or nickel target, a graphite target, and a copper or nickel target in a sputtering chamber to form a copper or nickel/carbon/copper or nickel layer on the substrate. An annealing process is performed in a vacuum furnace to form (amorphous) crystalline carbon/copper layer or nickel layer/slightly oxidized (amorphous) crystalline carbon on the substrate. When the annealing is carried out in an atmosphere containing hydrogen, a (amorphous) crystalline carbon/copper layer or a nickel layer/(amorphous) crystalline carbon structure is obtained. A variant of the third preferred embodiment is that the sputtering is performed when the temperature of the cavity is raised to a predetermined temperature. The predetermined temperature means that the cavity is sputtered at a temperature below 400° C., and after the sputtering is completed, annealing at 250° C. to 1100° C. or no annealing is performed. Wherein, if the annealing is carried out in a vacuum annealing furnace, after further etching to remove the copper layer/micro-oxidized crystalline carbon and the substrate, the lower crystalline carbon structure layer can be obtained.

Among them, the methods of the second and third preferred embodiments are beneficial to control the number of layers of crystalline carbon, for example, to obtain graphene with a thickness of one to several carbon atomic layers.

The present invention is also aimed at the terminal connection application of different structural layers, for example, after sputtering at room temperature and no annealing, it is provided to the LED industry (continuation application E) or used as an electrode plate of a supercapacitor. Crystalline carbon single layer or amorphous carbon single layer structure single layer or phase carbon/copper/crystalline carbon or amorphous carbon/copper/amorphous carbon three-layer structure can be applied to the electrode plate or soft Board substrate, heat dissipation substrate, ultra-thin and ultra-light body armor. The crystalline carbon/copper or nickel or amorphous carbon/copper or nickel double-layer structure can be applied to the electrode plate of a supercapacitor or the cathode plate of a lithium battery.

Features and advantages of the present invention are:

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

2. The cavity is sputtered with copper-carbon or nickel-carbon mixed layer at room temperature, and annealed at medium-high temperature and low (high) vacuum to obtain crystalline carbon single layer, crystalline carbon/copper or nickel double layer (or the microscopic layer on it) Oxidized crystalline phase carbon three-layer) structure, annealing at a medium and high temperature 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 supercapacitors, soft board substrates, heat dissipation substrates, and ultra-thin and ultra-light body armor. The double-layer structure can be applied to the electrode plate of the supercapacitor and the cathode plate of the lithium battery. And low-temperature annealing can also obtain single-layer, double-layer or three-layer structure, but the aforementioned crystalline phase carbon is replaced by amorphous phase carbon.

3. Not limited to sputtering at normal temperature, sputtering can also be carried out in a cavity heated to a predetermined temperature (the above-mentioned structure containing crystalline carbon/copper can be obtained at a medium or low temperature not exceeding 400°C), more preferably It is annealed at medium or high temperature for better quality.

The concept of not exceeding 400° C. of the present invention can also be applied to electron gun evaporation (only heating copper or nickel block and graphite) without heating (or maintaining low temperature) of the substrate.

Description of drawings

The following drawings only schematically illustrate and explain the present invention, and do not limit the scope of the present invention, wherein:

FIG. 1A is a schematic flow chart of pretreatment steps of a silicon substrate.

FIG. 1B is a schematic flow chart of the pretreatment steps of the glass substrate and the quartz substrate.

FIG. 1C is a schematic flow diagram of first depositing an oxide layer on a silicon substrate.

Fig. 2A is according to the first preferred embodiment of the present invention, using plasma to bombard a single target and carbon-containing reaction gas to form a (amorphous) crystal phase carbon structure single-component layer or (amorphous) phase carbon/copper two-component layer, (non-)phase carbon/copper two-component layer, ) sputtering preparation flow chart of crystalline carbon/copper or nickel/(amorphous) crystalline carbon three-component layer.

Fig. 2B is according to the second preferred embodiment of the present invention, which is a variant of the first preferred embodiment, the (amorphous) crystal phase carbon structure single component layer or (non) phase carbon/copper or nickel when the cavity is heated up Flow chart of sputtering preparation of (non-) two-component layer, (non-) phase carbon/copper or nickel/(amorphous) crystalline phase carbon three-component layer.

Fig. 3A is according to the third preferred embodiment of the present invention, using plasma bombardment single target and graphite target to form (amorphous) phase carbon structure single component layer or (non) phase carbon/copper or nickel two component layer, (non) ) phase carbon/copper or nickel/(amorphous) crystal phase carbon three-component layer sputtering preparation flow chart.

Fig. 3B is according to the fourth preferred embodiment of the present invention, which is a variant of the third preferred embodiment, the (amorphous) crystal phase carbon structure single component layer or (non) phase carbon/copper or nickel when the cavity is heated up Flow chart of sputtering preparation of two-component layer, (amorphous) phase carbon/copper or nickel/(amorphous) crystalline phase carbon three-component layer.

Fig. 4A is according to the fifth preferred embodiment of the present invention, the plasma bombards a single target and a graphite target according to a predetermined order to form a single layer of (amorphous) phase carbon structure or a double layer of (non) phase carbon/copper or nickel, Flow chart of sputtering preparation of (non-) phase carbon/copper or nickel/crystalline phase carbon three-component layer.

Fig. 4B is according to the variant of the fifth preferred embodiment of the present invention, the (amorphous) crystal phase carbon structure single component layer or (non) phase carbon/copper or nickel two component layer, (non) phase carbon structure when the cavity is heated up / copper or nickel / (amorphous) crystal phase carbon three-component layer sputtering preparation flow chart.

Symbol Description

VCH: Indicates that the product is crystalline carbon and high-temperature annealing is in progress in a vacuum furnace.

VAL: Indicates that the product is amorphous carbon and annealed at low temperature in the process of vacuum furnace.

RCH: Indicates that it is carried out under a reducing atmosphere of hydrogen, and the product is crystalline carbon, and it is annealed at medium and high temperature.

RAL: Indicates that it is carried out under a reducing atmosphere of hydrogen, the product is amorphous carbon, and low-temperature annealing.

B: The cathode plate application of the continuous lithium battery.

E: Continue LED industry application.

F: Continuous flexible board substrates, heat dissipation substrates, ultra-thin and ultra-light body armor applications.

S: Continuation of supercapacitor electrode plate application.

detailed description

In the following embodiments, the present invention discloses a low-temperature manufacturing (amorphous) crystalline carbon single-component layer, (amorphous) crystalline carbon/copper or nickel layer double-component layer, (amorphous) crystalline carbon/copper or nickel layer and (Amorphous) crystalline phase carbon/copper layer/(amorphous) crystalline phase carbon three-component layering method. The crystalline carbon (crystal carbon) refers to the regular arrangement of carbon atoms, and the amorphous carbon refers to amorphous carbon.

The substrate of the present invention may be a silicon substrate, a glass substrate, a quartz substrate, or a PET substrate, and the PET film here is a high-temperature-resistant (up to 350° C.) polyester film. Glass substrates are also substrates that can withstand high temperatures (up to 550°C).

The pre-cleaning of the silicon substrate is shown in Figure 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 at the same time, cleaned by an ultrasonic oscillator for 5-15 minutes. As shown in step 110, the test strip is removed and rinsed with D.I. Next, as shown in step 120 , soak the silicon substrate with diluted hydrofluoric acid (eg 0.1% HF) as a buffer solution for about 10-40 seconds. Next, as shown in step 130, the test piece is taken out and rinsed with D.I.water. Then, as shown in step 140, the test piece is blown off with nitrogen gas, and the process is completed. When the substrate is a glass substrate or a quartz substrate, the cleaning steps are slightly different, as shown in Figure 1B. As shown in step 105, the substrate is soaked in acetone and cleaned with an ultrasonic oscillator for 5-15 minutes, and then, as in the aforementioned step 110, D.I.water cleaning. Next, as shown in step 115, soak in isopropanol and clean with an ultrasonic oscillator for 5-15 minutes; then, as shown in step 130, take out the test piece and rinse it with D.I.water. As shown in the aforementioned step 140, the test piece is blown clean with nitrogen gas, and the process is completed.

According to a preferred embodiment of the present invention, if the above-mentioned substrate is a silicon substrate, in the subsequent deposition process, an oxide layer with a thickness of about 100 nm or more must be deposited first to prevent direct generation of copper, nickel, iron or cobalt and silicon during annealing. metal silicide. Nickel or cobalt or copper on the substrate helps to control the number of graphene layers more precisely, as shown in Figure 1C. Nickel or cobalt or iron on the substrate also contributes to the catalyst for accelerating the transformation of the carbon layer into crystalline carbon. The crystalline carbon layer referred to herein may be graphite or graphene, and graphene refers to graphene with crystal layers ranging from several to tens of atomic layers.

Both nickel and copper are catalysts that accelerate the transformation of carbon layers into crystalline carbon. Therefore, in the following embodiments, M appearing in FIG. 2A , FIG. 2B , FIG. 3A , FIG. 3B , FIG. 4A , and FIG. 4B of the flowchart represents one of nickel or copper. During the sputtering process, the copper target is not ferromagnetic and will not affect the magnetic field, which is beneficial to control the position of the plasma. Moreover, the nickel target is a ferromagnetic material, so the influence of the nickel target must be considered for the magnetron device at the rear end of the target. Compared with copper and nickel, the nickel layer is relatively beneficial to control the number of atomic layers of crystalline carbon, because the solubility of nickel to carbon is lower. Therefore, to control the carbon at a lower atomic layer, nickel is better. If you don't care about the number of carbon atomic layers, a copper target is better.

According to the first preferred embodiment of the present invention, as shown in FIG. 2A , plasma bombards copper or nickel single target and carbon-containing reaction gas to form (amorphous) crystal phase carbon structure single component layer or (amorphous) phase carbon/ Flow chart of sputtering preparation of copper or nickel two-component layer, (amorphous) phase carbon/copper or nickel/(amorphous) phase carbon three-component layer. 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 above-mentioned pre-cleaned substrate is placed on the anode, and a copper or nickel target is preset in the cathode in the cavity. Next, as shown in step 220, the reactive magnetron sputtering chamber is evacuated until 1E-6 torr. It is worth noting that if the substrate is a PET substrate or a glass substrate, regardless of whether it is covered with nickel, iron or cobalt, they are not suitable for annealing at temperatures above 350°C and 550°C respectively to avoid substrate disintegration.

Then, please refer to step 230 to clean the target. First cover the test piece with the anode preset, and then introduce an inert gas, such as argon, with a flow rate of about 50 sccm in the magnetron sputtering chamber, the chamber pressure is 7mTorr and a bias voltage is applied to make the argon gas form a plasma, The power is 230-260 watts to clean copper or nickel targets for about 10-30 minutes, more preferably about 15-25 minutes.

Subsequently, as shown in step 240, the shield is opened for copper or nickel layer sputtering. In the magnetron sputtering chamber, the chamber pressure is controlled at 3mTorr and a bias is applied: introduce an inert gas, such as argon, with a flow rate of about 30 sccm to make the argon gas form a plasma, and the pre-plating time is about 3-12 minutes, preferably The is about 10 minutes. In the embodiment the corresponding power is about 140-160 watts. In order to control the thickness of the copper or nickel layer at 5-300nm.

Next, please refer to step 250 to perform reactive magnetron sputtering. That is, in addition to the inert gas such as argon to form the plasma, the introduced gas also contains carbon reactive gas to plate a copper-carbon mixed layer with a predetermined thickness on the copper layer. In a preferred embodiment, the carbon-containing reaction gas is acetylene (C ₂ H ₂ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ) and the like. A more preferred reactive gas is acetylene. The parameter conditions are as follows: argon gas, the flow rate is about 30 sccm, and the acetylene flow rate is 1-3 sccm. The power is 150 watts. The cavity pressure is 3mTorr. The pre-plating time is about 30-120 minutes.

Next, release the vacuum of the sputtering chamber. Now, there are several options, one of which is (1) the substrate is taken out from the sputtering chamber, as in step 270, and the bottom-up structure on the substrate is copper or nickel layer/copper carbon or nickel carbon mixed layers. This product can be continuously applied to the substrate of light-emitting diode (LED), which is represented by "E" here and below, and can also be continuously applied to the electrode plate of supercapacitor, as shown in the figure with "S". (2) The substrate enters the vacuum annealing furnace for annealing, such as step 258 .

According to the continuous applicability of the final product, the substrate/copper or nickel layer/copper carbon or nickel carbon of the present invention can be annealed in a vacuum furnace or under a reducing atmosphere containing hydrogen. In order to facilitate the description of the annealing temperature and its target structure shown in the flow chart, the steps below the sputtering copper or nickel and carbon mixed layer will be represented by (xxx), and the first English letter "V" in the parentheses represents the vacuum furnace Annealing, the first English letter "R" represents annealing in a reducing atmosphere containing hydrogen, the second English letter "A" represents an amorphous phase, the second English letter "C" represents a crystalline phase, and the third English letter " H" stands for medium and high temperature, for example, annealing at 250°C-1100°C, and the third English letter "L" stands for low temperature annealing at 50-249°C. For example, the (VCH) step means that it is carried out in a vacuum furnace, the product is crystalline carbon, and it is annealed at high temperature, and the (VAL) step means that it is carried out in a vacuum furnace, and the product is amorphous carbon, and it is annealed at a low temperature. The (RCH) step means that it is carried out under a reducing atmosphere of hydrogen, the product is crystalline carbon, and medium/high temperature annealing, and the (RAL) step means that it is carried out under a reducing atmosphere of hydrogen, the product is amorphous carbon, and low temperature annealing. The vacuum annealing furnace annealing refers to a vacuum degree of 1E-1torr to 1E-2torr. At this time, a small amount of oxygen in the vacuum furnace will make the surface layer after annealing form oxidized crystalline carbon (medium and high temperature annealing), or oxidized amorphous carbon (low temperature annealing). The oxidized crystalline carbon in this layer is of poor quality, and at a higher degree of vacuum such as above 1E-3, the oxidized (amorphous) carbon will turn into slightly oxidized (amorphous) crystalline carbon. In addition, in the following description, unless otherwise specified, "single-layer", "double-layer", and "three-layer" only describe material layers, that is, refer to component layers rather than atomic-level layers. For example, a single layer of amorphous carbon and a single layer of crystalline carbon may be several atomic layers to tens of thousands of atomic layers, which is different from the known monolayer of single atomic layer carbon which is the definition of graphene.

Annealing is carried out in a vacuum furnace, and the product on the substrate after annealing will be a double-layer structure of crystalline carbon/copper or nickel, or amorphous carbon/copper or nickel (under low vacuum). This is because copper or nickel has almost no solubility for carbon. Therefore, when the above-mentioned vacuum furnace annealing is carried out, the carbon in the copper-carbon or nickel-carbon mixed layer will diffuse upward and downward, and the upwardly diffused carbon layer will be further mixed with the vacuum furnace. The micro-oxygen in the gas is combined into CO or CO ₂ in the gas phase and is taken away by the gas flow, as mentioned above, for example, the degree of vacuum is at 10 ^-1 torr-10 ^-2 torr. If the degree of vacuum is increased, for example above 10 ^-3 torr, the upper diffused carbon layer will be slightly oxidized, that is, a three-layer structure of crystalline carbon/copper layer or nickel layer/micro-oxidized crystalline carbon. The degree of oxidation depends on the degree of vacuum. Vacuum annealing ensures the quality of the (amorphous) crystalline phase of carbon adjacent to the substrate. In contrast, when annealed in a reducing atmosphere containing hydrogen, the product on the substrate after annealing will be a triple layer of crystalline carbon/copper or nickel/crystalline carbon, or amorphous carbon/copper or nickel/amorphous carbon The structure depends on the annealing temperature and time. This is because these annealing atmospheres can protect the uppermost carbon layer during annealing and prevent it from being oxidized when it is performed under hydrogen or ammonia gas.

Depending on the end application of the above final products, the uppermost copper or nickel layer can be removed or retained by wet etching. The above-mentioned double-layer structure of amorphous carbon/copper or nickel and double-layer structure of crystalline carbon/copper or nickel, when the copper or nickel layer is selected to be removed by wet etching, as shown in step 280, a preferred embodiment The copper or nickel layer is removed by ferric nitrate. When the copper or nickel layer is removed by wet etching, the double-layer structure of amorphous carbon/copper or nickel and crystalline carbon/copper or nickel will be stripped, leaving only amorphous carbon or crystalline carbon, which is better Applications include: continuous application to soft board substrates, heat dissipation substrates, and ultra-thin and ultra-light body armor. Denoted here and hereafter by "F". Another preferred continuous application is as an electrode plate of a supercapacitor, denoted by "S".

In addition, the final product of the RCH step is crystalline carbon/copper or nickel/crystalline carbon or the RAL step, and the final product is a three-layer structure of amorphous carbon/copper or nickel/amorphous carbon. The bond between the crystalline carbon and the substrate is very poor, so it is easy to separate the three-layer structure from the substrate by physical film pulling. 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, the preferred subsequent applications are F and S.

In addition, when the above-mentioned (VAL) step or (VCH) step does not do the above-mentioned wet etching, what is obtained will be a double-layer structure of amorphous carbon/copper or nickel and a double-layer of crystalline carbon/copper or nickel, such that The preferred application of the structure includes S (continuous application of supercapacitor electrode plate) and continuous application to the negative electrode of lithium battery, which is represented by B hereafter, wherein the above-mentioned amorphous carbon is used in the manufacturing process of the negative pool of lithium battery , will be heated to form crystalline carbon.

The above-mentioned first preferred embodiment of the present invention can also be further changed into a second preferred embodiment. The second preferred embodiment is to heat up the cavity to the first predetermined annealing temperature before sputtering the copper-carbon mixed layer, and then sputter the copper-carbon or nickel-carbon mixed layer, and keep the temperature until the target structure is formed after sputtering Formation of crystalline carbon/copper or nickel layer, amorphous carbon/copper or nickel layer, crystalline carbon/copper or nickel layer/crystalline carbon, or amorphous carbon/copper or nickel layer/amorphous carbon.

See Figure 2B for the process. Steps 210 to 240 are as described above, and then, before the step of sputtering copper-carbon or nickel-carbon, the cavity is heated to the first predetermined temperature. Such as step 245. Immediately afterwards, step 251 is carried out at the first predetermined temperature to bombard the copper or nickel target and the carbon-containing reaction gas with plasma, and the copper carbon or nickel carbon on the copper or nickel layer when the first predetermined temperature is 250 to 400° C. The mixed layer will also form a crystalline copper/copper layer on the substrate, and the copper-carbon or nickel-carbon mixed layer on the copper layer will also form an amorphous copper/copper layer when the first predetermined temperature is a low temperature of 50 to 250°C on the substrate. The flow rate, cavity pressure and power of the carbon-containing reaction gas are as described in the first preferred embodiment.

The substrate of the above-mentioned amorphous phase copper/copper or nickel layer can be taken out, as shown in step 262, the subsequent application is S or B, on the other hand, the substrate taken out in step 262 can also be taken out for wet etching shown in step 280 to remove In addition to copper or nickel plate and substrate, the subsequent application includes S or E or F.

When sputtering is carried out at a predetermined temperature of 250-400°C, a crystalline copper/copper or nickel layer is formed on the substrate, which can then be moved to a vacuum annealing furnace for medium or high temperature annealing to form a better quality crystalline phase structure, as shown in step 260, and then perform wet etching to remove the copper or nickel layer and the substrate according to the purpose of subsequent application, as shown in step 280. When the sputtering is performed at a predetermined temperature of 250-400° C., a crystalline copper/copper or nickel layer is formed on the substrate, which can be taken out directly, as shown in step 275 .

On the other hand, after the chamber is heated to the first predetermined temperature, it is also possible to simultaneously bombard the copper or nickel target and the carbon-containing reaction gas with a plasma in an atmosphere containing hydrogen to form crystalline carbon/copper or nickel /Crystal phase carbon (cavity preheating temperature is 250-400 ℃) or amorphous carbon/copper or nickel/amorphous carbon (cavity preheating temperature is 50-249 ℃) on the substrate, such as step 255 shown.

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

In order to more accurately control the copper or nickel and carbon weight percentage (wt%) of the copper or nickel and carbon mixed layer, to accurately obtain the number of amorphous carbon layers or the number of crystalline carbon layers, please refer to the process of the third preferred embodiment Figure 3A. Among them, the cathode target is a double target (copper or nickel target and graphite target). Steps 210-220 are as in the previous embodiment, and then, when proceeding to step 232, first cover the shield above the substrate, and clean the target for several minutes, and then proceed to step 242, simultaneously bombard the copper or nickel target and graphite Target for several minutes, and start sputtering a predetermined thickness of copper or nickel, carbon mixed layer on the substrate after the rate is stable.

Then, after the vacuum step, there are several options, including (1) taking out the substrate, and the subsequent application includes the S or E option. (2) The substrate is transferred to the annealing furnace, step 258 to perform the VCH step or the VAL step; or the annealing furnace under a hydrogen-containing atmosphere, as shown in step 259 , to perform the RCM step or the RAL step. In addition, after the VCH step or the VAL step, as mentioned above, depending on the end application, the copper or nickel layer (and the substrate) can be further removed by wet etching, as shown in step 280, to form crystalline carbon or amorphous carbon Single-layer structure, or keep the copper or nickel layer to form a crystalline carbon/copper or nickel or amorphous carbon/copper or nickel double-layer structure, that is, the copper or nickel layer is not etched.

A variant of the third preferred embodiment is the fourth preferred embodiment, please refer to FIG. 3B. Steps 210 to 232 are as described above, and then, the cavity is heated to a predetermined temperature, such as step 245 . That is, at a medium temperature of 250-400°C or a low temperature of 50-249°C, and then conduct plasma bombardment of copper or nickel and graphite double target sputtering, as shown in step 252, at a medium temperature of 250-400°C or at a temperature of 50-249°C The structure of crystal phase carbon/copper or nickel or amorphous phase carbon/copper or nickel double layers on the substrate can be formed respectively at low temperature.

Next, when the sputtering is at a predetermined temperature of 250-400 ° C, the substrate formed by the crystalline copper/copper or nickel layer is moved to a vacuum annealing furnace for medium or high temperature annealing to form a crystalline carbon with a higher quality. For a good structure, as shown in step 260 , 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 at a predetermined temperature of 250-400° C., a crystalline copper/copper or nickel layer is formed on the substrate, which can also be taken out directly, as shown in step 275 .

On the other hand, after the chamber is heated to the first predetermined temperature, it is also possible to simultaneously bombard the copper or nickel target and the graphite target with a plasma in an atmosphere containing hydrogen to form a crystal phase carbon/copper or nickel/crystal phase Carbon (the preheating temperature of the cavity is 250-400° C.) or amorphous carbon/copper or nickel/amorphous carbon (the preheating temperature of the cavity is 50-249° C.) on the substrate, as shown in step 256 .

Next, on the above-mentioned substrate: After forming crystalline carbon/copper or nickel/crystalline carbon, the substrate is transferred to a vacuum annealing furnace under a hydrogen-containing atmosphere to anneal at the above-mentioned medium or high temperature, and the annealing is preset for a time to improve the crystalline carbon. As shown in step 265, the substrate is taken out, and as shown in step 276, a three-layer structure of crystalline carbon/copper or nickel/crystalline carbon is formed on the substrate. The sputtering is carried out in a relatively low temperature (50-249°C) chamber, and a three-layer structure of amorphous carbon/copper or nickel/amorphous carbon on the substrate is formed on the substrate, which can also be taken out directly. As shown in step 263 .

Another variation of the present invention is the fifth preferred embodiment shown in the flowchart of FIG. 4A. The same as the third preferred embodiment is the same as copper or nickel and graphite double target, the difference is that the sputtering of the third preferred embodiment copper or nickel and graphite double target is carried out simultaneously to form a mixed layer, and the fifth In a preferred embodiment, it is performed in a predetermined order. That is, copper or nickel target, graphite target, copper target. The product after sputtering is copper/carbon/copper.

When the annealing furnace does not contain hydrogen, as shown in step 258, a VCH step or a VAL step is selected to obtain a crystalline carbon/copper or nickel or an amorphous carbon/copper or nickel double-layer structure respectively. Then remove the copper or nickel layer (and the substrate) by wet etching to obtain a monolayer structure of crystalline carbon or amorphous carbon, as in step 280 . Without etching but removing the substrate, a crystalline carbon/copper or nickel (after the VCH step) or an amorphous carbon/copper or nickel bilayer structure (after the VAL step) is formed. In addition, in an annealing furnace with a hydrogen-containing atmosphere, such as step 259, the RCH step or the RAL step can be performed to obtain crystalline carbon/copper or nickel/crystalline carbon or amorphous carbon/copper or nickel/amorphous carbon respectively Three-tier structure.

A modification of the fifth preferred embodiment: the sixth preferred embodiment. Step 210 to step 245 are as described in the fourth preferred embodiment. Bombarding a copper or nickel target, a graphite target, and a copper or nickel target is performed sequentially at a predetermined chamber temperature. As shown in step 253, when the sputtering is at a predetermined temperature of 250 to 400°C, there will be a two-layer structure of crystal phase carbon/copper or nickel layer on the substrate, although the order of the bombardment target is copper or nickel target, graphite target, copper or nickel target. Then move to the annealing furnace to proceed to step 260, step 262, step 280 or step 275, as described above.

On the other hand, after the chamber is heated to the first predetermined temperature, it is also possible to bombard copper or nickel targets, graphite targets, copper or nickel targets with plasma sequentially in an atmosphere containing hydrogen to form crystalline carbon/copper Or nickel/crystalline carbon or amorphous carbon/copper or nickel/amorphous carbon three-layer structure on the substrate, as shown in step 254 . Then move to an annealing furnace under a hydrogen-containing atmosphere to perform medium or high temperature annealing, as shown in step 265, to form a crystalline carbon/copper or nickel/crystalline carbon three-layer structure with better crystal phase quality. In addition, when the sequential bombardment of copper or nickel targets, graphite targets, copper or nickel targets in a hydrogen-containing atmosphere is carried out in a chamber at a lower temperature than 50 to 249 ° C, the resulting amorphous carbon/copper or The nickel/amorphous carbon three-layer structure, see step 254, can also be taken out directly, as shown in step 263, and then its subsequent application, such as S or B.

The application of the final product of the above-mentioned third-sixth preferred embodiments is very extensive, as described in the first preferred embodiment, including: when the sputtering is finished at room temperature and no annealing is performed, it is provided to the LED industry for continued application (E) Or as an electrode plate (S) for continuous application in supercapacitors. Crystalline carbon single layer or amorphous carbon single layer structure Single layer or phase carbon/copper or nickel/crystalline carbon or amorphous carbon/copper or nickel/amorphous carbon three-layer structure can be applied to supercapacitors If the electrode plate is continuously applied to S or the soft board substrate, the heat dissipation substrate, and the ultra-thin and ultra-light body armor is continuously applied to F. The crystalline carbon/copper or nickel or amorphous carbon/copper or nickel double-layer structure can be applied to the electrode plate of a supercapacitor (continued application S) or the cathode plate of a lithium battery such as continued application B.

According to the above-mentioned first to sixth preferred embodiments, when the number of carbon layers is properly controlled, graphene with excellent electrical and thermal conductivity can be obtained. Among them, in the third preferred embodiment and the fifth preferred embodiment and its variants, the double target sputtering is compared with the single target and carbon-containing Reactive gases make it easier to control the number of carbon layers. It doesn't matter whether the double-target sputtering is simultaneous bombardment or sequential bombardment.

In the above-mentioned embodiments, the annealing in the vacuum furnace is mainly based on not intentionally introducing reducing gas. The hydrogen-containing atmosphere annealing furnace refers to a general annealing furnace that introduces hydrogen. Of course, it is not limited thereto, and the hydrogen-containing atmosphere annealing furnace can also be applied to a vacuum furnace, but reducing oxygen such as hydrogen or nitrogen is deliberately used to purge the micro-oxygen inside the furnace body.

In addition, the annealing in the scope of the claims, unless otherwise specified, is annealing in a hydrogen-containing atmosphere, all refer to a low vacuum degree, such as 1E-1torr to 1E-2torr. As mentioned before, when the high vacuum is above 1E-3torr, there may be micro-oxidized (amorphous) crystalline carbon on the substrate/(amorphous) crystalline carbon metal layer, that is, the substrate/(amorphous) crystalline carbon/copper layer or Nickel layer/slightly oxidized (amorphous) crystalline carbon.

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

2. The cavity is sputtered with copper-carbon or nickel-carbon mixed layer at room temperature, and annealed at medium-high temperature and low (high) vacuum to obtain crystalline carbon single layer, crystalline carbon/copper or nickel double layer (or the microscopic layer on it) Oxidized crystalline phase carbon three-layer) structure, and annealing at a high temperature 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 supercapacitors, soft board substrates, heat dissipation substrates, and ultra-thin and ultra-light body armor. The double-layer structure can be applied to the electrode plate of the supercapacitor and the cathode plate of the lithium battery. And low-temperature annealing can also obtain single-layer, double-layer or three-layer structure, but the aforementioned crystalline phase carbon is replaced by amorphous phase carbon.

3. Not limited to sputtering at normal temperature, sputtering can also be carried out in a cavity heated to a predetermined temperature (the above-mentioned structure containing crystalline carbon/copper can be obtained at a medium or low temperature not exceeding 400°C), more preferably It is annealed at medium or high temperature for better quality.

4. The concept of not exceeding 400° C. of the present invention can also be applied to electron gun evaporation (only heating of copper or nickel block and graphite) without heating (or maintaining low temperature) of the substrate.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention; all other equivalent changes or modifications that do not deviate from the disclosed content of the present invention should be included in within the claims.

Claims (10)

1. a kind of carbon/layers of copper is formed at the manufacture method of substrate, it is characterised in that the manufacture method includes following step Suddenly：

Substrate is provided；

Impose M metal sputtering techniques, plasma-based bombardment M metallic targets, to deposit M metal levels on the substrate, The M metals are to be selected from copper or nickel one kind therein；

Carbon containing reacting gas and M metallic targets are bombarded with plasma-based to form M metal/carbons mixed layer in the M metals On layer；

Annealing process is imposed with 250 DEG C -1100 DEG C of annealing temperature to form crystalline phase carbon/M metal levels in the substrate On, or, annealing process is imposed with 50 DEG C -250 DEG C of annealing temperature to form amorphous phase carbon/M metal levels in described On substrate.

2. manufacture method as claimed in claim 1, it is characterised in that described that carbon containing reaction gas is bombarded with plasma-based The step of body and M metallic targets, sputter is carried out under hydrogen atmosphere, and is annealed under hydrogen atmosphere, When annealing temperature is not higher than 1100 DEG C of temperature, crystalline phase carbon/M metal levels/crystalline phase carbon is formed on the substrate, when When annealing temperature is not higher than 250 DEG C of temperature, amorphous phase carbon/M metal levels/amorphous phase carbon is formed on the substrate.

3. manufacture method as claimed in claim 1, it is characterised in that described that carbon containing reaction gas is bombarded with plasma-based The step of body and M metallic targets, it is held in 250 DEG C -400 DEG C included in sputter cavity and carries out and carried out under hydrogen atmosphere Sputter, and annealed under hydrogen atmosphere, when annealing temperature is at 250 DEG C -1100 DEG C, form crystalline phase carbon/M Metal level/crystalline phase carbon is on the substrate, when no longer being annealed, formed amorphous phase carbon/M metal levels/amorphous phase carbon in On the substrate.

4. manufacture method as claimed in claim 1, it is characterised in that with plasma-based bombard carbon containing reacting gas and M metallic target sputter steps, also it is held at 250 DEG C -400 DEG C and is carried out to obtain substrate/crystalline phase carbon/M included in cavity Metal-layer structure.

5. manufacture method as claimed in claim 4, it is characterised in that the manufacture method is also included in sputter and walked 250 DEG C -1100 DEG C of annealing steps are carried out after rapid again.

6. a kind of carbon/M metal levels are formed at the low-temperature preparation method of substrate, it is characterised in that comprise the steps of：

Substrate is provided；

Sputtering process is imposed, M metallic targets and graphite target are bombarded with plasma-based simultaneously, to deposit M metals, carbon mixed layer In on the nickel dam on the substrate, the M metals are one kind in copper or nickel；

Annealing process is imposed with 250 DEG C -1100 DEG C of annealing temperature to form crystalline phase carbon/M metal levels in the substrate On, or, annealing process is imposed with 50 DEG C -250 DEG C of annealing temperature to form amorphous phase carbon/M metal levels in described On substrate.

7. a kind of carbon/M metal levels are formed at the manufacture method of substrate, it is characterised in that comprise the steps of：

Substrate is provided；

Sputtering process is imposed, with plasma-based order bombardment M metallic targets, graphite target, M metallic targets, to deposit M gold Belong to layer/carbon/M metal levels on the substrate, the M metals are one kind in copper or nickel；

Annealing process is imposed with 250 DEG C -1100 DEG C of annealing temperature with formed crystalline phase carbon/M metal levels/oxidation crystalline phase carbon in On the substrate, or, with 50 DEG C -250 DEG C of annealing temperature impose annealing process with amorphous phase carbon/M metal levels/ Amorphous phase carbon is aoxidized on the substrate.

8. manufacture method as claimed in claim 7, it is characterised in that it is described with plasma-based order implant steps, go back Comprising：Sputter is carried out under hydrogen atmosphere, and is annealed under hydrogen atmosphere, or is moved in vacuum annealing furnace Annealed, when annealing temperature is at 250 DEG C -1100 DEG C, form crystalline phase carbon/M metal levels/crystalline phase carbon in the substrate On, when annealing temperature is at 50 DEG C -250 DEG C, formation amorphous phase carbon/M metal levels/amorphous phase carbon/on the substrate.

A kind of 9. structure, it is characterised in that the structure includes the M metal/carbons/M metal levels being formed on substrate, The M metals are one kind in copper or nickel.

10. a kind of structure, it is characterised in that the structure includes the oxidizing and crystallizing carbon/M metals being formed on substrate Layer, the M metals are one kind in copper or nickel.