WO2014035068A1

WO2014035068A1 - Method for manufacturing graphene, said graphene, and apparatus for manufacturing same

Info

Publication number: WO2014035068A1
Application number: PCT/KR2013/006955
Authority: WO
Inventors: 문진산; 노종현; 박수범; 김태형; 홍병희; 박원배; 정명희
Original assignee: 엘지전자 주식회사
Priority date: 2012-08-30
Filing date: 2013-08-01
Publication date: 2014-03-06

Abstract

The present invention provides a method for manufacturing graphene, said graphene, and an apparatus for manufacturing same. The method for manufacturing graphene comprises the steps of: loading a catalytic metal layer into a chamber; applying tensile force to the catalytic metal layer; and forming graphene on the catalytic metal layer by supplying a carbon source into the chamber while the tension is applied to the catalytic metal layer. Therefore, the size of the grains on the catalytic metal layer can be increased by applying tension to the catalytic metal layer, and high quality uniform graphene can be grown through the use of the catalytic metal layer.

Description

【Specification】

[Name of invention]

Graphene manufacturing method and graphene and its manufacturing apparatus

Technical Field

[1] The present invention relates to graphene, and more particularly, to a method for producing graphene using a tension allol, and a graphene and a manufacturing apparatus thereof.

Background Art

[2] Materials composed of carbon atoms include fullerene, carbon nanotube, graphene and graphite. Of these, graphene is a structure in which carbon atoms are composed of a single layer of atoms in a two-dimensional plane.

[3] In particular, graphene is not only very stable and excellent in electrical, mechanical, and chemical properties, but also as a good conductive material, it can move electrons much faster than silicon and carry a much larger current than copper. As a method of separating graphene has been discovered, it has been proved through experiments.

[4] These graphenes can be formed in large areas, have electrical, mechanical, and chemical stability, as well as excellent conductive properties, and thus are attracting attention as a base material for electron furnaces.

[5] ^{■ In} addition, graphene generally has electrical characteristics that can be changed according to the crystal orientation of graphene having a given thickness, so that the user can express electrical characteristics in a selected direction, and thus the device can be easily designed. . Therefore, graphene can be effectively used for carbon-based electrical or electromagnetic devices.

[Detailed Description of the Invention]

[Technical problem]

The problem to be solved by the present invention is to provide a graphene manufacturing method and a graphene and its manufacturing apparatus capable of producing high quality uniform graphene.

Technical Solution

[7] In order to achieve the above object, as an aspect of the invention, the present invention provides a method for producing graphene. The graphene manufacturing method includes loading a catalyst metal charge into a chamber, applying tension to the catalyst metal charge, and applying the catalyst metal charge to the catalyst metal charge. And supplying a carbon source into the chamber under tension to form graphene on the catalyst metal charge.

[8] Another aspect of the present invention for achieving the above object, the present invention, the chamber comprising a gas inlet and outlet, the catalyst metal layer is loaded; And a tensioning device for tensioning the catalytic metal layer loaded into the chamber. [Favorable effect]

According to the present invention, the grain size of the catalyst metal layer can be increased by applying tension to the catalyst metal charge, and high quality uniform graphene can be grown using the catalyst metal layer.

In addition, by applying tension to the catalyst metal layer, the orientation of the catalyst metal layer can be changed to the (111) orientation, and the catalyst metal filling can be used to grow high quality uniform graphene.

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

[Brief Description of Drawings]

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

2 shows images of grain size of a catalyst metal charge after synthesis of graphene according to Comparative Examples and Preparation Examples.

3 shows images obtained by measuring the orientation of a catalyst metal layer after synthesizing graphene according to Comparative Examples and Preparation Examples.

4 is a schematic view showing an example of a graphene manufacturing apparatus.

5 is a schematic view showing another example of a graphene manufacturing apparatus.

[Form for implementation of invention]

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

While the invention allows various modifications and variations, specific embodiments thereof are illustrated by way of example in the drawings and will be described in detail below. However, it is not intended to be exhaustive or to limit the invention to the precise form disclosed. It includes all modifications, equivalents, and substitutes consistent with the spirit of the invention as defined by the claims. ·

[18] When an element such as a layer, region or substrate is referred to as being on another component "on", it is understood that it may be directly on another element or additional elements may be present therebetween. You can do it.

[19] Although the terms first and second may be used to describe various elements, components, regions, layers and / or regions, such elements, components, regions, layers and It will be understood that regions should not be limited by these terms. Example

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

Referring to FIG. 1, the method for preparing graphene includes loading a catalyst metal charge into a chamber (S1), applying a tension to the catalyst metal layer (S2), and graphene on the catalyst metal layer. Forming step (S3).

The loading of the catalytic metal layer into the chamber (S1) may use, for example, chambers of various deposition apparatus. For example, it may be a horizontal CVD chamber or a vertical CVD chamber which is a chamber of a chemical vapor deposition (CVD) apparatus. For example, a catalyst metal layer can be loaded into a horizontal CVD chamber.

[23] The catalytic metal layer is a metal capable of forming graphene, including nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (A1), and creme (0) ， Copper (Cu), Magnesium (Mg), Manganese (Mn), Molybdenum (Mo), Rhodium (Rh), Silicon (Si), Tantalum (Ta), Titanium (Ti), Tungsten Uranium (U), Banarum ( V), any one selected from the group consisting of zirconium (Zr) may be used, and any one of these cases may be used as a single layer or at least two alloys of these cases.

The catalyst metal layer may be a single metal layer composed only of the catalyst metal, or may be combined with other members. For example, the catalytic metal may be in a state disposed on one side of the silicon substrate having silicon oxide (Si0 ₂ ).

Meanwhile, the catalyst metal layer may be in the form of a wafer or a foil. For example, the catalytic metal layer may be a copper foil.

The thickness of the catalyst metal charge may be 10 to 50. If the thickness of the catalyst metal layer is less than 10, the magnitude of the tension applied to the catalyst metal layer cannot be sufficiently increased.

In addition, when the thickness of the catalyst metal layer exceeds 50, the area of contact with the carbon source is constant, and the economical efficiency may be reduced because the thickness of the catalyst metal layer is increased.

In the step (S2) of applying a tension to the catalyst metal layer, the catalyst metal layer may be tensioned by using a component capable of applying tension to the catalyst metal layer.

For example, when the catalyst metal charge is loaded vertically in the chamber, tension may be applied to the catalyst metal layer vertically or horizontally.

For example, a catalyst metal layer is loaded in a vertical CVD chamber, and the loaded catalyst metal layer can be hanged in a batch type, and by connecting a component capable of applying tension to the lower portion of the catalyst metal layer. In addition, tension can be applied to the catalyst metal layer up and down.

In addition, when the catalyst metal layer is horizontally loaded in the chamber, tension can be applied to both sides of the catalyst metal charge.

[32] On the other hand, when the catalyst metal layer is loaded in a so-called roll-to-roll manner, which can be continuously supplied by the oiler, the catalyst metal layer on either the inlet or outlet side of the chamber. Tension can be applied or tension can be applied from both sides.

As described above, details of a manufacturing apparatus capable of forming graphene by applying tension to the catalyst metal layer will be described later.

The size of the tension may be 0.1 kg / m to 5 kg / m. If the magnitude of the tension is less than 0.1 kg / m, the grain size of the catalyst metal layer cannot be increased as desired, and if the magnitude of the tension exceeds 5 kg / m, the catalyst metal layer cannot tolerate the force and is torn. Damage may occur.

This tension can increase the grain size of the catalyst metal layer. For example, the average grain size of this tensioned catalytic metal layer may be between 100 urn and 500. By increasing the grain size of the catalytic metal layer in this way, Since the area where carbon atoms can be uniformly diffused inside the grains increases, high quality graphene can be formed.

In addition, the tension may change the orientation of the catalyst metal layer. For example, when tension is applied to a copper foil having a (001) orientation, it may be changed to a (111) orientation.

[37] This suggests that the (111) orientation is higher and stable than the (001) orientation in terms of surface energy due to the crystal structure. Also, the (111) orientation is similar to the crystal structure of graphene. Therefore, when graphene is synthesized in the catalyst metal layer having the ( _m ) orientation, graphene is more uniform and has fewer defects than those synthesized at the (001) orientation.

Therefore, by changing the orientation of the catalyst metal layer to the (111) orientation by such tension, high quality graphene can be formed.

On the other hand, the step of applying all the tension to the catalyst metal filling (S2) may further comprise the step of heat-treating the catalyst metal layer. This heat treatment temperature may be 3 (xrc or more).

The addition of heat treatment under tension to the catalyst metal charge helps to change the orientation of the catalyst metal layer and allows the catalyst metal layer to have a more single orientation structure. As the orientation of the catalyst metal layer has more unit orientation, high quality uniform graphene may be synthesized.

In the forming of graphene on the catalyst metal charge (S3), the graphene may be formed on the catalyst metal charge by supplying a carbon source into the chamber while applying tension to the catalyst metal layer.

In this case, graphene may be formed on the catalyst metal layer using various deposition methods. For example, in the chamber, graphene may be synthesized by chemical vapor deposition using a catalytic metal.

[43] As chemical vapor deposition, for example, high temperature chemical vapor deposition (T-CVD), inductively coupled plasma chemical vapor deposition (ICP-CVD), and plasma chemical vapor deposition Chemical vapor deposition (Plasma Enhanced Chemical Vapor Deposition, PE-CVD), microwave CVD (Microwave CVD) can be used. In addition, various methods such as rapid thermal annealing (RTA), atomic layer deposition (ALD), and physical vapor deposition (PVD) may be used.

[45] Examples of carbon sources can be supplied in the form of gases such as methane (CH ₄ ), acetylene (C ₂ ¾), solid forms such as powders and polymers, and liquid forms such as bubbling alcohols. Supply is possible.

[46] In addition, various carbon sources such as ethane, ethylene, ethanol, acetylene, propane, butane, butadiene, pentane pentene, cyclopentadiene, nucleic acid, cyclonucleic acid, benzene and toluene may be used.

The case of using copper (Cu) as the material of the catalyst metal charge and methane (CH ₄ ) as the carbon source will be described as an example.

Methane gas is introduced in a hydrogen atmosphere while maintaining a suitable temperature on the copper catalyst metal layer. When the inside of the chamber is raised to a certain temperature, methane gas is separated into carbon atoms and hydrogen atoms, and the separated carbon atoms are absorbed or deposited on the surface of the catalytic metal.

Next, the separated carbon atoms diffuse into the grains of the catalytic metal. At this time, the temperature in the chamber may be made at a silver condition of approximately 300 V to 1500 ^° C.

Subsequently, graphene is formed by remarking the catalytic metal charge in which carbon atoms are absorbed or deposited on the surface. Carbon atoms absorbed on the surface of the catalyst metal layer are synthesized on the surface of the catalyst metal charge as the catalyst metal layer cools.

The angle of the catalyst metal layer can be carried out within a relatively short time. In addition, the cooling of the catalyst metal layer may be performed inside the chamber, or may be performed outside the chamber after removing the catalyst metal layer from the chamber.

As a catalyst metal layer, copper has a low solubility in carbon, and thus may be advantageous for forming a mono-layer grapheneol.

Meanwhile, after forming the graphene, the method may further include removing the catalyst metal charge (not shown). The catalytic metal layer can be removed by a method such as etching. If desired, for example, the nickel catalyst metal layer can be removed using a FeCl ₃ etching solution.

In addition, the catalyst metal layer may be removed after laminating the carrier member on the graphene. have. For example, the catalyst metal layer may be removed using polydimethylsiloxane (PDMS).

By this process, it is possible to increase the grain size of the catalyst metal charge by applying tension to the catalyst metal charge and to grow high quality uniform graphene using the catalyst metal layer having the increased grain size. .

In addition, the orientation of the catalyst metal charge is changed to the (111) orientation by applying tension to the catalyst metal layer, and high quality uniform graphene can be grown using the catalytic metal layer which has been changed to the (111) orientation. Production Example

Graphene was synthesized using a vertical CVD apparatus. A copper catalyst metal layer was loaded into the vertical CVD chamber and a carbon source was fed into the chamber to form graphene with a tension of about 1 kg / m applied up and down the catalyst metal charge.

At this time, 50 sccm to 100 seem of CH ₄ gas was supplied to the carbon source, and the pressure inside the chamber was 0.2 Torr to 1 Torr.

In addition, grapheneol was formed on the catalyst metal charge while raising the temperature in the chamber to about loocrc. Comparative example

[0060] Graphene was formed in the same manner as in the preparation example except for the fact that no tension was applied to the catalyst metal layer. Experimental Example

After the graphene was synthesized according to Comparative Examples and Preparation Examples, grain and orientation mapping was performed on the catalytic metal layer.

2 is a graph illustrating grain size of a catalyst metal layer after synthesis of graphene according to Comparative Examples and Preparation Examples.

FIG. 2 (a) is a graph illustrating grain mapping of a catalyst metal charge after synthesizing graphene according to a comparative example. FIG. . FIG. 2 (b) is a graph showing grain mapping of the catalyst metal layer after synthesis of graphene according to the preparation example, and graphene was synthesized in a state in which tension was applied to the catalyst metal charge.

2 (a) and 2 (b), it can be seen that the grain size of the catalyst metal layer of the preparation example was significantly increased compared to the catalyst metal layer of the comparative example. Accordingly, it can be seen that the grain size of the catalyst metal layer increases by applying tension to the catalyst metal layer.

3 is images obtained by measuring orientation of a catalyst metal layer after graphene synthesis according to Comparative Examples and Preparation Examples.

3 (a) and 3 (b) are images obtained by orientation mapping of a catalyst metal layer after synthesizing graphene according to a comparative example. 3 (a) and 3 (b) are the same image, and FIG. 3 (b) is colored according to the direction.

3 (c) and 3 (d) are images obtained by orientation mapping of a catalyst metal charge after synthesizing graphene according to a preparation example. 3 (c) and 3 (d) are the same image, and FIG. 3 (d) is displayed in color according to the direction.

3 (a) to 3 (d), it can be seen that the orientation of the catalyst metal layer of the Comparative Example is the (001) orientation, and the orientation of the catalyst metal layer of the Preparation Example is the (111) orientation. Therefore, it can be seen that by applying tension to the catalyst metal layer, the orientation of the catalyst metal layer was changed from the (001) orientation to the (111) orientation. Manufacturing equipment

4 and 5 are examples of a manufacturing apparatus for synthesizing graphene according to the preparation example of the present invention.

4 shows an apparatus in which the catalyst metal layer 20 is vertically loaded into the chamber 10, and FIG. 5 shows that the catalyst metal layer 10 is loaded in a roll-t method. 10 shows a device to be supplied.

First, the apparatus shown in FIG. 4 will be described. The graphene manufacturing apparatus includes a chamber 10 in which the catalyst metal filling 20 is vertically disposed and loaded, and the chamber 10 is equipped with a gas inlet 11 and a gas outlet 12.

In the chamber 10, a support 13 is disposed to provide the catalyst metal layer 20. Support so that the catalytic metal layer 20 can be loaded vertically.

In this way, the tension portion 30 may be connected to the opposite side of the catalyst metal packed 20 supported by the support 13.

An example of such tension unit 30 may be a weight weight having a predetermined weight.

Another example may be an elastic member having elasticity. One example of such an elastic member may be a spring member. At this time, one end of the spring member may be connected to the catalyst metal layer 20 and the other end may be fixed to the chamber 10.

The tension applied to the catalyst metal layer 20 may be adjusted to a fixed value by using the tension unit 30 exemplified as the weight member or the spring member fixed as described above. ^'

However, it is also possible to configure the tension applied to the catalytic metal charge 20 to be variable. That is, the tension can be adjusted.

For example, the other end of the tension portion 30, such as the weight or spring member is connected to the tension control portion 40 that is installed to be movable, by the operation of such a tension control portion 40 It may be possible to control the tension applied to the catalytic metal layer 20.

The following describes the rate roll device shown in FIG. The same reference numerals are used for the same configuration as in FIG. 4.

The catalyst metal layer 20 is released from the supply roll 50 and supplied to the chamber 10 in the A direction, and wound around the winding rule 60.

As mentioned above, the chamber 10 is provided with a gas inlet 11 and a gas outlet 12.

One side of the chamber 10, for example, an outer side of the inlet side to which the catalyst metal layer 20 is supplied, may be provided with a tension unit 31 for tensioning the catalyst metal layer 20.

An example of such a tension part 31 can be configured using a lor.

In addition, it is possible to provide a tension control unit 41 which can adjust the tension allol so that the tension allotted to the catalyst metal layer 20 can be varied.

That is, the tension section 31 is connected to a tension control section 41 in which the tension section 31 is movable so that the catalyst metal layer 20 can be operated by the operation of the tension control section 41. You can adjust the tension on).

At this time, the tension applied to the catalyst metal layer 20 by the tension section 31 can be measured. The tension measuring unit 42 may be further provided. Therefore, the tension adjusting unit 41 can more precisely adjust the tension to be applied to the catalyst metal layer 20 according to the measured value of the tension measuring unit 42, and this process can be made automatically.

The tension portion 31 may be provided with an elastic structure such as a spring therein to be elastically and in contact with the catalytic metal layer 20.

As another example, the tension unit 31 and the tension control unit 41 may be connected by using a separate elastic member.

On the other hand, in FIG. 5, the tension portion 31 shows an example in which the tension portion 31 is located at the inlet side of the chamber 10 into which the catalyst metal layer 20 is introduced. In some cases, the catalyst metal layer 20 It is also possible to provide in the position of the exit side discharged from this chamber 10. FIG.

In addition, both the inlet and the outlet side of the chamber 10 may be provided, and in some cases, it may be provided inside the chamber 10.

On the other hand, the embodiments of the present invention disclosed in the specification and drawings are merely presented specific examples to aid understanding, and are not intended to limit the scope of the present invention. It is apparent to those skilled in the art that other modifications based on the technical idea of the present invention can be carried out in addition to the embodiments disclosed herein.

Industrial Applicability

According to the present invention, high-quality uniform graphene can be grown by applying tension to the catalyst metal layer.

Such high quality graphene has excellent electrical and physical properties and may be used in various electronic devices such as display devices.

Claims

[Range of request]

[Claim 1]

Loading a catalyst metal layer into the chamber;

Applying tension to the catalyst metal layer; And

Supplying a carbon source into the chamber under tension on the catalyst metal layer to form graphene on the catalyst metal layer.

[Claim 2]

The method of claim 1, wherein the tension is in a range of about 0.1 kg to about 5 kg / m.

[Claim 3]

The method according to claim 1, wherein the average grain size of the tensioned catalyst metal layer is 100! M to 500 ί «η.

[Claim 4]

The method of claim 1, wherein the applying of the tension to the catalyst metal layer comprises applying tension to change the orientation of the catalyst metal layer.

[Claim 5]

The method of claim 4, wherein the orientation of the catalyst metal charge is changed to the (111) orientation.

【Claim 6】.

The method of claim 1, wherein the catalyst metal layer has a thickness of 10 to 50.

[Claim 71

The method of claim 1, wherein applying the tension to the catalyst metal layer comprises performing heat treatment while applying tension to the catalyst metal layer.

[Claim 8]

The method of claim 1, wherein applying tension to the catalyst metal layer comprises tension in a loaded first direction of the catalyst metal charge or in a second direction perpendicular to the first direction. Graphene manufacturing method characterized in that the addition.

[Claim 9]

The method of claim 1, wherein the loading of the catalyst metal layer into the chamber comprises loading the catalyst metal charge perpendicular to the ground.

[Claim 10]

The method of claim 9, wherein applying the tension to the catalyst metal layer comprises applying tension to the catalyst metal layer.

[Claim 11]

The method of claim 1, wherein applying tension to the catalyst metal layer increases the grain size of graphene formed on the catalyst metal layer.

[Claim 12]

12. The method of claim 11, wherein the average grain size of the catalyst metal is from 100 ΑΛΠ to 500 ¬.

[Claim 13]

Graphene prepared by the method of any one of claims 1 to 12.

[Claim 14]

A chamber including a gas inlet and an outlet, the catalyst metal layer being loaded; And

Graphene manufacturing apparatus characterized in that it comprises a tension portion for imparting a tension to the catalyst metal layer loaded in the chamber.

[Claim 15]

The graphene manufacturing apparatus of claim 14, wherein the tension part comprises a weight or an elastic member connected to one end of the catalyst metal layer. ^"

[Claim 16]

15. The graphene manufacturing apparatus of claim 14, further comprising a tension control unit connected to the tension unit to vary a tension applied to the catalyst metal layer.

[Claim 17] The graphene manufacturing apparatus of claim 16, further comprising a tension measurement unit capable of measuring a tension applied to the catalyst metal layer by the tension unit.

[Claim 18]

18. The graphene manufacturing apparatus of claim 17, wherein the tension control unit adjusts the tension applied to the catalyst metal layer according to the measured value by the tension measurement unit.

[Claim 19]

The method of claim 11, wherein in the chamber,

Supplying the catalyst metal layer; And

An apparatus for producing graphene, comprising a winding to wind the catalyst metal layer, the catalyst metal layer being supplied in a form.

[Claim 20]

20. The graphene manufacturing apparatus of claim 19, wherein the tension unit includes a ruler installed outside the chamber at a position between the supply roll and the take-up roll.