TW201619420A - Method of forming double-layer of carbon/metal and triple-layer of carbon/metal/carbon on a substrate and structure thereof - Google Patents

Abstract

A method of forming double-layer of carbon/M and triple-layer of carbon/M/carbon on a substrate is disclosed wherein the "M" is a copper or nickel. In an embodiment, the reaction gas containing carbon and M sputtering cathode are bombarded by plasma. In the other embodiments, the M, graphite double-sputtering-cathodes are bombarded by plasma at a temperature about room temperature-400 DEG C. The products are then annealed at a predetermined temperature in an atmosphere ambient or hydrogen gas containing ambient in accordance with the successively industrial application.

Description

The carbon and metal double layers are formed on the substrate, and the low temperature system is formed on the substrate by three layers of carbon, metal and carbon. Manufacturing method and structure

The present invention relates to a carbon single-component layer, or a carbon, copper double-layer or carbon, copper layer, carbon three-layer low-temperature manufacturing method, in particular, a substrate is subjected to plasma bombardment of copper at a temperature of from room temperature to 400 ° C, The carbon-containing reaction gas or the copper target, the graphite target dual target are simultaneously bombarded or bombarded in a predetermined order, and then annealed at a predetermined temperature or not annealed to form a structure of interest for subsequent industrial industry utilization.

A perfect graphene refers to a film in which a carbon atom is bonded to each other along a plane by sp2 and is covalently bonded to each other to form a film having a single carbon atom layer thickness and having a regular hexagonal lattice structure. Graphene is known to have excellent carrier mobility (5000~10000cm2/Vs), hardness (1050Gpa), thermal conductivity (5000W/mk), current carrying capacity (108A/cm ² ) and extremely large reaction surface-to-volume ratio. (2630m ² /g). All aspects of the advantages make graphene the next generation of biomedical, electronic, optoelectronic components, and the combination of excellent materials. Therefore, since the discovery of graphene in 2004, all walks of life have been actively developing the preparation method of graphene. However, in each of the various preparation methods, almost every method is accompanied by double layers or even more layers and numbers. There are hundreds of layers of graphene, and in addition, there are graphenes having a non-negative hexagonal lattice structure containing defects.

The more common practice includes mechanical peeling (mechanical Exfoliation), high temperature carbonization, thermal cracking, and chemical vapor deposition (CVD). The mechanical stripping method utilizes graphene by destroying a highly oriented thermally cracked graphite layer and a weak van der Waals bond between the layers. The preparation of graphene by this method is not only fast and convenient, but also attractive without the need for expensive process equipment, and only a small amount of cost such as tape and graphite sheet can be used. Further, the graphite mother sheet to be peeled off is a highly oriented thermally cracked graphite having high purity and excellent crystallinity, and thus the obtained graphene has almost no defects. Unfortunately, what is ultimately obtained is the incorporation of uneven graphite fragments ranging from single layers, double layers to several layers, and thus is not advantageous for introduction into the standard manufacturing process of the semiconductor industry.

Chemical vapor deposition (CVD) is currently the most common method for preparing graphene. This method is currently the most suitable method for integration with standard processes in the semiconductor industry today, while at the same time achieving large area and high Quality graphene. Therefore, it is a currently popular technique for preparing graphene. In order to reduce the cracking temperature of a reaction gas such as methane (CH ₄ ) or the like, a conventional technique is to use a transition metal element such as cobalt, nickel, copper or the like as a catalyst to lower the cracking temperature. Especially copper. For example, in 2011, a research team led by Ching-Yuan Su of the Central Research Institute of Taiwan Academia Sinica directly grew wafer-level graphene on an insulating substrate. They first deposited a copper film with a thickness of about 300 nm on the SiO2/Si substrate by sputtering, and then placed the substrate into the CVD cavity and raised the temperature of the cavity to 900 ° C before introducing methane gas; The carbon atoms from the methane cracking will deposit on the surface of the copper. At the same time, the carbon atoms deposited on the copper surface will gradually diffuse through the grain boundary of the copper film to the interlayer between the copper film and the substrate, further forming Nuclear and form graphene. This method can save the step of substrate transfer, directly grow graphene on the target substrate, and at the same time, because the transfer step is omitted, the probability of film breakage during the transfer process can be reduced, thereby improving production. Yield. The cracking temperature of the hydrocarbon gas of the above carbon source gas must be maintained at a high temperature of about 900 °C. This may still be an obstacle to the future introduction of graphene into the component.

The above process must be followed by a copper metal removal process. That is, use A solution such as hydrochloric acid or nitric acid is removed by wet etching. When completely etched, the graphene floats in the etching solution. At this time, the graphene is lifted from the etching solution by using different substrates, and subsequent instrument analysis can be performed. In the process of film transfer, in order to ensure the integrity of graphene, an organic polymer is coated on the surface of graphene as an etching protection film before etching the metal. This layer of organic polymer is mostly a long-chain hydrocarbon without a crystalline substance. Once it touches the surface of graphene, it cannot be completely removed. The organic polymer remaining on the surface of graphene will shield graphene and the environment. The contact reduces the high sensitivity of graphene to environmental changes and limits the application of graphene in the sensor.

The above-mentioned graphene generally means that the carbon atoms are arranged in a single layer or When several layers or even tens of atomic layers. However, when the number of stacked layers of carbon atoms is several hundred to tens of thousands of layers, it is generally not referred to as graphene, and there is also a very good continuous application in the industry, but the premise still needs to be preferably prepared at a low temperature. The above processes are all prepared at high temperatures, at least 750 ° C or more.

In view of the problems that conventional techniques have at high temperatures, the present invention will provide The invention relates to a low-temperature manufacturing method for preparing carbon and copper double-layers formed on a substrate and carbon, a copper layer and a carbon three layer on a substrate, and a method for preparing a carbon single-component layer, and even a method for preparing graphene.

An object of the present invention is to provide a low temperature manufacturing (non)crystalline carbon layer

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

It is still another object of the present invention to provide a method of producing a (non)crystalline carbon/copper layer or a nickel layer/(non)crystalline phase carbon at a low temperature.

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 applying a copper or nickel sputtering process, and the plasma bombards the copper or nickel target to deposit a copper or nickel. Laying on a substrate; bombarding the carbon-containing reaction gas and the copper or nickel target with plasma to form a copper or carbon mixed layer on the copper or nickel layer; applying an annealing process in the atmosphere to form (non)crystalline carbon / Copper layer or nickel layer on the substrate. Annealing in a hydrogen-containing atmosphere results in a (non)crystalline carbon/copper layer or a nickel/(non)crystalline carbon structure.

A variation of the first embodiment is that the sputtering is performed while the chamber is heated to a predetermined temperature. The predetermined temperature means that the cavity is sputtered at a temperature below 400 ° C. After the sputtering is completed, annealing is performed at 250 ° C to 1100 ° C or annealing is not performed. Wherein, after the crystal phase carbon/copper layer or the nickel layer is further etched to remove the copper layer and the substrate, a crystalline carbon structure layer can be obtained.

In the second embodiment, the copper or nickel target and the graphite target are simultaneously bombarded with plasma in the sputtering chamber to form a copper or nickel, carbon mixed layer on the substrate. An annealing process is applied to the atmosphere to form a (non)crystalline carbon/copper layer or a nickel layer on the substrate. Annealing in a hydrogen-containing atmosphere results in a (non)crystalline carbon/copper layer or a nickel/(non)crystalline carbon structure.

A variation of the second embodiment is that the temperature of the cavity is raised to the pre-spray during sputtering. It is carried out at a constant temperature. The cavity is sputtered at a temperature below 400 ° C. After the sputtering is completed, annealing is performed at 250 ° C to 1100 ° C or without annealing. Wherein, after the crystalline carbon/copper layer or the nickel layer is further etched to remove the copper layer or the nickel layer and the substrate, a crystalline carbon structure layer can be obtained.

In a third embodiment, a copper or nickel target, a graphite target, a copper or nickel target is bombarded in a plasma sequence in a sputtering chamber to form a layer of copper or nickel/carbon/copper or nickel on the substrate. An annealing process is applied to the atmosphere to form a (non)crystalline carbon/copper layer or a nickel layer on the substrate. Annealing in a hydrogen-containing atmosphere results in a (non)crystalline carbon/copper layer or a nickel/(non)crystalline carbon structure. A variation of the third embodiment is that the sputtering is performed while the chamber is heated to a predetermined temperature. The predetermined temperature means that the cavity is sputtered at a temperature below 400 ° C. After the sputtering is completed, annealing is performed at 250 ° C to 1100 ° C or annealing is not performed. After the crystalline carbon/copper layer or the nickel layer is further etched to remove the copper or nickel layer and the substrate, a crystalline carbon structure layer can be obtained.

Among them, the methods of the second and third embodiments are advantageous for controlling the number of layers of crystalline carbon, for example, obtaining graphene having a thickness of one to several carbon atoms.

The invention also applies to the terminal connection application of different structural layers, for example, when the sputtering is completed at normal temperature, and is not used for annealing, it is provided to the LED industry (continuous application E) or as an electrode plate of a super capacitor. Single-layer structure single-phase or phase carbon/copper/crystalline phase carbon or amorphous phase carbon/copper/amorphous phase carbon three-layer structure of crystalline carbon monolayer or amorphous phase carbon can be applied to supercapacitor electrode plates or soft Plate substrate, heat sink 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 super capacitor or the cathode plate of a lithium battery.

100, 105, 110, 120, 130, 140, 150, 210, 220, 230, 232, 240, 245, 250, 251, 252, 253, 254, 255, 256, 258, 259, 260, 262, 263, 265, 276, 275, 280‧‧ ‧ flowchart steps

ACH‧‧‧ means that the product is in the atmosphere, the product is crystalline carbon, high temperature annealing

AAL‧‧‧ indicates that the product is amorphous carbon and low temperature annealing in the atmosphere.

RCH‧‧‧ indicates that it is carried out under a reducing atmosphere of hydrogen, and the product is crystalline carbon, medium and high temperature annealing.

RAL‧‧‧ indicates that the product is amorphous carbon and low temperature annealed under a reducing atmosphere of hydrogen.

B‧‧‧Continuous cathode battery application for lithium batteries

E‧‧‧Continuous LED industry application

F‧‧‧Continuous soft board substrate, heat sink substrate, ultra-thin and ultra-light body armor application

S‧‧‧Continuous super capacitor electrode plate application

FIG. 1A is a schematic flow chart showing the processing steps before the substrate.

Figure 1B shows. Schematic diagram of the process steps of the glass substrate and the quartz substrate.

FIG. 1C is a schematic flow chart showing the deposition of an oxide layer on a germanium substrate.

2A is a view showing a first embodiment of the present invention, in which a single target and a carbon-containing reaction gas are bombarded with a plasma to form a (non)crystalline carbon structure single-component layer or a (non)phase carbon/copper two-component layer, A flow chart for the sputtering of a (three-phase) three-component layer of (non) crystalline carbon/copper or nickel/(non)crystalline phase carbon.

2B shows a variant of the first preferred embodiment in accordance with a second preferred embodiment of the present invention, wherein the (non)crystalline carbon structure is a single component layer or (non) phase carbon/copper or when the cavity is warmed up. A flow chart for the sputtering of a nickel (non) two-component layer, a (non) phase carbon/copper or a nickel/(non)crystalline phase carbon three-component layer.

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

FIG. 3B shows a variant of the third preferred embodiment according to the fourth preferred embodiment of the present invention, wherein the (non)crystalline carbon structure is a single component layer or (non) phase carbon/copper or when the cavity is warmed up. A flow chart for the sputtering preparation of a nickel two-component layer, a (non)phase carbon/copper or a nickel/(non)crystalline phase carbon three-component layer.

4A shows a fifth preferred embodiment of the present invention, in which a plasma strikes a single target and a graphite target according to a predetermined order to form a (non)crystalline carbon structure single component layer or (non) phase carbon/copper or nickel two component. A flow chart for the preparation of a layer, (non) phase carbon/copper or nickel/crystalline carbon three-component layer.

4B shows a variation of the fifth preferred embodiment according to the fourth preferred embodiment of the present invention, wherein the (non)crystalline carbon structure is a single component layer or (non) phase carbon/copper or when the cavity is warmed up. A flow chart for the sputtering preparation of a nickel two-component layer, a (non)phase carbon/copper or a nickel/(non)crystalline phase carbon three-component layer.

In the following examples, the present invention discloses a low-temperature (non)crystalline carbon single-component layer, a (non)crystalline carbon/copper or nickel two-component layer, a (non)crystalline carbon/copper or nickel layer, and (non- A method of a crystalline phase carbon/copper layer/(non)crystalline phase carbon three-component layer. The crystal carbon means that the carbon atoms are regularly arranged, and the amorphous phase carbon naturally refers to the amorphous carbon.

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

The front substrate cleaning is as shown in Figure 1A. As shown in step 100, the substrate is immersed in a mixture of sulfuric acid, hydrogen peroxide, and deionized water (D.I. water) for several minutes while cleaning with an ultrasonic oscillator for 5 to 15 minutes. As shown in step 110, the test piece is taken out and rinsed with D.I. Next, as shown in step 120, the substrate is immersed in diluted buffered hydrofluoric acid (e.g., 0.1% HF) for about 10 to 40 seconds. Next, as shown in step 130, the test piece is taken out and rinsed off with D.I.water. Then, as shown in step 140, the test piece is blown off with nitrogen gas to complete. When the substrate is a glass substrate or a quartz substrate, the cleaning steps are slightly different. As shown in step 105, the substrate is immersed in acetone and cleaned for 5-15 minutes using an ultrasonic oscillator, followed by D.I. water cleaning as previously described in step 110. Next, as shown in step 115, immerse in isopropanol and clean with an ultrasonic oscillator for 5-15 minutes; then, as shown in step 130 above, try Remove the pieces and rinse them off with D.I.water. As shown in the foregoing step 140, the test piece is blown off with nitrogen gas to complete.

According to a preferred embodiment of the present invention, if the substrate is a germanium substrate, a subsequent deposition process must first deposit an oxide layer having a thickness of about 100 nm or more to prevent direct copper, nickel, iron or cobalt and germanium during annealing. A metal halide is produced. Nickel or cobalt or copper on the substrate helps to control the number of layers of graphene more precisely. Nickel or cobalt or iron on the substrate also contributes to the accelerated conversion of the carbon layer to crystalline phase carbon. The crystalline carbon layer referred to herein may be graphite or graphene, and graphene is of course referred to when the number of layers is several to several tens of atomic layers.

Both nickel and copper have a catalyst for accelerating the conversion of the carbon layer into crystalline carbon. Thus, in the following examples, M appearing in Flowcharts 2A, 2B, 3A, 3B, 4A, 4B represents one of nickel or copper. Moreover, during the sputtering process, the copper target is not ferromagnetic, does not affect the magnetic field, and is beneficial for controlling the position of the plasma. However, the nickel target is a ferromagnetic material, and therefore, the magnetron of the rear end of the target must take into account the influence of the nickel target. Further, compared with nickel, the nickel layer is relatively advantageous for controlling the number of atomic layers of the crystalline phase carbon because the solubility of nickel to carbon is lower. Therefore, to control the carbon in the lower atomic layer, nickel is preferred. If the number of carbon atoms is not concerned, a copper target is preferred.

According to a first preferred embodiment of the present invention, please refer to FIG. 2A to bombard a copper or nickel single target with a plasma and a carbon-containing reaction gas to form a (non)crystalline carbon structure single component layer or (non) phase carbon/ A flow chart for the sputtering of a copper or nickel two-component layer, a (non)phase carbon/copper or a nickel/(non)crystalline phase carbon three-component layer. In accordance with a preferred embodiment of the present invention, the sputtering process is performed in a sputtering chamber. First, as shown in step 210, the substrate that has been pre-cleaned is placed on the anode, and a cathode or a nickel target is preset in the cathode. Next, as shown in step 220, a reactive magnetron sputtering chamber is evacuated until 1E-6torr. It is worth noting that if the substrate is a PET substrate or a glass substrate, whether or not it is covered with nickel or an iron or cobalt layer, they are not suitable for annealing at temperatures of 350 ° C and above, respectively, to avoid disintegration of the substrate.

Subsequently, please refer to step 230 for target cleaning. Mask first The anode pre-set test piece is covered, and an inert gas such as argon gas is introduced, and the flow rate is about 50 sccm in the magnetron sputtering chamber, the chamber pressure is 7 mTorr, and a bias voltage is applied to form argon gas into the plasma. 230 to 260 watts to clean copper or nickel targets for a duration of about 10 to 30 minutes, more preferably about 15 to 25 minutes.

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

Next, please refer to step 250 for reactive magnetron sputtering. That is, the introduced gas contains, in addition to an inert gas such as argon gas to form a plasma, a reaction gas of carbon to be plated with a copper-carbon mixed layer of 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 ), or the like. A more preferred reaction gas is acetylene. The parameters are as follows: argon, flow rate is about 30 sccm, and acetylene flow rate is 1 to 3 sccm. The power is 150 watts. The chamber pressure was 3 mTorr. The pre-plating time is about 30~120 minutes.

Immediately thereafter, the vacuum of the sputtering chamber is released. At this point, there are several options, One of them is the step (1) of taking out the substrate from the sputtering chamber as in step 270, where the bottom-up structure on the substrate is a copper or nickel layer/copper carbon or nickel-carbon mixed layer. This product can be used for the substrate of a light-emitting diode (LED), which is indicated here and later by "E". It can be applied to the electrode plate of the super capacitor, as shown by "S". (2) If the step substrate enters the annealing furnace for annealing, as in step 258.

The substrate/copper or nickel layer/copper carbon or nickel carbon of the present invention is based on its final The subsequent applicability of the product may alternatively be annealed in the atmosphere or annealed under a reducing atmosphere containing hydrogen. For convenience of explanation, the flow chart indicates the annealing temperature and the end purpose structure. The steps below the sputtered copper or nickel, carbon mixed layer will be indicated by (xxx), the first English letter "A" in parentheses. Representing annealing under the atmosphere, the first English letter "R" represents annealing under 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 The English letter "H" stands for medium and high temperature, for example, annealing at 250 ° C ~ 1100 ° C. The third English letter "L" represents a low temperature annealing of 50~249 °C. For example, the (ACH) step indicates that the product is in the atmosphere, the product is crystalline carbon, and the high temperature annealing, and the (AAL) step indicates that the product is in the atmosphere, the product is amorphous carbon, and the low temperature annealing. The (RCH) step is carried out under a reducing atmosphere of hydrogen, the product is crystalline carbon, medium and high temperature annealing, and the (RAL) step is carried out under a reducing atmosphere of hydrogen, and the product is amorphous carbon and low temperature annealing.

In addition, in the following description, unless otherwise specified, "single "Layer", "double layer", "three layers" are merely illustrative of a material layer, that is, a component layer, and do not refer to an atomic layer. For example, an amorphous phase carbon single layer, a crystalline phase carbon single layer may be A few atomic layers to tens of thousands of atomic layers are different from a single layer in which the known monoatomic layer carbon is a graphene.

Annealing in the atmosphere, the product on the substrate after annealing will be crystalline carbon / Copper or nickel, or a two-layer structure of amorphous phase carbon / copper or nickel. This is because copper or nickel has almost no solubility to carbon. Therefore, when the above annealing is performed in the atmosphere, carbon in the copper-carbon or nickel-carbon mixed layer will diffuse upward and downward, and the upwardly diffused carbon layer will be further and large. The oxygen in the gas combines with the CO or CO2 in the gas phase and is carried away by the gas stream. In contrast, when annealed under a hydrogen-containing reducing atmosphere, the product on the substrate after annealing will be crystalline carbon/copper or nickel/crystalline carbon, or amorphous carbon/copper or nickel/amorphous carbon. Structure, depending on annealing temperature and time. This is because under the conditions of hydrogen or under the introduction of ammonia gas, these annealing atmospheres protect the uppermost carbon layer during annealing from being oxidized.

The above final product is different according to the terminal application surface, the uppermost The copper or nickel layer can be removed or retained by wet etching. The above-mentioned amorphous phase carbon/copper or nickel double layer structure and crystalline phase carbon/copper or nickel double layer, when the copper or nickel layer is selectively removed by wet etching, as shown in step 280, a preferred An example is the removal of a copper or nickel layer with ferric nitrate. When the copper or nickel layer is removed by wet etching, the two-layer structure of the amorphous phase carbon/copper or nickel and the crystalline phase carbon/copper or nickel are stripped, leaving only the amorphous phase carbon or the crystalline phase carbon. The preferred applications include: continuous application to soft board substrates, heat sink substrates, ultra-thin and ultra-light body armor. This is indicated by "F" hereafter. Another preferred continuation application is that the electrode plate as a supercapacitor is indicated by S.

In addition, the final product of the RCH step is crystalline carbon/copper or nickel/crystalline carbon. Or the RAL step, the final product is a three-layer structure of amorphous phase carbon/copper or nickel/amorphous phase carbon. Since the underlying crystalline phase carbon or amorphous phase carbon and the bonding of the substrate are very poor, it is easy to The physical film pulling method separates the three-layer structure from the substrate. When the final product is a three-layer structure of crystalline carbon/copper or nickel/crystalline carbon, or amorphous phase carbon/copper or nickel/amorphous phase carbon, the preferred applications are F and S.

In addition, when the above (AAL) step or (ACH) step is not performed In the wet etching process, the obtained double layer structure of amorphous phase carbon/copper or nickel and the double layer of crystalline phase carbon/copper or nickel, a preferred application of the structure of the crucible includes S (continuous application super Capacitor plate) and the cathode used in the lithium battery, here and later to the B table It is shown that the amorphous phase carbon described above is heated to form crystalline phase carbon during the manufacture of the cathode cell of the lithium battery.

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

Please refer to the flow of Figure 2B. Steps 210 to 240 are as follows, Next, the chamber is heated to the first predetermined temperature prior to the step of sputtering copper carbon or nickel carbon. As step 245. Next, step 251 is performed to bombard the copper or nickel target and the carbon-containing reaction gas by plasma at a first predetermined temperature, and the copper 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. When the first predetermined temperature is 50 to a low temperature of 250 ° C, the copper carbon or nickel carbon mixed layer on the copper layer will also form an amorphous phase copper/copper layer. On the substrate. The flow rate of the carbon-containing reaction gas, the pressure of the chamber, and the power are as described in the first embodiment.

A substrate having an amorphous phase copper/copper or nickel layer can be taken out, as in the steps As shown in 262, the connection application is S or B. On the other hand, the substrate taken out in step 262 can also be taken out to perform the wet etching shown in step 280 to remove the copper or nickel plate and the substrate, and then the application includes S or E. Or F.

When the sputtering is at a predetermined temperature of 250 to 400 ° C, on the substrate There is a crystal phase copper/copper or nickel layer formed thereon, which can be moved to an annealing furnace for further annealing or high temperature annealing to form a structure with better crystal phase quality as shown in step 260, and then according to the purpose of the subsequent application. Wet etching removes the copper or nickel layer and the substrate, as in step 280 Shown. When the sputtering is at a predetermined temperature of 250 to 400 ° C, a substrate having a crystalline phase copper/copper or nickel layer on the substrate can also be directly removed, as shown in step 275.

On the other hand, when the cavity is heated to the first predetermined temperature, Alternatively, the copper or nickel target and the carbon-containing reaction gas may be simultaneously bombarded with plasma in a hydrogen-containing atmosphere to form crystalline carbon/copper or nickel/crystalline carbon (when the cavity is at a predetermined temperature of 250 to 400 ° C) or Amorphous phase carbon/copper or nickel/amorphous phase carbon (when the cavity is at a predetermined temperature of 50 to 249 ° C) is applied to the substrate as shown in step 255.

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

For more precise control of copper or nickel, carbon mixed layer of copper or nickel, carbon Weight percent (wt%). To accurately obtain the number of amorphous phase carbon layers or the number of crystalline carbon layers, a flow of a third preferred embodiment is shown in FIG. 3A. Among them, the cathode target is a dual target (copper or nickel target and graphite target). Steps 210 to 220 are as in the previous embodiment. Then, proceeding to step 232, the mask above the substrate is first covered, the target is cleaned for a few minutes, and then, proceeding to step 242, while bombarding the copper or nickel target and the graphite target After the rate is stabilized, a predetermined thickness of copper or a mixed layer of nickel or carbon is sputtered onto the substrate.

Then, after the vacuum is loaded, there are several options, including (1), taken out. Substrate, continuation applications include S, or E options. (2) The substrate is transferred to the annealing furnace at step 258 to carry out an (ACH) step or an (AAL) step or an annealing furnace under a hydrogen-containing atmosphere. As shown in step 259, an RCM step or a (RAL) step is performed. In addition, after the (ACH) step or the (AAL) step, the wet etching may be further removed as described above depending on the terminal application. The copper or nickel layer (and substrate) is as shown in step 280 to form a single layer structure of crystalline carbon or amorphous phase carbon, or to retain a copper or nickel layer to form a crystalline phase of carbon/copper or nickel or amorphous carbon/copper. Or nickel double-layer structure, that is, no copper or nickel layer is etched.

A variation of the third preferred embodiment is the fourth preferred embodiment, See Figure 3B. Step 21032 is as described above, and then the chamber is heated to a predetermined temperature, as in step 245. That is, a medium temperature of 250 to 400 ° C or a low temperature of 50 to 249 ° C, followed by plasma bombardment of copper or nickel and graphite dual target sputtering, as shown in step 252, at a medium temperature of 250 to 400 ° C or 50 to 249 ° C The structure of the crystalline carbon/copper or nickel or amorphous phase carbon/copper or nickel double layer on the substrate can be separately formed at a low temperature.

Then, when the sputtering is at a predetermined temperature of 250 to 400 ° C, A substrate formed by a crystalline phase copper/copper or nickel layer is transferred to an annealing furnace for annealing or high temperature annealing to form a crystal phase carbon having a better quality structure as shown in step 260, and then wet according to the application purpose. The copper or nickel layer and substrate are removed by etching as shown in step 280. When the sputtering is at a predetermined temperature of 250 to 400 ° C, the substrate having the crystal phase copper/copper or nickel layer thereon may also be directly taken out as shown in step 275.

On the other hand, when the cavity is heated to the first predetermined temperature, It is optional to simultaneously bombard the copper or nickel target and the graphite target with plasma in a hydrogen-containing atmosphere to form crystalline carbon/copper or nickel/crystalline carbon (when the cavity is at a predetermined temperature of 250 to 400 ° C) or an amorphous phase. Carbon/copper or nickel/amorphous phase carbon (when the cavity is at a predetermined temperature of 50 to 249 ° C) is applied to the substrate as shown in step 256.

Next, the structure on the substrate: crystalline carbon/copper or nickel/crystalline carbon After formation, the substrate is transferred to an annealing furnace under a hydrogen-containing atmosphere and annealed at the above-mentioned medium or high temperature for annealing for a predetermined period of time to improve the quality of the crystalline phase carbon. As shown in step 265, the substrate is removed, step 276, on the substrate. Will have a three-layer junction of crystalline carbon/copper or nickel/crystalline carbon Structure. The sputtering is performed on a relatively low-temperature cavity (at 50 to 249 ° C), and a three-layer structure of amorphous phase carbon/copper or nickel/amorphous phase carbon on the substrate is on the substrate. The direct extraction is as shown in step 263.

Yet another variation of the present invention is as shown in the flow chart of Figure 4A. Five preferred embodiments. The same as the third embodiment, all of which are copper or nickel and graphite dual targets, except that the sputtering of the copper or nickel and graphite dual targets of the third embodiment is simultaneously performed to form a mixed layer, and the fifth preferred embodiment In the example, it is performed in a predetermined order. That is, a copper or nickel target, a graphite target, or a copper target. The product after sputtering is copper/carbon/copper.

When in an annealing furnace that does not contain hydrogen, as shown in step 258, reselect The ACH step or the AAL step is optionally performed to obtain a crystalline 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 phase carbon, as in step 280. When the substrate is not etched but the substrate is removed, a phase of carbon/copper or nickel (after the ACH step) or an amorphous phase carbon/copper or nickel double layer structure (after the AAL step) is formed. In addition, in the annealing furnace containing a hydrogen atmosphere, as in step 259, the RCH step or the RAL step may be performed to obtain crystal phase carbon/copper or nickel/crystalline phase carbon or amorphous phase carbon/copper or nickel/amorphous phase carbon, respectively. Layer structure.

A variation of the fifth preferred embodiment: a sixth preferred embodiment. step Steps 210 to 245 are as described in the fourth preferred embodiment. The copper or nickel target, the graphite target, the copper or the nickel target are sequentially bombarded at a predetermined cavity 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 a crystalline phase carbon/copper or nickel layer on the substrate, although the order of bombarding the target is copper or nickel target, graphite. Target, copper or nickel target. Moving to the annealing furnace is followed by step 260, step 262, step 280 or step 275, as described above.

On the other hand, when the cavity is heated to the first predetermined temperature After that, it is also possible to bombard the copper or nickel target, graphite target, copper or nickel target in a plasma sequence under a hydrogen-containing atmosphere to form a crystalline phase carbon/copper or nickel/crystalline carbon or amorphous carbon/copper or nickel. / Amorphous phase carbon three layer structure on the substrate, as shown in step 254. The annealing furnace which is moved to a hydrogen-containing atmosphere is successively performed or high-temperature annealed as shown in step 265 to form a crystal phase carbon/copper or nickel/crystalline carbon three-layer structure having a better crystal phase quality. In addition, when a copper or nickel target, a graphite target, a copper or a nickel target is bombarded in a plasma-containing atmosphere in a hydrogen-containing atmosphere in a lower temperature chamber at 50 to 249 ° C, the resulting amorphous carbon/copper or The three-layer structure of nickel/amorphous phase carbon, see step 254, can also be taken directly as shown in step 263, followed by its subsequent application such as S or B.

The application of the final product of the above third to sixth comparative examples is not Generally, as described in the first embodiment, it is provided to the LED industry for continuous application (E) or as an electrode plate (S) for continuous application to the super capacitor when the sputtering is not performed at normal temperature. Single-layer structure single-layer or phase carbon/copper or nickel/crystalline phase carbon or amorphous phase carbon/copper or nickel/amorphous phase carbon three-layer structure of crystalline carbon monolayer or amorphous phase carbon can be applied to supercapacitor The electrode plate is connected to the S or soft board substrate, the heat dissipation substrate, and the ultra-thin and ultra-light body armor. The crystalline carbon/copper or nickel or amorphous phase carbon/copper or nickel double layer structure can be applied to the electrode plate of the super capacitor (continuous application S) or the cathode plate of the lithium battery such as the connection application B.

According to the first to sixth embodiments described above, when the number of layers of the carbon layer is controlled When appropriate, graphene having excellent conductivity and thermal conductivity can be obtained. Wherein the third embodiment and the fifth preferred embodiment and variations thereof, the single target and the carbon-containing reaction gas are compared with the first preferred embodiment and the modified second preferred embodiment by double target sputtering It is easier to control the number of layers of the carbon layer. Whether the double target sputtering is simultaneous bombardment or sequential bombardment.

The invention has the following advantages:

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

2. The cavity is sputtered with a copper-carbon or nickel-carbon mixed layer at room temperature, and a medium-high temperature annealing can be performed to obtain a crystal phase carbon single layer, a crystalline phase carbon/copper or nickel double-layer structure, and a medium-high temperature in a hydrogen-containing atmosphere. Annealing can obtain a three-layer structure of crystalline carbon/copper or nickel/crystalline carbon. The single-layer structure can be applied to electrode plates of super capacitors, soft board substrates, heat-dissipating substrates, and ultra-thin and ultra-light body armor. The two-layer structure can be applied to an electrode plate of a super capacitor or a cathode plate of a lithium battery. For low-temperature annealing, a single layer, a double layer, or a three-layer structure can be obtained, except that the aforementioned crystalline phase carbon is exchanged for amorphous phase carbon.

3. It is not limited to sputtering at normal temperature, and sputtering can be performed in a cavity that is heated to a predetermined temperature (the above-mentioned structure containing crystal phase carbon/copper can be obtained at a medium or low temperature of not more than 400 ° C), and more preferably It is annealed at medium or high temperature for better quality.

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

The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; all other equivalent changes or modifications which are not departing from the spirit of the present invention should be included. Within the scope of the patent application. For example, the above-mentioned nickel or iron or cobalt layer on a substrate having a nickel or iron or cobalt layer is a catalyst which accelerates conversion into a phase carbon as a carbon layer, and a metal having such a characteristic also contains a metal such as a nickel-iron-cobalt alloy. Results similar to the examples described.

210, 220, 230, 240, 250, 258, 259, 280 ‧ ‧ flow chart steps

ACH‧‧‧ means that the product is in the atmosphere, the product is crystalline carbon, high temperature annealing

AAL‧‧‧ indicates that the product is amorphous carbon and low temperature annealing in the atmosphere.

RCH‧‧‧ indicates that it is carried out under a reducing atmosphere of hydrogen, and the product is crystalline carbon, medium and high temperature annealing.

RAL‧‧‧ indicates that the product is amorphous carbon and low temperature annealed under a reducing atmosphere of hydrogen.

B‧‧‧Continuous cathode battery application for lithium batteries

E‧‧‧Continuous LED industry application

F‧‧‧Continuous soft board substrate, heat sink substrate, ultra-thin and ultra-light body armor application

S‧‧‧Continuous super capacitor electrode plate application

Claims (14)

A low-temperature manufacturing method for forming a carbon/copper layer on a substrate comprises at least the steps of: providing a substrate; applying an M metal sputtering process, bombarding the M metal target with a plasma to deposit an M metal layer on the substrate; The M metal is one selected from the group consisting of copper or nickel; the carbon-containing reaction gas and the M metal target are bombarded with a plasma to form an M metal and carbon mixed layer on the M metal layer; and an annealing process is performed to form a crystal phase. The carbon/M metal layer is on the substrate when the annealing temperature is between 250 ° C and 1100 ° C or the amorphous carbon/M metal layer is on the substrate when the annealing temperature is between 50 ° C and 250 ° C. The manufacturing method according to claim 1, wherein the step of bombarding the carbon-containing reaction gas and the M metal target by the plasma further comprises performing sputtering under a hydrogen-containing atmosphere and performing under a hydrogen-containing atmosphere. Annealing to form a crystalline phase carbon/M metal layer/crystalline carbon on the substrate, when the annealing temperature is not higher than 1100 ° C or amorphous phase carbon / M metal layer / amorphous phase carbon / on the substrate When the annealing temperature is not higher than the temperature of 250 ° C. The manufacturing method according to claim 1, wherein the step of bombarding the carbon-containing reaction gas and the M metal target by the plasma further comprises performing the sputtering chamber at 250 ° C to 400 ° C and including Sputtering under a hydrogen atmosphere and annealing under a hydrogen-containing atmosphere to form a crystalline phase carbon/M metal layer/crystalline carbon on the substrate, when the annealing temperature is between 250 ° C and 1100 ° C or amorphous carbon / M metal layer/amorphous phase carbon/on the substrate, no annealing is performed. The manufacturing method of claim 1, wherein the step of bombarding the carbon-containing reaction gas and the M metal target sputtering step by the plasma is further included in the cavity. The film is maintained at 250 ° C to 400 ° C to obtain at least a substrate/crystalline carbon/M metal layer structure. The manufacturing method according to claim 4, further comprising performing an annealing step of 250 ° C to 1100 ° C after the sputtering step. A low-temperature manufacturing method for forming a carbon/M metal layer on a substrate comprises at least the steps of: providing a substrate; applying a sputtering process to simultaneously bombard the M metal target and the graphite target with a plasma to deposit a M metal and carbon mixture Layered on the nickel layer on the substrate, the M metal is selected from one of copper or nickel; an annealing process is performed to form a crystalline carbon/M metal layer on the substrate, and the annealing temperature is between 250 ° C and 1100 At °C, or, an amorphous phase carbon/M metal layer is on the substrate when the annealing temperature is between 50 ° C and 250 ° C. The manufacturing method according to claim 6, wherein the step of bombarding the M metal target and the graphite target by the plasma further comprises performing sputtering under a hydrogen-containing atmosphere and annealing in a hydrogen-containing atmosphere. Forming a crystalline phase carbon/M metal layer/crystalline carbon on the substrate, when the annealing temperature is between 250 ° C and 1100 ° C or amorphous phase carbon / M metal layer / amorphous phase carbon / on the substrate, when the annealing temperature At 50 ° C ~ 250 ° C. The manufacturing method according to claim 6, wherein the step of bombarding the M metal target and the graphite target by the plasma further comprises performing the sputtering chamber at 250 ° C to 400 ° C and containing a hydrogen atmosphere. Sputtering is performed to form a crystalline carbon/M metal layer/crystalline carbon on the substrate or an amorphous phase carbon/M metal layer/amorphous phase carbon/on the substrate without annealing. The manufacturing method according to claim 8, further comprising performing an annealing step of 250 ° C to 1100 ° C after the sputtering step. A low-temperature manufacturing method for forming a carbon/M metal layer on a substrate comprises at least the steps of: providing a substrate; applying a sputtering process to bombard the M metal target, the graphite target, and the M metal target in a plasma sequence to deposit an M a metal, carbon/M metal layer on the substrate, the M metal being selected from one of copper or nickel; an annealing process to form a crystalline carbon/M metal layer on the substrate, when the annealing temperature is 250 ° C At ~1100 ° C, or an amorphous phase carbon / M metal layer on the substrate, when the annealing temperature is between 50 ° C ~ 250 ° C. The manufacturing method according to claim 10, wherein the above-mentioned plasma sequential bombardment step further comprises performing sputtering under a hydrogen-containing atmosphere and annealing in a hydrogen-containing atmosphere to form a crystalline phase carbon/ M metal layer/crystalline carbon on the substrate, when the annealing temperature is between 250 ° C and 1100 ° C or amorphous phase carbon / M metal layer / amorphous phase carbon / on the substrate, when the annealing temperature is between 50 ° C and 250 °C. a structure comprising at least a carbon, M metal mixed layer formed on a substrate, wherein the M metal is one selected from the group consisting of copper or nickel; A structure comprising at least an M metal/carbon/M metal layer formed on a substrate, the M metal being one selected from the group consisting of copper or nickel. A structure comprising at least a crystalline phase carbon/M metal layer/crystalline carbon formed on a substrate, the M metal being selected from the group consisting of copper or nickel.