KR101760653B1 - Apparatus for manufacturing graphene and method of manufacturing graphene - Google Patents

Apparatus for manufacturing graphene and method of manufacturing graphene Download PDF

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KR101760653B1
KR101760653B1 KR1020150109898A KR20150109898A KR101760653B1 KR 101760653 B1 KR101760653 B1 KR 101760653B1 KR 1020150109898 A KR1020150109898 A KR 1020150109898A KR 20150109898 A KR20150109898 A KR 20150109898A KR 101760653 B1 KR101760653 B1 KR 101760653B1
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roll
rotating roll
rotating
chamber
graphene
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KR20160141350A (en
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김근수
조성원
김영재
이임복
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세종대학교산학협력단
(주) 싸이엔텍
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Abstract

A graphene manufacturing apparatus and a graphene manufacturing method are provided. The slag manufacturing apparatus includes a first rotating roll and a second rotating roll capable of winding and unwinding a metal thin film roll in a chamber, and includes a roll driving unit for forward and reverse rotation of the first rotating roll and the second rotating roll . Therefore, it is possible to provide a graphene manufacturing apparatus capable of performing the heat treatment step and the graphene growth step separately in the same chamber. Therefore, in the field of graphene growth using chemical vapor deposition, the quality of graphene produced by a roll-to-roll process can be improved by the quality of graphene produced using a single thin sheet, Graphene production is possible.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a graphene manufacturing apparatus and a graphene manufacturing method,

The present invention relates to a method and apparatus for efficiently growing graphene on a metal thin film by chemical vapor deposition.

The structure of graphene has a honeycomb two-dimensional crystal structure in which hexagon-shaped connections extend in a two-dimensional direction by an sp 2 bonding structure having three bonds at one vertex. Graphene has a stable molecular structure, even though it is a thin film of atomic thickness. Graphene is very transparent because it is a film of one atom thick, and it shows only absorption of 2.3% in white light. In addition, even if the physical strength is increased by 20% due to the strong elasticity, various electric and electronic properties are preserved and not destroyed. It is stable chemically, and it shows good resistance to various acids and bases without breaking the structure.

The expected applications of graphene include touch panels, flexible displays, high efficiency solar cells, heat dissipation films, coating materials, ultrathin loudspeakers, seawater desalination filters, electrodes for secondary batteries, ultra-fast chargers and more. Research is underway. Graphene has unusual electrical properties that can not be obtained from another material, so it has a band structure that is characteristic of semiconductors and is classified as semimetal. By using this, it is possible to make a semiconductor through a doping process.

Many graphene production methods from powder to thin film have been studied, but in recent years, many researchers have focused on chemical vapor deposition. The chemical vapor deposition method can grow large area of graphene, and it has the highest commerciality because it has a production speed comparable to that of semiconductors. In the chemical vapor deposition method, when a carbon source gas such as methane is decomposed into high temperature or high energy and a transition metal (Cu, Ni, Co, Fe, Ge, Ru, Pt, etc.) And an appropriate amount of carbon is dissolved or adsorbed in the catalyst layer. After cooling, the carbon atoms contained in the catalyst layer are crystallized on the surface to form a graphene crystal structure. The synthesized graphene can be separated from the substrate by removing the catalyst layer and then used for a desired application.

However, in the field of graphene growth using chemical vapor deposition, the quality of graphene produced by the roll-to-roll process is lower than the quality of graphene produced using a single thin sheet. The growth of graphene by chemical vapor deposition on a single thin sheet consists of the process of heating → heat treatment → graphening → cooling, but it is not easy to process each process at the desired time and temperature in roll growth.

Therefore, it is necessary to study a suitable method and a device capable of obtaining graphene of the same quality as that of a single thin film sheet while using the roll-to-roll method for graphene growth of the chemical vapor deposition method.

Korean Patent Publication No. 10-2014-0121664

A problem to be solved by the present invention is to provide a graphene producing method capable of obtaining graphene of the same quality as a single thin sheet while using the roll rheol method for graphene growth of the chemical vapor deposition method and a graphene producing apparatus suitable for the method .

According to an aspect of the present invention, there is provided a graphene manufacturing apparatus. The apparatus for manufacturing a roll-to-roll type graphene according to the present invention comprises a chamber formed to be hermetically sealed to the outside, a first rotary roll and a second rotary roll provided in the chamber, A gas supply part formed at one side of the chamber to supply gas into the chamber, and a gas discharge part formed at one side of the chamber to discharge a gas inside the chamber, And a roll driving unit for rotating the first rotating roll and the second rotating roll forward and backward.

The gas supply unit may include a reducing gas supply unit and a carbon source gas supply unit.

When the first rotating roll and the second rotating roll rotate normally, a reducing gas is supplied into the chamber. When the first rotating roll and the second rotating roll rotate in opposite directions, a carbon source gas is supplied into the chamber .

In the case where the first rotating roll and the second rotating roll rotate normally, a heat treatment step of the metal thin film is performed in the chamber, and when the first rotating roll and the second rotating roll rotate in opposite directions, And a step of growing graphene on the thin film is performed.

In addition, the reducing gas may include hydrogen, helium, argon or ammonia.

In addition, the carbon source gas may include a hydrocarbon gas.

In addition, the roll driving unit may include a reverse rotating device for rotating the first rotating roll and the second rotating roll in reverse.

When the metal thin film roll is moved to any one of the first rotating roll and the second rotating roll by more than a certain amount, the reverse rotating device automatically reverses the first rotating roll and the second rotating roll to move to the other side And rotating it.

According to another aspect of the present invention, there is provided a method of manufacturing graphene. The method of manufacturing a roll-to-roll type graphene according to the present invention includes the steps of preparing a metal thin film roll having both sides connected to a first rotating roll and a second rotating roll, respectively, and rotating the first rotating roll and the second rotating roll in one direction Performing only a heat treatment on the metal thin film moved between the first rotating roll and the second rotating roll while moving the metal thin film and rotating the first rotating roll and the second rotating roll in the opposite direction, And growing graphene on the metal thin film moved between the first rotating roll and the second rotating roll while moving the metal film.

Further, the step of performing only the heat treatment is performed in a reducing gas atmosphere.

The step of performing only the heat treatment may be performed at a temperature of 600 ° C or higher.

The step of growing the graphene is characterized in that graphene is grown on the metal thin film in an atmosphere of a carbon source gas.

The step of growing the graphene is performed at a temperature of 800 ° C or higher.

Further, the present invention is characterized in that the heat treatment step and the graphene growth step are separately performed in the same chamber.

According to an aspect of the present invention, there is provided a graphene manufacturing apparatus. The apparatus for manufacturing a roll-to-roll type graphene according to the present invention comprises a chamber formed to be hermetically sealed to the outside, a first rotary roll and a second rotary roll provided in the chamber, A heating furnace for heating the metal thin film between the first rotating roll and the second rotating roll, a gas supply part formed at one side of the chamber and supplying gas into the chamber, a gas discharge part formed at one side of the chamber, And a reverse rotation device for reversely rotating the first rotating roll and the second rotating roll.

According to the present invention, it is possible to provide a graphene manufacturing apparatus capable of performing the heat treatment step and the graphene growth step separately in the same chamber.

Therefore, the heat treatment effect and the graphene growth efficiency can be improved by controlling the atmosphere of the gas injected into the chamber while performing the heat treatment step and the graphene growth step separately in the same chamber.

Therefore, in the field of graphene growth using chemical vapor deposition, the quality of graphene produced by a roll-to-roll process can be improved by the quality of graphene produced using a single thin sheet, Graphene production is possible.

The technical effects of the present invention are not limited to those mentioned above, and other technical effects not mentioned can be clearly understood by those skilled in the art from the following description.

1 is a schematic view of a graphene manufacturing apparatus according to an embodiment of the present invention.
2 is a schematic view of a graphene manufacturing apparatus according to an embodiment of the present invention.
3 is a flowchart illustrating a method of manufacturing graphene according to an embodiment of the present invention.
FIG. 4 is an actual photograph of a continuous graphene synthesizing apparatus according to an embodiment of the present invention.
5 is a graph showing Raman spectroscopic characteristics of graphene according to Comparative Example 1. FIG.
6 is a graph showing Raman spectroscopic characteristics of graphene according to Production Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. Rather, the intention is not to limit the invention to the particular forms disclosed, but rather, the invention includes all modifications, equivalents and substitutions that are consistent with the spirit of the invention as defined by the claims.

It will be appreciated that when an element such as a layer, region or substrate is referred to as being present on another element "on," it may be directly on the other element or there may be an intermediate element in between .

Although the terms first, second, etc. may be used to describe various elements, components, regions, layers and / or regions, such elements, components, regions, layers and / And should not be limited by these terms.

1 is a schematic view of a graphene manufacturing apparatus according to an embodiment of the present invention.

1, a graphene manufacturing apparatus according to an embodiment of the present invention includes a chamber 10, a first rotary roll 20, a second rotary roll 30, a heating unit 40, a gas supply unit 50 A gas discharging portion 60, and a roll driving portion (not shown).

The chamber 10 may have a hollow space therein and may be hermetically sealed with the outside.

The first rotating roll 20 and the second rotating roll 30 are provided in the chamber 10, and the metal thin film roll can be wound and unwound. For example, the first rotary roll 20 and the second rotary roll 30 must be able to manually unwind and roll the metal foil roll 70 by adjusting the direction of rotation.

The first rotary roll 20 and the second rotary roll 30 are disposed in the chamber 10 at a predetermined interval and the both sides of the metal thin film roll 70 are rotated by the first rotary roll 20 and the second rotary The metal foil can be moved between the first rotating roll 20 and the second rotating roll 30 while being wound or unwound.

Meanwhile, the metal thin film roll 70 at this time serves as a catalyst for growing graphene. For example, the metal thin film may include at least one selected from the group consisting of Ni, Co, Fe, Pt, Au, Ag, Al, Cr, (Cu), magnesium (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), tungsten (W) And may include at least one or more of an alloy selected from the group consisting of vanadium (V), palladium (Pd), yttrium (Y), and zirconium (Zr).

The heating section 40 is arranged to heat the metal foil between the first rotating roll 20 and the second rotating roll 30.

Therefore, when the metal thin film roll 70 is released from one rotary roll and moves to the other rotary roll, the metal thin film moved between the first rotary roll 20 and the second rotary roll 30 is heated by the heating unit 40 Lt; / RTI >

The heating unit 40 can use various heating type apparatuses used in general chemical vapor deposition. For example, the heating unit can use various apparatuses such as resistance heating, high frequency induction heating, microwave heating, infrared heating or near infrared heating.

For example, the heating section 40 may include a heating furnace. For example, one or more heating furnaces may be disposed between the first rotating roll and the second rotating roll. Therefore, the metal thin film between the first rotating roll and the second rotating roll can be heated while being in contact with or contactless with the heating furnace.

The gas supply unit 50 may be formed at one side of the chamber 10 to supply gas into the chamber 10. For example, the gas supply unit 50 may include a reducing gas supply unit and a carbon source gas supply unit.

For example, the gas supply unit 50 may include a gas inlet provided at one side of the chamber 10, a reducing gas supply line connected to the gas inlet, and a carbon source gas supply line and a gas supply valve for opening and closing the supply lines have.

The gas discharging part 60 is formed at one side of the chamber 10 to discharge the gas inside the chamber 10.

For example, the gas discharge unit 60 may include a gas discharge port provided at one side of the chamber 10, a gas discharge line connected to the gas discharge port, and a gas discharge valve for opening and closing the gas discharge line. Further, the gas discharging portion 60 may further include a vacuum pump, as the case may be, to bring the chamber 10 into a vacuum state.

The roll driving unit rotates the first rotary roll 20 and the second rotary roll 30 forward and reverse.

In particular, the roll driving unit may include a reverse rotation device to rotate the first rotary roll 20 and the second rotary roll 30 in reverse. The reverse rotation device may be a manual, semi-automatic or automatic reverse rotation device.

For example, the automatic reverse rotation device can use a tension sensor and a controller such as a road-cell, an encoder (revolution counter), a servo motor, or a drive driver.

The automatic reverse rotation device at this time is characterized in that the metal thin film roll 70 is automatically rotated in the reverse direction when the metal thin film roll 70 is moved over a certain distance to either the first rotary roll 20 or the second rotary roll 30 do.

If the metal thin film is manually moved, there is a risk that the last portion of the metal thin film roll 70 is exposed to heat for a long time and is broken. Accordingly, when the metal thin film roll 70 is moved over a predetermined distance from the one side to the other side by using the automatic reverse rotation device, the rotation of the rotating roll is automatically detected by detecting the thin metal roll 70, Time can be reduced.

For this automatic reverse rotation, the roll driving part preferably includes a sensor.

For example, it is preferable that the tension sensor is attached to the rotary roll so that the metal thin film is loosened to the rotary roll in which the metal thin film is loosened so that the reverse rotation is started when the tension of the rotary roll for winding the thin metal film is increased. Furthermore, it is also preferable to interlock the system so that the type of gas injected into the chamber can be changed with the start of the reverse rotation.

As another example, when the metal thin film is completely unrolled by attaching the proximity sensor to the rotating roll on which the metal thin film is unwound, the rotating roll axis made of plastic may be exposed and detected to start the reverse rotation.

In addition, it is possible to implement automatic reverse rotation by various known sensors. In some cases, it is possible to manually rotate the roll in the middle.

Therefore, in the roll-to-roll type graphene manufacturing apparatus according to the present invention, the reducing gas is supplied into the chamber 10 when the first rotating roll 10 and the second rotating roll 20 are rotated forward, The carbon source gas is supplied into the chamber 10 when the first rotary roll 10 and the second rotary roll 20 are rotated in opposite directions.

For example, the reducing gas at this time may be supplied into the chamber through the reducing gas supply line and the gas inlet. At this time, the reducing gas may include hydrogen, helium, argon or ammonia.

Further, the carbon source gas at this time may be supplied into the chamber through the carbon source gas supply line and the gas inlet. The carbon source gas may include a hydrocarbon gas.

Therefore, when the first rotary roll 20 and the second rotary roll 30 are rotated in the normal direction, the heat treatment step of the metal thin film is performed in the chamber 10, and the first rotary roll 20 and the second rotary roll 30 The step of growing graphene on the metal thin film in the chamber 10 is performed when the rotary roll 30 is rotated in the reverse direction.

2 is a schematic view of a graphene manufacturing apparatus according to an embodiment of the present invention.

In the graphene manufacturing apparatus shown in Fig. 1, the metal thin film moves from the first rotating roll 20 to the second rotating roll 30, and in the graphene manufacturing apparatus of Fig. 2, (30) to the first rotating roll (20).

1, when the metal foil is moved in the direction of the second rotating roll 30 from the first rotating roll 20 and when the metal foil is moved in the direction of the first rotating roll 20 from the second rotating roll 30 as shown in FIG. It is possible to perform different process steps in the same chamber under different atmospheres because the time when the metal thin film is moved can be divided temporally.

According to the present invention, it is possible to provide a graphene manufacturing apparatus capable of performing the heat treatment step and the graphene growth step separately in the same chamber.

Therefore, when the heat treatment step and the graphene growth step are separately performed in the same chamber, the atmosphere of the gas injected into the chamber can be controlled differently, and an atmosphere suitable for each step can be made, The efficiency can be improved.

In addition, in the field of graphene growth using chemical vapor deposition, the quality of graphene produced by the roll-to-roll process can be improved by the quality of graphene produced using a single thin sheet, Graphene production is possible.

In addition, the process sequence was rearranged to make the apparatus and the time efficient so that the heat treatment can be performed in a reductive gas atmosphere which was not possible in the conventional Rule Golgulin growth apparatus. For example, a rotating roll equipped with a metal thin film is first rotated and heat-treated in a hydrogen atmosphere. When the movement of the metal thin film is completed, reverse rotation starts and graphen growth starts. This enables a large number of high-quality graphenes to be obtained in a single process, which can save time and effort required for lowering and elevating the temperature of the furnace, and forming vacuum conditions.

A method of manufacturing graphene according to an embodiment of the present invention will be described.

2 is a flowchart illustrating a method of manufacturing graphene according to an embodiment of the present invention.

Referring to FIG. 2, a method of manufacturing a graphene according to an embodiment of the present invention includes preparing a metal thin film roll having both sides connected to a first rotating roll and a second rotating roll S100, A step (S200) of performing only heat treatment on the metal thin film to be moved by rotating the second rotating roll in one direction, and a step (S200) of growing the graphene on the metal thin film moved by rotating the first rotating roll and the second rotating roll in the opposite direction (S300).

First, the metal thin film rolls connected to the first rotating roll and the second rotating roll are prepared on both sides (S100).

The step of preparing the metal thin film roll (S100) can be prepared by using the apparatus for producing graphene according to the present invention. For example, both sides of the metal foil roll may be connected to the first rotating roll and the second rotating roll in the chamber of the apparatus for producing graphene according to the present invention.

For example, the metal thin film may include at least one selected from the group consisting of Ni, Co, Fe, Pt, Au, Ag, Al, Cr, (Cu), magnesium (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), tungsten (W) And may include at least one or more of an alloy selected from the group consisting of vanadium (V), palladium (Pd), yttrium (Y), and zirconium (Zr).

Then, the first rotating roll and the second rotating roll are rotated in one direction to perform the heat treatment only on the moving metal thin film (S200).

That is, the first rotating roll and the second rotating roll may be rotated in one direction to move the metal thin film, and only the heat treatment may be performed on the metal thin film moved between the first rotating roll and the second rotating roll. That is, the heat treatment step (S200) is performed before the graphene growth step (S300).

In this case, any of the heating methods used in general chemical vapor deposition can be used, and resistance heating, high frequency induction heating, microwave heating, infrared heating, or near infrared heating can be used.

The step S200 of performing only the heat treatment is performed in a reducing gas atmosphere. For example, the reducing gas may include hydrogen, helium, argon or ammonia. For example, the metal thin film can be heat-treated while hydrogen gas (10 to 100 sccm) is supplied into the chamber.

In addition, the step of performing only the heat treatment (S200) is performed at a temperature of 600 ° C or higher. That is, the heat treatment temperature is required to be 600 ° C or higher, preferably 800 ° C to 1100 ° C, at a temperature required for hydrogen decomposition.

The heat treatment effect of the metal thin film is classified into two kinds. One is the growth effect of metallic crystal by heat. As the metal crystal grows, the surface roughness decreases, which helps to grow graphene crystals and reduce defects.

The other is that when heat treatment is performed in a reducing gas atmosphere, the metal oxide is reduced to metal, which prevents contaminants and defects as starting points of graphene growth. Therefore, it can be said that the reducing gas atmosphere is more important for improving the quality of graphene, because the reducing gas atmosphere has an effect of lowering the recrystallization temperature of the metal and increasing the speed. Particularly, in graphene growth using Cu and Ni metal thin films, the residual metal oxide produced in a natural state is not easily lost only by heat treatment, so that the reducing atmosphere is particularly useful for removing metal oxides.

Next, the first rotating roll and the second rotating roll are rotated in opposite directions to grow graphene on the moving metal thin film (S300).

That is, the first rotating roll and the second rotating roll are rotated in opposite directions to move the metal thin film, and graphenes can be grown on the metal thin film moved between the first rotating roll and the second rotating roll.

In this case, the roll-to-roll method also has an advantage in that the annealing step (S200) in the same chamber is performed in a specific atmosphere and then the graphene growth step (S300) is performed in another atmosphere.

The step (S300) of growing the graphene is characterized by supplying a carbon source gas for forming graphene on the metal thin film in a carbon source gas atmosphere. That is, graphene can be grown by chemical vapor deposition.

The carbon source gas at this time is a reaction gas for graphene formation. These carbon source gases include carbon and may be of a gas species that can exist in the gas phase at the graphene growth temperature and pressure.

For example, the carbon source gas may comprise a hydrocarbon gas. For example, the hydrocarbon gases are methane (CH 4), carbon monoxide (CO), ethane (C 2 H 6), ethylene (CH 2), ethanol (C 2 H 5), acetylene (C 2 H 2), propane ( CH 3 CH 2 CH 3), propylene (C 3 H 6), butane (C 4 H 10), pentane (CH 3 (CH 2) 3 CH 3), pentene (C 5 H 10), dicyclopentadiene (C 5 H 6 ), hexane (C 6 H 14 ), cyclohexane (C 6 H 12 ), benzene (C 6 H 6 ), or toluene (C 7 H 8 ).

For example, methane gas (0.1 to 50 sccm) may be supplied into the chamber to form graphene on the metal thin film.

Alcohols composed of C, H, and O can also be used as a raw material for graphene growth by vaporizing them at room temperature.

Optionally, step (S300) of growing the graphene can grow graphene with controlled quality by controlling the partial pressure in an atmosphere of a mixture of carbon source gas and hydrogen gas. Further, the step of growing the graphene (S300) is performed at a temperature of 800 ° C or higher.

This graphene growth temperature is possible above the decomposition temperature of the carbon source gas and below the melting point of the metal thin film.

Therefore, the step of growing graphene (S300) is preferably performed at a temperature of 800 占 폚 or higher, and more preferably 800 占 폚 to 1100 占 폚.

Meanwhile, the temperature of the heat treatment step (S200) and the temperature of the graphene growth step (S300) may be different from each other, but it is preferable to make them similar. It is preferable that the temperature difference between the temperature of the heat treatment step (S200) and the temperature of the graphene growth step (S300) be equal to or less than 50 DEG C for the device operation.

Good and bad quality of graphene produced by chemical vapor deposition is classified as follows. The larger the size of the graphene domain grown on the metal catalyst thin film, the higher the physical strength, the higher the electrical conductivity and chemical stability, and the better the quality. The higher the physical strength and chemical stability, the better the quality without any crystal defects between the domain and the domain or within the domain. As a result of Raman analysis, it is considered that the higher the crystallinity and the higher the quality, the higher the G (graphite) peak and 2D (double-resorance) peak and the almost no D (defect) peak. It is reported that graphene quality is best when metal catalyst thin films of the same kind are heat treated in a hydrogen gas atmosphere and graphene is mixed with hydrocarbons and hydrogen.

On the other hand, it may further include cooling after the graphen growth step (S300). For example, after the graphene growth step (S300), the chamber central temperature can be lowered under an inert atmosphere.

Therefore, according to the present invention, the production speed and quality of high-quality graphene produced by the chemical vapor deposition method are increased to make the development and manufacture of electronic parts such as semiconductors and sensors cheaper and easier.

In addition, when the roll-to-roll process using the chemical vapor deposition process is performed, the process sequence is rearranged to enable heat treatment in a reducing gas atmosphere, thereby making the apparatus and the time efficient.

For example, a rotating roll equipped with a metal thin film roll is first rotated to move the metal thin film, and heat treatment is performed in a reducing gas atmosphere. When the metal thin film is moved to another rotating roll, reverse rotation starts and graphen growth starts. As a result, it is possible to obtain high quality graphene in a large amount in a single process, and it is possible to save the time required for the temperature lowering and rising of the heating part, the time and effort required for forming the vacuum condition, .

Production Example 1

Graphene was produced using the graphene production apparatus of Fig.

In Fig. 1, the diameter of the chamber 10 was 0.1 m. The heating section 40 uses a heater, and the length of the heater 40 is 0.35 m.

A copper foil having a length of 30 m, a width of 5 cm and a thickness of 30 占 퐉 was prepared using a metal thin film roll (70).

Then, a copper foil 29 m is wound around a tube 10 cm in diameter, which is the first rotating roll 10, and the remaining 1 m is passed through the chamber 10 of the graphene production apparatus to form a second rotary roll 20 The other tube was wound 20 cm.

The inner pressure of the chamber 10 of the graphene production apparatus was set to a vacuum of 0.01 mbar and the central temperature was raised to 1000 캜 under an inert atmosphere by supplying argon gas (100 sccm) into the chamber 10.

Then, the first rotary roll 10 and the second rotary roll 20 were rotated forward to move the copper foil in the direction of the second rotary roll 20 at a speed of 0.5 m per minute. At this time, hydrogen gas (50 sccm) was supplied into the chamber and the copper foil was heat-treated in a reducing atmosphere.

After the copper foil has been all moved to the second rotary roll 20, the supply of hydrogen gas into the chamber is continued and the first rotary roll 10 and the second rotary roll (not shown) are supplied with methane gas (10 sccm) 20) was rotated counterclockwise to move the copper foil back to the opposite side at a rate of 0.25 m / min and graphene was grown on the copper foil.

The heater was turned off during the last cooling step (about 60 ° C / min), the supply of hydrogen and methane gas was stopped, the temperature of the central temperature was lowered to 70 ° C or less under an inert atmosphere by supplying argon gas (100 sccm) The copper foil synthesized with the pin was taken out.

Comparative Example 1

Graphene was prepared by a heat treatment in one direction and a graphene synthesis process.

At this time, as in Production Example 1, graphene was produced by using the graphene production apparatus shown in FIG. 1, but the graphene was produced by simultaneously moving the metal thin film roll in one direction and performing heat treatment and graphene synthesis.

Therefore, hydrogen gas (50 scc) and methane gas (10 sccm) were simultaneously supplied into the chamber, and the heat treatment and the graphene synthesis were carried out together.

FIG. 4 is an actual photograph of a continuous graphene synthesizing apparatus according to an embodiment of the present invention.

4 (a) is an actual photograph of a continuous graphene synthesizing apparatus designed and manufactured with the present invention. 4 (b) is a photograph of the inside of the chamber in which the copper foil is loaded in the graphene continuous synthesis equipment for graphene synthesis. 4 (c) is a photograph of a continuous graphene synthesis apparatus undergoing a graphene synthesis process at a temperature of about 1000 ° C. Figure 4 (d) is a graphene coated copper foil roll photo produced using the graphene continuous synthesis equipment.

5 is a graph showing Raman spectroscopic characteristics of graphene according to Comparative Example 1. FIG.

Referring to FIG. 5, when graphene was manufactured by moving a metal thin film roll in one direction as in the conventional synthesis method, the peak of D (about 1530 cm -1 ) was very large in Raman spectroscopic characteristics, and 2D (about 27000 cm -1 ) peaks are very weak and the quality is not good.

6 is a graph showing Raman spectroscopic characteristics of graphene according to Production Example 1. FIG.

Referring to FIG. 6, Raman spectroscopic characteristics of graphene obtained through the graphene synthesis process proposed in the present invention show almost no peak at D (about 1530 cm -1 ), a peak at G (about 1580 cm -1 ) About 27000 cm -1 ), the peak is clearly visible, and it can be confirmed that the quality is good.

It should be noted that the embodiments of the present invention disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

10: chamber 20: first rotating roll
30: second rotating roll 40: heating part
50: gas supply part 60: gas discharge part
70: metal thin film roll

Claims (15)

A chamber formed to be hermetically sealed with the outside;
A first rotating roll and a second rotating roll provided in the chamber, the first rotating roll and the second rotating roll being capable of winding and unwinding the metal thin film roll;
A heating unit for heating the metal thin film between the first rotating roll and the second rotating roll;
A gas supply unit formed at one side of the chamber to supply gas into the chamber;
A gas discharge portion formed at one side of the chamber and discharging gas inside the chamber; And
And a roll driving unit for normally rotating and rotating the first rotating roll and the second rotating roll, wherein the gas supplying unit includes a reducing gas supplying unit and a carbon source gas supplying unit,
A reducing gas is supplied into the chamber when the first rotating roll and the second rotating roll rotate forward and a carbon source gas is supplied into the chamber when the first rotating roll and the second rotating roll rotate in opposite directions Wherein the graphene is produced by a roll-to-roll method. delete delete The method according to claim 1,
Wherein when the first rotating roll and the second rotating roll are rotated normally, a heat treatment step of the metal thin film is performed in the chamber,
Wherein when the first rotating roll and the second rotating roll are rotated in opposite directions, graphening is performed on the metal thin film in the chamber. The method according to claim 1,
Wherein the reducing gas comprises hydrogen, helium, argon or ammonia. The method according to claim 1,
Wherein the carbon source gas comprises a hydrocarbon gas. The method according to claim 1,
Wherein the roll driving unit includes a first rotating roll and a second rotating roll, and the roll driving unit includes a reverse rotating device for rotating the first rotating roll and the second rotating roll in reverse. 8. The method of claim 7,
The reverse rotation device automatically rotates the first rotating roll and the second rotating roll back so that the metal thin film roll moves to the other side when the metal thin film roll moves to one of the first rotating roll and the second rotating roll by more than a certain amount Wherein the graphene is fed by a roll-to-roll method. Preparing a metal foil roll having both sides connected to the first rotating roll and the second rotating roll, respectively;
Performing only heat treatment on the metal thin film moved between the first rotating roll and the second rotating roll while rotating the first rotating roll and the second rotating roll in one direction to move the metal thin film; And
And rotating the first rotating roll and the second rotating roll in opposite directions to move the thin metal film while growing graphene on the thin metal film moved between the first rotating roll and the second rotating roll, Wherein the graphening step is performed by dividing the heat treatment step and the graphene growth step in the same chamber. 10. The method of claim 9,
Wherein the step of performing only the heat treatment is a step of performing a heat treatment in a reducing gas atmosphere. 11. The method of claim 10,
Wherein the step of performing only the heat treatment is performed at a temperature of 600 ° C or higher. 10. The method of claim 9,
Wherein the step of growing the graphenes comprises growing graphene on the metal thin film under a carbon source gas atmosphere. 13. The method of claim 12,
Wherein the step of growing the graphenes is performed at a temperature of 800 DEG C or higher. delete A chamber formed to be hermetically sealed with the outside;
A first rotating roll and a second rotating roll provided in the chamber, the first rotating roll and the second rotating roll being capable of winding and unwinding the metal thin film roll;
A heating furnace for heating the metal foil between the first rotating roll and the second rotating roll;
A gas supply unit formed at one side of the chamber to supply gas into the chamber;
A gas discharge portion formed at one side of the chamber and discharging gas inside the chamber; And
And a reverse rotation device for reversely rotating the first rotary roll and the second rotary roll,
Wherein the gas supply portion includes a reducing gas supply portion and a carbon source gas supply portion,
A reducing gas is supplied into the chamber when the first rotating roll and the second rotating roll rotate forward and a carbon source gas is supplied into the chamber when the first rotating roll and the second rotating roll rotate in opposite directions Wherein the graphene is produced by a roll-to-roll method.
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