KR101797216B1 - Catalyst Metal Film, Graphene Structure Employing The Same and Manufacturing Method of Graphene Structure - Google Patents

Catalyst Metal Film, Graphene Structure Employing The Same and Manufacturing Method of Graphene Structure Download PDF

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KR101797216B1
KR101797216B1 KR1020150167503A KR20150167503A KR101797216B1 KR 101797216 B1 KR101797216 B1 KR 101797216B1 KR 1020150167503 A KR1020150167503 A KR 1020150167503A KR 20150167503 A KR20150167503 A KR 20150167503A KR 101797216 B1 KR101797216 B1 KR 101797216B1
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metal layer
metal
graphene
catalytic
layer
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KR20170062094A (en
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원동관
류재철
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해성디에스 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper

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  • Organic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)

Abstract

A catalyst metal film for graphene synthesis, a graphene structure containing the same, and a method for producing the graphene structure are disclosed. The catalytic metal film according to an embodiment of the present invention includes a first catalytic metal layer including a first metal and a second catalytic metal layer including a second metal different from the first metal on the first catalytic metal layer .

Description

Technical Field [0001] The present invention relates to a catalyst metal film for graphene synthesis, a graphene structure employing the catalyst metal film, and a method for manufacturing a graphene structure,

Embodiments of the present invention relate to a catalyst metal film for graphene synthesis, a graphene structure employing the same, and a method of manufacturing a graphene structure.

At present, fullerenes, carbon nanotubes, diamond, graphite, graphene and the like are being studied in various fields as carbon based materials.

Of these, carbon nanotubes have been attracting attention since the 1990s, but in recent years, graphene has attracted much attention. Graphene is a thin-film material in which carbon atoms are arranged two-dimensionally. Since electrons act as zero effective mass particles inside of it, they have a very high electrical conductivity and have high thermal conductivity, elasticity and the like It is known to have.

Therefore, many studies on graphene have been conducted since the study of graphene, and researches are being conducted to utilize it in various fields. In particular, graphene can be applied to wirings of circuit boards, transparent displays or warpable displays, which are essentially installed in electrical and electronic devices.

In order to utilize such graphene in the industrial field, attempts have been actively made to synthesize graphene in a large area. Graphene can be synthesized using chemical vapor deposition (CVD) using a catalytic metal.

Embodiments of the present invention provide a catalyst metal film for graphene synthesis and a method for producing graphene using the same.

The catalyst metal film according to the exemplary embodiment is for graphene synthesis,

A first catalytic metal layer comprising a first metal; And

A second catalyst metal layer including a second metal different from the first metal is coated on the first catalyst metal layer.

The second catalyst metal layer may have a thickness of 1 nm to 5 μm.

The melting point of the second metal may be lower than the melting point of the first metal.

The first catalyst metal layer may contain 99.9% of the first metal.

The first metal may be at least one selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co), titanium (Ti), platinum (Pt), zirconium (Zr), vanadium (V), rhodium It can be either.

The second metal may be one of silver (Ag), gold (Au), and aluminum (Al).

And a third catalytic metal layer including the second metal below the first catalytic metal layer.

A graphene structure, according to an exemplary embodiment,

A first catalytic metal layer comprising a first metal and a second catalytic metal layer comprising a second metal different from the first metal on the first catalytic metal layer; And

And graphene synthesized on the second catalytic metal layer.

The second catalyst metal layer may have a thickness of 1 nm to 5 μm.

The melting point of the second metal may be lower than the melting point of the first metal.

In a method of manufacturing a graphene structure according to an exemplary embodiment,

Preparing a catalyst metal film having a second catalyst metal layer formed on a first catalyst metal layer including a first metal, the second catalyst metal layer including a second metal different from the first metal; And

Providing a gaseous carbon source to the catalytic metal film, and heating the reaction gas to a reaction temperature to cause graphene to synthesize on the catalytic metal film,

The graphene is formed on the second catalytic metal layer.

The second catalyst metal layer may have a thickness of 1 nm to 5 μm.

The melting point of the second metal may be lower than the melting point of the first metal.

The reaction temperature may be higher than the melting point of the second metal and lower than the melting point of the first metal.

The first catalyst metal layer may contain 99.9% of the first metal.

Other aspects, features, and advantages other than those described above will be apparent from the following detailed description, claims, and drawings.

As described above, the catalyst metal film and the graphene structure including the catalyst metal film according to the present invention can form a graphene layer having a large grain size, so that the quality of graphene can be improved.

Of course, the scope of the present invention is not limited by these effects.

1 is a cross-sectional view illustrating a graphene structure according to an embodiment of the present invention.
2 is a cross-sectional view illustrating a graphene structure according to another embodiment of the present invention.
3A and 3B are schematic cross-sectional views illustrating a method of manufacturing a graphene structure according to embodiments of the present invention.
4A is an image showing the crystal orientation of the Cu / Ag laminated structure catalyst metal film after heat treatment according to an embodiment of the present invention.
4B is an image showing the crystal orientation of the graphene layer of the Cu / Ag / graphene laminated structure according to an embodiment of the present invention.
FIG. 5A is an image showing crystal orientation of a Cu single-layer structure catalyst metal film after heat treatment according to a comparative example of the present invention. FIG.
5B is an image showing the crystal orientation of the graphene layer of the Cu / graphene laminate structure according to the comparative example of the present invention.

Hereinafter, the structure and operation of the graphene transfer method according to the present invention will be described in detail with reference to the accompanying drawings. In the drawings, like reference numerals refer to like elements, and the size and thickness of each element may be exaggerated for clarity of explanation.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are not to be construed as limiting for the invention as set forth in the appended claims. And the present invention is only defined by the scope of the claims.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. As used in the specification, "comprises" and / or "comprising" do not exclude the presence or addition of the stated components, steps, operations, and / or elements. The terms first, second, etc. may be used to describe various elements, but the elements should not be limited by terms. Terms are used only for the purpose of distinguishing one component from another.

In the drawings, components may be exaggerated or reduced in size for convenience of explanation. For example, the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of explanation, and thus the present invention is not necessarily limited to those shown in the drawings.

1 is a cross-sectional view of a graphene structure 100 according to an embodiment of the present invention. Referring to FIG. 1, the graphene structure 100 includes a catalytic metal film 10 and a graphene layer 140.

The graphene layer 140 is a two-dimensional flat sheet formed by connecting a plurality of carbon atoms to each other through a covalent bond. The carbon atoms connected by covalent bonds form a 6-membered ring as a basic repeating unit, but a 5-membered ring and / It is also possible to further include a torus. Thus, the graphene layer 140 can be composed of a single layer of covalently bonded carbon atoms (typically sp2 bonds) to each other. However, the present invention is not limited thereto, and the graphene layer 140 may have a structure in which a plurality of single layers of a two-dimensional flat sheet are laminated. The graphene layer 140 may have a variety of structures, and such a structure may vary depending on the content of the five-membered ring and / or the seven-membered ring which may be contained in the graphene layer 140.

The graphene layer 140 is a grain boundary region in which carbon atoms continuously covalently bond to form a grain region having a certain crystal structure and a region in which a covalent bond of carbon atoms is disrupted and contains other impurities, Region.

The larger the grain size, the greater the surface conductivity or mobility of graphene. The size of the grain may vary depending on the type of the catalyst metal film 10.

The catalytic metal film 10 is for graphene synthesis and comprises a first catalytic metal layer 110 comprising a first metal and a second catalytic metal layer 130 comprising a second metal. The first metal and the second metal are different metals, and the second catalyst metal layer 130 is coated on the first catalyst metal layer 110.

Generally, the catalytic metal for synthesizing graphene is made of a metal having a single layer made of a single metal and having high purity.

According to the embodiments of the present invention, the structure in which the first catalyst metal layer 110 and the second catalyst metal layer 130, which are different from each other, is introduced to form a structure having a grain size ) Can be synthesized.

In order to synthesize the graphene layer 140, a chemical vapor deposition (CVD) method, a thermal chemical vapor deposition (TCVD) method, a rapid thermal chemical vapor deposition (PTCVD) method, Various processes such as an inductively coupled plasma enhanced chemical vapor deposition (ICP-PECVD) method and an atomic layer deposition (ALD) method may be used.

When the graphene layer 140 is synthesized by the above process, a reaction gas (CH 4 , C 2 H 2 , C 2 H 4 , CO, etc.) containing the catalyst metal film 10 and carbon is put into the chamber, By heating to the temperature, the catalyst metal film 10 is allowed to absorb carbon. Next, graphene is grown by cooling rapidly to crystallize the carbon.

The second metal of the second catalytic metal layer 130 may be absorbed by the first catalytic metal layer 110 and may be alloyed with the first metal in a series of heat treatment processes such as cooling after heating. The first catalytic metal layer 110 may be recrystallized to increase the grain size of the first catalytic metal layer 110 and the catalytic metal film 110 The grain size of the graphene layer 140 formed on the substrate 10 can be increased. It can be understood that the first catalyst metal layer 110 is crystallized in the same direction and the graphene layer formed thereon is grown in the same direction.

The first catalyst metal layer 110 may be a main metal layer involved in the synthesis of the graphene layer 140. The first catalytic metal layer 110 comprises a first metal from which graphene can be synthesized. The first catalyst metal layer 110 may contain 99.9% or more of the first metal. In some embodiments, the first metal is selected from the group consisting of copper, nickel, cobalt, titanium, platinum, zirconium, vanadium, rhodium, Ruthenium (Ru). The first catalytic metal layer 110 may have a thickness of from 5 [mu] m to 75 [mu] m.

The second catalytic metal layer 130 may be thinly coated on the first catalytic metal layer 110 to participate in recrystallization of the first catalytic metal layer 110. The second catalytic metal layer 130 may have a thickness of 1 nm to 5 um. When the thickness of the second catalytic metal layer 130 is 1 nm or less, the amount of the second metal capable of reacting with the first metal is small so that the first catalytic metal layer 110 can not have a large grain. The first catalyst metal layer 110 may not be a main metal layer involved in the synthesis of the graphene layer 140 and may be disadvantageous for the synthesis of the high quality graphene layer 140. [

The melting point of the second metal contained in the second catalytic metal layer 130 may be lower than the melting point of the first metal. The reaction temperature for heating the catalyst metal film 10 and the reaction gas (CH 4 , C 2 H 2 , C 2 H 4 , CO, etc.) containing carbon during the synthesis of the graphene layer 140 is preferably a melting point And may be lower than the melting point of the first metal. Accordingly, when the graphene layer 140 is synthesized, the second metal may melt and penetrate into the first catalyst metal layer 110, react with the first metal, and participate in recrystallization of the first catalyst metal layer 110.

The second catalyst metal layer 130 may contain 99.9% or more of the second metal. In some embodiments, the second metal may be one of silver (Ag), gold (Au), and aluminum (Al). However, the present invention is not limited thereto. The second metal may be at least one selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co), titanium (Ti), platinum (Pt), zirconium (Zr), vanadium And ruthenium (Ru).

The catalyst metal film 10 may have various laminated structures such as Cu / Ag, Cu / Au, Ni / Ag, Ni / Au, Pt / Cu, and Rh / Ni.

Although not shown in the figure, the graphene structure 100 may further include an additional graphene layer under the catalytic metal film 10.

2 is a cross-sectional view of a graphene structure 200 according to another embodiment of the present invention. Referring to FIG. 2, the graphene structure 200 includes a catalytic metal film 20, an upper graphene layer 240, and a lower graphene layer 260.

The upper graphene layer 240 and the lower graphene layer 260 are graphene layers formed on the upper and lower portions of the catalytic metal film 20 and have the same structure as the graphene layer 140 described with reference to FIG. .

The catalytic metal film 20 includes a first catalytic metal layer 210, a second catalytic metal layer 230, and a third catalytic metal layer 250. The catalytic metal film 20 differs from the catalytic metal film 10 of FIG. 1 in that it further includes a third catalytic metal layer 250 below. The first catalytic metal layer 210 and the second catalytic metal layer 230 have the same structure and function in the same manner as the first catalytic metal layer 110 and the second catalytic metal layer 130 of FIG.

The third catalytic metal layer 250 includes a second metal contained in the second catalytic metal layer 230. And may be thinly coated on the bottom of the third catalytic metal layer 250 to participate in recrystallization of the first catalytic metal layer 210. The third catalytic metal layer 250 may have a thickness of 1 nm to 5 um.

The third catalyst metal layer 250 may contain 99.9% or more of the second metal. In some embodiments, the second metal may be one of silver (Ag), gold (Au), and aluminum (Al). However, the present invention is not limited thereto. The second metal may be at least one selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co), titanium (Ti), platinum (Pt), zirconium (Zr), vanadium And ruthenium (Ru).

The catalyst metal film 20 may have various laminated structures such as Ag / Cu / Ag, Au / Cu / Au, Ag / Ni / Ag, Au / Ni / Au, Cu / Pt / .

The upper and lower graphene layers 240 and 260 formed on the upper and lower portions of the catalytic metal film 20 can form graphene grains of a large size by the catalyst metal film 20, respectively.

3A and 3B are schematic cross-sectional views for explaining a method of manufacturing the graphene structures 100 and 200 according to the embodiments of the present invention. In this example, the manufacturing process of the graphene structure 100 disclosed in Fig. 1 is illustrated.

Referring to FIG. 3A, a first catalyst metal layer 110 is prepared and cleaned. The first catalytic metal layer 110 comprises a first metal capable of synthesizing graphene. The first catalyst metal layer 110 may contain 99.9% of the first metal. In some embodiments, the first metal is selected from the group consisting of Cu, Ni, Co, Ti, Pt, Zr, V, Rh, (Ru). The thickness of the first catalytic metal layer 110 may be varied. In some embodiments, the thickness of the first catalytic metal layer 110 may have a value between 5 um and 75 um.

A pretreatment process may be performed to clean the surface of the first catalyst metal layer 110 before the second catalyst metal layer 130 is formed. The pretreatment process is for removing foreign substances existing on the surface of the first catalytic metal layer 110, and hydrogen gas may be used. Alternatively, the surface of the first catalytic metal layer 110 may be cleaned using an acid / alkali solution or the like to reduce defects in the subsequent steps.

Referring to FIG. 3B, a catalyst metal film 10 is prepared by forming a second catalyst metal layer 130 on the first catalyst metal layer 110.

The second catalyst metal layer 130 includes a second metal different from the first metal included in the first catalyst metal layer 110. The melting point of the second metal contained in the second catalytic metal layer 130 may be lower than the melting point of the first metal. The reaction temperature for heating the catalyst metal film 10 and the reaction gas (CH 4 , C 2 H 2 , C 2 H 4 , CO, etc.) containing carbon during the synthesis of the graphene layer 140 is preferably a melting point And may be lower than the melting point of the first metal. Accordingly, when the graphene layer 140 is synthesized, the second metal may melt and penetrate into the first catalyst metal layer 110, react with the first metal, and participate in recrystallization of the first catalyst metal layer 110.

The second catalyst metal layer 130 may contain 99.9% or more of the second metal. In some embodiments, the second metal may be one of silver (Ag), gold (Au), and aluminum (Al). However, the present invention is not limited thereto. The second metal may be at least one selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co), titanium (Ti), platinum (Pt), zirconium (Zr), vanadium And ruthenium (Ru).

The second catalytic metal layer 130 may have a thickness of 1 nm to 5 um. Various deposition processes may be performed to form the second catalytic metal layer 130. For example, the second catalytic metal layer 130 may be formed by a chemical vapor deposition method, a plasma enhanced CVD (PECVD) method, a low pressure CVD (LPCVD) method, a physical vapor deposition (PVD) method, a sputtering method sputtering, atomic layer deposition (ALD), or the like. However, the present invention is not limited thereto.

Referring to FIG. 3C, a graphene layer 140 is formed on the catalyst metal film 10 to complete the graphene structure 100.

When the catalyst metal film 10 is prepared, the catalyst metal film 10 is transported to the graphene formation space (for example, a chamber). Thereafter, a reaction gas (CH 4 , C 2 H 2 , C 2 H 4 , CO, etc.) containing carbon is introduced into the chamber and heated to the reaction temperature so that carbon is absorbed into the catalyst metal film 10. Next, graphene is grown by cooling rapidly to crystallize the carbon. The reaction temperature may be higher than the melting point of the second metal contained in the second catalytic metal layer 130 and lower than the melting point of the first metal. In some embodiments, the reaction temperature may be at least 900 < 0 > C.

The second metal of the second catalytic metal layer 130 may be absorbed by the first catalytic metal layer 110 and may be alloyed with the first metal in a series of heat treatment processes such as cooling after heating. The first catalytic metal layer 110 may be recrystallized to increase the grain size of the first catalytic metal layer 110 and the catalytic metal film 110 The grain size of the graphene layer 140 formed on the substrate 10 can be increased.

Although not shown in the figure, the graphene structure 100 may further include an additional graphene layer under the catalytic metal film 10. Additional graphene layers can be synthesized at the same time as the graphene layer 140 is synthesized.

4A and 4B are graphs showing the crystal structure and the crystal structure of the Cu / Ag / graphene layer after the heat treatment (900 DEG C, 1000 DEG C) of the catalyst metal film having the Cu / Ag laminated structure according to an embodiment of the present invention, respectively to be.

5A and 5B are images showing a crystal structure and a crystal structure of a Cu / graphene layer after a heat treatment (900 ° C, 1000 ° C) of a catalyst metal film composed of a Cu single layer according to a comparative example of the present invention.

Referring to FIGS. 4A and 4B, it can be seen that the catalyst metal film according to the embodiment of the present invention has crystals formed in the (001) direction as a whole, and the graphene layer formed on the catalyst metal film is also crystallized .

On the other hand, referring to FIGS. 5A and 5B, it can be seen that the crystal structure of the catalyst metal film composed of a single layer according to the comparative example of the present invention and the crystal structure of graphene formed thereon show various directions of the crystal.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

10, 20: catalytic metal film
100, 200: graphene structure
110, 210: first catalyst metal layer
130, 230: a second catalyst metal layer
250: Third catalytic metal layer
140: graphene layer
240: upper graphene layer
260: Lower graphene layer

Claims (15)

As a catalytic metal film for graphene synthesis,
A first catalytic metal layer comprising a first metal; And
A second catalyst metal layer comprising a second metal different from the first metal on the first catalyst metal layer;
Wherein the thickness of the first catalytic metal layer is thicker than the thickness of the second catalytic metal layer,
Wherein the second catalytic metal layer has a thickness between 1 nm and 5 um. The method according to claim 1,
Wherein the first catalytic metal layer has a thickness between 5 [mu] m and 75 [mu] m. The method according to claim 1,
Wherein the melting point of the second metal is lower than the melting point of the first metal. The method according to claim 1,
Wherein the first catalyst metal layer contains 99.9% of the first metal. The method according to claim 1,
The first metal may be at least one selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co), titanium (Ti), platinum (Pt), zirconium (Zr), vanadium (V), rhodium Lt; / RTI > The method according to claim 1,
Wherein the second metal is one of silver (Ag), gold (Au), and aluminum (Al). The method according to claim 1,
And a third catalyst metal layer below the first catalyst metal layer, the third catalyst metal layer including the second metal,
And the third catalytic metal layer has a thickness between 1 nm and 5 um. A first catalytic metal layer comprising a first metal and a second catalytic metal layer comprising a second metal different from the first metal on the first catalytic metal layer; And
And graphene synthesized on the second catalytic metal layer,
Wherein the thickness of the first catalytic metal layer is thicker than the thickness of the second catalytic metal layer,
Wherein the second catalytic metal layer has a thickness between 1 nm and 5 um. 9. The method of claim 8,
Wherein the first catalytic metal layer has a thickness between 5 um and 75 um. 9. The method of claim 8,
Wherein the melting point of the second metal is lower than the melting point of the first metal. Preparing a catalyst metal film having a second catalyst metal layer formed on a first catalyst metal layer including a first metal, the second catalyst metal layer including a second metal different from the first metal; And
Providing a gaseous carbon source to the catalytic metal film, and heating the reaction gas to a reaction temperature to cause graphene to synthesize on the catalytic metal film,
Wherein the graphene is formed on the second catalytic metal layer,
Wherein the thickness of the first catalytic metal layer is thicker than the thickness of the second catalytic metal layer,
Wherein the second catalyst metal layer has a thickness between 1 nm and 5 um. 12. The method of claim 11,
Wherein the first catalytic metal layer has a thickness between 5 um and 75 um. 12. The method of claim 11,
Wherein the melting point of the second metal is lower than the melting point of the first metal. 12. The method of claim 11,
Wherein the reaction temperature is higher than a melting point of the second metal and lower than a melting point of the first metal. 12. The method of claim 11,
Wherein the first catalyst metal layer contains 99.9% of the first metal.
KR1020150167503A 2015-11-27 2015-11-27 Catalyst Metal Film, Graphene Structure Employing The Same and Manufacturing Method of Graphene Structure KR101797216B1 (en)

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