Substrate having upper surface oriented to (111) crystal plane, graphene laminated structure including same, and electric device including same

Abstract

The present invention relates to: a substrate having an upper surface oriented to a (111) crystal plane; and a graphene laminated structure including same. Particularly, disclosed is a substrate having an upper surface oriented to a (111) crystal plane, the substrate comprising: a metal foil substrate; a metal oxide thin film formed by deposition of a cubic metal oxide on the substrate, and crystal-oriented so that the orientation of the (001) crystal plane of the metal oxide is parallel to the perpendicular direction to the surface of the substrate; a (001) crystal plane-oriented first thin film formed on the metal oxide thin film by deposition of a first metal having a hexagonal crystal structure, and crystal-oriented so that the orientation of the (001) crystal plane of the first metal is parallel to the perpendicular direction to the surface of the substrate; and a (111) crystal plane-oriented second thin film formed on the first thin film by deposition of a cubic metal oxide, and crystal-oriented so that the orientation of the (111) crystal plane of the second metal is parallel to the perpendicular direction to the surface of the substrate.

Description

A substrate having a top surface oriented in a (111) crystal plane, a graphene laminate structure including the same, and an electrical device including the same

[0001] The present invention relates to a substrate having an upper surface oriented in a (111) crystal plane, a graphene laminate structure including the substrate, and an electrical and electronic device including the substrate.

[0002] Graphene is a two-dimensional material composed of carbon atoms arranged in a hexagonal pattern. Its exceptional electrical, mechanical, and optical properties make it a promising candidate for diverse applications. Graphene's fundamental structure is a hexagonal arrangement of carbon atoms via sp2 hybridization. This structure gives graphene exceptional electrical and thermal conductivity, excellent mechanical strength, and transparency.

[0003] Graphene can be manufactured using a variety of methods, but vacuum deposition is the most widely used. Vacuum deposition involves depositing graphene onto a substrate, offering the advantage of easy control over the quality and properties of the graphene.

[0004] A metal catalyst layer is a layer of metal atoms deposited on a substrate, which promotes graphene growth. This layer is effective in improving graphene crystal quality and growth rate.

[0005] The metal catalyst layer must bond with carbon atoms to promote graphene growth. Therefore, metals with strong bonding properties to carbon atoms are suitable as the metal catalyst layer. Representative examples include copper, nickel, cobalt, titanium, and iron.

[0006] Graphene was first discovered in 2004 by Professor Geim and Professor Novoselov of the University of Manchester by separating atomic layers from graphite using Scotch tape, leading to the 2010 Nobel Prize in Physics. Recently, several research institutes have been conducting research on large-scale production of graphene using the roll-to-roll method. Since the roll-to-roll method is a method for mass-producing graphene through a continuous process, it is expected to contribute to expanding the various applications of graphene, reducing the production cost of graphene, and improving production efficiency.

[0007] However, for industrial use, it is important to uniformly produce a single layer of graphene film. However, in conventional technology, when using a copper film as a metal catalyst layer, there is a problem in that multilayer graphene exists in island form here and there or the epitaxial graphene layer does not grow well.

[0008] Meanwhile, in graphene production, the surface energy of the metal catalyst layer is crucial for epitaxial graphene growth as close to a single layer as possible. If the surface energy of the metal catalyst layer is high, carbon atoms will adsorb more easily onto it. When carbon atoms adsorb onto the metal catalyst layer, a reaction that promotes graphene growth occurs. For example, copper thin films are known to have high surface energy. When graphene is vacuum-deposited onto a copper thin film, carbon atoms readily adsorb onto the copper film, leading to graphene growth. The surface energy of the metal catalyst layer varies depending on the structure of its crystal planes. Generally, the crystal planes of the metal catalyst layer with a regular atomic arrangement have high surface energy.

[0009] To illustrate with a concrete example, the (111) crystal plane of a copper thin film is the crystal plane with the highest surface energy. Therefore, when graphene is vacuum-deposited on the (111) crystal plane of a copper thin film, epitaxial graphene growth is most promoted.

[0010] On the other hand, the (100) crystal plane of a copper thin film is the crystal plane with the lowest surface energy, and when graphene is vacuum-deposited on the (100) crystal plane of a copper thin film, the growth of graphene is most inhibited.

[0011] If a metal catalyst layer with a polycrystalline structure composed of different crystal planes on its surface has an uneven energy state, the rate at which carbon atoms are adsorbed varies across different regions. This problem results in graphene growing in multiple layers and becoming graphitized in some areas. Therefore, for carbon atoms to evenly settle on copper and grow into a graphene film, a metal layer composed solely of the (111) crystal plane, with a uniform energy state and densely packed atoms, is an effective catalyst. The material most suited to these conditions is a single-crystal metal.

[0012] There have been many studies on this, such as Hori's study, which used single crystal metals with a hexagonal structure of FCC metals with (111) or (100) crystal planes, or single crystal metals with (001) planes in HCP metals (J. Phys. Chem. B., Vol. 106, No.1 15-17, 2002, Y. Hori et al.). However, in reality, only small single crystal metals are possible, and it is impossible to obtain large areas on an industrial scale, so the research results have not been industrialized.

[0013] Accordingly, the inventors of the present invention have developed a technology for aligning a thin film of a metal catalyst layer on a substrate surface with a (111) crystal plane by depositing an oxide thin film oriented with a (100) crystal plane on a flexible metal foil surface of a thin thickness that can be manufactured using existing technology. In this case, since the degree of crystal orientation of the metal crystal grains is close to that of a single crystal, a method for suppressing the non-uniformity of the graphene thin film caused by grain boundaries as much as possible has been implemented. In addition, since a flexible metal foil substrate is used, a technology capable of continuously manufacturing a graphene laminate using a roll-to-roll method has been developed, and the present invention has been completed.

[0014] Therefore, the present invention aims to provide a substrate whose upper surface is oriented toward the (111) crystal plane as a technical solution.

[0015] In addition, the present invention provides a graphene laminate structure including the substrate and the graphene layer as another technical solution.

[0016] In addition, the present invention has as another technical problem to solve the problem of providing an electric and electronic device including the graphene laminate structure.

[0017] In order to solve the above problem, the present invention,

[0018] metal foil substrate;

[0019] A metal oxide thin film in which a cubic metal oxide is deposited and formed on the substrate, and the (001) crystal plane direction of the metal oxide is oriented parallel to the vertical direction of the substrate surface;

[0020] A first metal having a hexagonal crystal structure is deposited and formed on the metal oxide thin film, and the (001) crystal plane direction of the first metal is oriented parallel to the vertical direction of the substrate surface, and a (001) crystal plane-oriented first thin film; and

[0021] A substrate having an upper surface oriented toward a (111) crystal plane is provided, characterized in that it includes a (111) crystal plane-oriented second thin film, in which a cubic second metal is deposited and formed on the first thin film, and the (111) crystal plane direction of the second metal is oriented parallel to the direction perpendicular to the substrate surface.

[0022] In the present invention, the cubic metal oxide is characterized in that it is at least one selected from MgO, CeO2, LaMnO3, Y2O3, Gd2O3, BaZrO3, NiO, LiO2, ZnO, BaO, Er2O3, PdO, Bi2O3, and IrO2.

[0023] In addition, in the present invention, the first metal of the hexagonal crystal structure is characterized in that it is at least one selected from among Zr, Co, Y, Ti, Mg, Be, La, Hf, Re, Ru, Os, Zn, B, Tl, Se, Te, and Sc.

[0024] In addition, in the present invention, the cubic second metal is characterized in that it is an alloy of one or two or more kinds selected from Cu, Ni, and Ag.

[0025] In addition, in order to solve the above other technical problems, the present invention provides a graphene layered structure characterized by including a substrate having the upper surface oriented as the (111) crystal plane as described above; and a graphene layer formed by epitaxial growth on the substrate.

[0026] In addition, in order to solve the above-described further technical problem, the present invention provides an electrical and electronic device including the above-described graphene laminated structure.

[0027] According to the present invention described above, when a metal oxide thin film oriented in the (001) crystal plane is deposited on the surface of a metal foil, and a first thin film of a hexagonal metal is deposited thereon as a metal catalyst layer, and then a second thin film of a cubic metal is deposited, the deposition is performed with the orientation changed to the (111) crystal plane, so that a substrate whose upper surface is oriented in the (111) plane can be provided. In this way, since the substrate has the highest crystal plane with the upper surface oriented in the (111) plane, when graphene is vacuum-deposited on the substrate, the growth of epitaxial graphene can be most promoted, so that a graphene layered structure can be provided. In addition, the graphene layered structure of the present invention has the effect of enabling commercialization through mass production because the roll-to-roll method can uniformly and continuously deposit thin film layers on a large-area substrate.

[0028] Figure 1 shows a laminated structure of a (111)-plane crystal-oriented substrate according to the present invention.

[0029] Figure 2 shows the structure of a graphene laminate structure according to the present invention.

[0030] Figures 3 and 4 illustrate examples of graphene laminate structures according to the present invention.

[0031] Figure 5 illustrates the structure of a graphene layered structure according to one embodiment of the present invention.

[0032] Figure 6 shows the Cu(100) pole figure for crystal plane control of a (111) crystal-oriented Cu thin film according to one embodiment of the present invention.

[0033] Figure 7 shows the results of EBSD analysis for a (111) crystal-oriented Cu thin film according to one embodiment of the present invention.

[0034] Figure 8 schematically illustrates a reel-to-reel device used in one embodiment of the present invention.

[0035] Figure 9 shows an XRD pattern of a (111) crystal-oriented Cu thin film according to one embodiment of the present invention.

[0036] FIG. 10 is a photograph of a reel-to-reel device used in one embodiment of the present invention.

[0037] Figure 11 shows the results of Raman measurements according to graphene deposition temperature in a graphene laminate structure according to one embodiment of the present invention.

[0038]

[0039] Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the attached drawings.

[0040] The degree of orientation of a crystal described herein means the degree to which the directions of the orientation axes of grains in a polycrystal are identical to each other, and a grain means each crystal within the polycrystal.

[0041]

[0042] FIG. 1 illustrates a laminated structure of a (111) plane crystal-oriented substrate according to the present invention, and the present invention relates to a substrate whose upper surface is crystal-oriented in the (111) plane. Accordingly, in one aspect, the present invention comprises: a metal foil substrate; a metal oxide thin film on which a cubic metal oxide is deposited and formed on the metal foil substrate, and the (001) crystal plane direction of the metal oxide is crystal-oriented parallel to the direction perpendicular to the substrate surface; a (001) crystal plane-oriented first thin film on which a first metal having a hexagonal crystal structure is deposited and formed, and the (001) crystal plane direction of the first metal is crystal-oriented parallel to the direction perpendicular to the substrate surface; and a cubic second metal is deposited and formed on the first thin film, and the (111) crystal plane direction of the second metal is crystal-oriented parallel to the direction perpendicular to the substrate surface. (111) A second thin film having a crystal plane orientation; characterized in that it includes a substrate having a top surface oriented in a (111) crystal plane.

[0043] The substrate of the present invention comprises a first thin film formed of a hexagonal metal that induces the formation of a metal thin film having a (111) plane as an upper surface, using a substrate having a metal oxide thin film oriented in the (001) plane as a base substrate, and a second thin film deposited on the first thin film with a cubic metal so as to be crystal-oriented in the (111) plane.

[0044] In the present invention, the metal oxide thin film, the first thin film, and the second thin film formed on the metal foil substrate are thin films formed by vacuum deposition through heat treatment, and as the thin film is deposited while the crystal grains of the substrate are crystal-oriented within several tens of nm from each interface, a thin film ranging from several hundred nm to several ㎛ can be formed. In addition, various methods such as chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), spin-on-glass (SOG), plating, and the like can be used as the deposition method for each of the thin films. Preferably, the step of forming the thin film can use a CVD method using heat or plasma, or a PVD method using thermal evaporation, electron beam, or sputtering to form a thin film by vacuum deposition in order to control the structure of the thin film and improve the crystal orientation.

[0045] In addition, preferably, the metal foil substrate may be a flexible metal foil substrate having a thin thickness of several millimeters or less. In this case, the metal foil substrate may use a commercially available metal foil substrate.

[0046] In addition, in the present invention, the metal oxide thin film is formed by depositing and forming a cubic metal oxide on the substrate, and the (001) crystal plane direction of the metal oxide is oriented parallel to the vertical direction of the substrate surface. Preferably, the metal oxide thin film can satisfy the following relational expression 1.

[0047] [Relationship 1]

[0048] 0°< FWHM2≤ 10°

[0049] (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the thin film grain boundary.)

[0050] In addition, the cubic metal oxide forming the metal oxide thin film may be at least one selected from MgO, CeO2, LaMnO3, Y2O3, Gd2O3, BaZrO3, NiO, LiO2, ZnO, BaO, Er2O3, PdO, Bi2O3, and IrO2. More preferably, the metal oxide thin film may be an MgO thin film having a FWHM2 of 6° to 8°.

[0051] In addition, in the present invention, the first thin film is formed by depositing a first metal having a hexagonal crystal structure on the metal oxide thin film, and the (001) crystal plane direction of the first metal is oriented parallel to the direction perpendicular to the substrate surface. The first thin film is epitaxially deposited on the metal oxide thin film oriented to the (001) crystal plane by the cubic metal oxide, and is oriented to have a (001) plane. Preferably, the first metal having the hexagonal crystal structure may be at least one selected from Zr, Co, Y, Ti, Mg, Be, La, Hf, Re, Ru, Os, Zn, B, Tl, Se, Te, and Sc.

[0052] In addition, in the present invention, the second thin film is formed by depositing and forming a cubic second metal on the first thin film so that the (111) crystal plane direction of the second metal is oriented parallel to the direction perpendicular to the substrate surface. Since the first thin film is oriented to the (001) plane by the hexagonal crystal structure, when the cubic second metal is deposited, the crystals grow densely in the FCC structure, and the (111) crystal plane direction is oriented parallel to the direction perpendicular to the substrate surface, so that the crystal orientation changes to the (111) crystal plane. In other words, the first thin film is deposited and formed using a metal having a hexagonal crystal structure so as to induce crystal orientation to the (111) plane, and then the second thin film is deposited and formed using a cubic metal thereon.

[0053] Also preferably, the second metal may be a cubic metal, and may be an alloy of one or two or more metals selected from Cu, Ni, and Ag.

[0054]

[0055] In addition, since the substrate of the present invention has a crystal plane with the highest surface energy as the upper surface is crystal-oriented in the (111) plane, when graphene is vacuum-deposited on the substrate, the growth of epitaxial graphene can be most promoted.

[0056] As shown in Fig. 2, the structure of such a graphene laminate structure can further include a graphene layer on the substrate. Accordingly, in another aspect, the present invention relates to a graphene laminate structure characterized by including a substrate having the upper surface oriented in the (111) crystal plane as described above; and a graphene layer formed by epitaxial growth on the substrate. That is, the substrate of the present invention as described above is a substrate having a (111) crystal plane oriented thin film in which atoms are most densely packed, and can be used for producing high-quality graphene. Accordingly, when using a general copper foil in the prior art, the problem of multilayer graphene existing here and there in the form of islands or an epitaxial graphene layer not growing well is solved, and the graphene thin film can be uniformly formed as a single layer.

[0057] FIG. 3 illustrates a structure further comprising a cubic metal thin film layer on top of the graphene laminate structure. In the present invention, it is preferable to further include a (111) crystal plane oriented thin film layer in which a cubic second metal is again deposited and formed on the graphene layer so that the (111) crystal plane direction of the second metal is oriented parallel to the vertical direction of the substrate surface. By further including the thin film layer, not only is the electrical conductivity of the graphene layer improved, but it can also be processed to an appropriate thickness, making commercialization possible. In other words, since graphene, a two-dimensional material, has a tendency to exhibit lower intrinsic properties as its thickness increases, a technology for manufacturing graphene while controlling its thickness in nanoscale dimensions and using a thin graphene layer and a (111) substrate layer in an alternating structure can maintain the intrinsic properties of graphene and increase the current carrying capacity.

[0058] Therefore, more preferably, the graphene layer and the thin film layer can be laminated in multiple layers. As shown in Fig. 4, a multilayer laminated structure can be formed in which the graphene layer and the thin film layer are sequentially repeated N times on the thin film layer made of the cubic metal. In this case, when the multilayer is laminated, it is possible to laminate at least 10 layers, and preferably 30 layers or more.

[0059] FIG. 5 illustrates an embodiment of a graphene laminate structure of the present invention. When hexagonal Ti is vacuum-deposited on a base substrate, the crystal orientation is oriented toward the (001) plane, and when cubic Cu is deposited again using the same method, the crystal orientation changes to the (111) plane and the deposition occurs. Thereafter, by repeating the deposition of graphene and Cu using a PVD method, a graphene laminate structure having a 30-layer repeated laminate structure can be formed.

[0060] In addition, in a graphene laminated structure in which graphene is deposited on a Cu(111) thin film manufactured according to the embodiment of the above-mentioned FIG. 5 and 30 layers are deposited in a cross-structure of Gr / Cu, a current density of 3 x 10 6 [A / cm 2 ] was confirmed (results not shown), and it was confirmed that high current density can be achieved by nanographene.

[0061] Figure 6 illustrates the crystal plane control of a substrate (Cu / Ti / base substrate) having a (111) crystal-oriented Cu thin film manufactured in the embodiment of Figure 5, and shows a Cu(100) pole figure. Referring to this, it can be confirmed that the crystal plane alignment on the in-plane can be controlled depending on the deposition process of the first layer metal.

[0062] Figure 7 shows the results of EBSD analysis for the (111) crystal-oriented Cu thin film of the substrate (Cu / Ti / base substrate) having the (111) crystal-oriented Cu thin film manufactured in the embodiment of Figure 5 above. Referring to this, it can be clearly confirmed that the Cu thin film is smoothly formed and has a (111) plane in the z-axis direction, confirming that the upper surface is crystal-oriented in the (111) plane.

[0063] At this time, the multilayer structure can be formed by stacking graphene layers and thin film layers in multiple layers while controlling crystal orientation only through a reel-to-reel continuous vacuum deposition process as shown in Fig. 8. Accordingly, a wire-shaped graphene laminated structure can be manufactured, and thus, according to the present invention, a commercially viable graphene laminated structure can be manufactured.

[0064] Accordingly, the present invention can provide, in another aspect, an electrical / electronic device including the laminated structure. Preferably, the electrical / electronic device may be a semiconductor device, a lithium secondary battery, a fuel cell, a solar cell, an electric wire, or the like.

[0065] For example, when the graphene laminated structure of the present invention is manufactured in a wire shape, an electric wire including the laminated structure can exhibit high electrical conductivity due to the graphene layer, and thus can replace a conventional copper wire and be lightweight.

[0066]

[0067] Hereinafter, embodiments of the present invention will be described in more detail. However, the following embodiments are provided merely to aid understanding of the present invention, and the scope of the present invention is not limited thereby.

[0068] <Example 1>

[0069] After preparing the MgO polycrystalline substrate, it was placed in a vacuum chamber and the vacuum level was set to 10 -6After pumping the vacuum chamber to below 10 Torr, the metal substrate was heated by radiant heat to 300°C. After flowing argon inert gas into the vacuum chamber to a partial pressure of 5 mTorr, the Ti material was deposited on the substrate using the DC magnetron sputtering deposition method, and the shutter was closed.

[0070] Thereafter, Cu was deposited on the Ti thin film using the same method, but at different temperatures. The Cu deposition temperature was varied from 400 to 600 degrees Celsius at 50-degree intervals. Samples were collected at each Cu deposition temperature and subjected to XRD measurements. The results are shown in Fig. 9.

[0071] Referring to Fig. 9, it was confirmed that the XRD intensity was the greatest at a Cu deposition temperature of 500 degrees. This shows that the Cu deposition temperature affects the crystal orientation of Cu, and that a temperature of at least 400 degrees to 550 degrees is appropriate, and that the temperature is optimal around 500 degrees.

[0072] <Example 2>

[0073] Cu / Graphene thin films were manufactured using a roll-to-roll continuous process.

[0074] First, the deposition system used is shown in Figs. 8 and 10. The deposition system consists of a roll-to-roll moving system, a halogen lamp substrate heating device, a QCM deposition rate measuring device, a dual sputtering gun, and a shutter.

[0075] The tape-shaped substrate on which Cu(111) was deposited was moved at regular intervals while varying the deposition temperature to 400 degrees, 450 degrees, 500 degrees, 550 degrees, 600 degrees, and 660 degrees. At this time, the deposition rate was fixed at 0.25 nm / sec, argon partial pressure at 4 mTorr, dischager current at 0.6 A, and discharge voltage at 859 V.

[0076] Raman spectrum analysis was performed to confirm the deposition results, and the results are shown in Fig. 11.

[0077] Referring to this, at a deposition temperature of 450 degrees or less, the 2D equivalent to the first layer of graphene (2680 cm -1 ) does not exist, and as the temperature increases above 500 degrees, the intensity of the 2D peak increases and relatively D (1350 cm -1 ), G (1580 cm -1 ~1585 cm -1 ) can be seen to be relatively decreased. This shows that the D and G peaks are dominant over the 2D peak, which indicates that the defects (D peak) and the number of graphene layers (G peak) of the thin film must be reduced. It can also be confirmed that the substrate temperature must be increased to increase the 2D peak.

[0078] In addition, 660-1, 660-2, 660-3, and 660-4 in Fig. 11 are the results of measurements taken while keeping the substrate temperature constant at 660 degrees and increasing the thickness of the graphene film. It can be seen that the D, G, and 2D peaks increase simultaneously as the thickness increases. This means that a better graphene phase can be obtained through defect removal, increasing the substrate temperature, etc.

[0079]

[0080] From the results of the above examples, when a first thin film of a hexagonal metal is deposited as a metal catalyst layer on a substrate surface using a substrate tape on which a metal oxide thin film oriented in the (001) crystal plane is deposited on a metal foil surface, and then a second thin film of a cubic metal is deposited, the deposition is performed with the orientation changed to the (111) crystal plane, so that a substrate having an upper surface oriented in the (111) plane can be obtained, and graphene can be deposited on the substrate. Furthermore, according to the method of the present invention, a graphene layered structure can be laminated in multiple layers using a continuous roll-to-roll method or the like, so that commercialization of graphene through mass production can become possible.

[0081]

[0082] The above description is merely an example of the technical idea of ​​the present invention, and those skilled in the art will appreciate that various modifications and variations can be made without departing from the essential characteristics of the present invention.

[0083] Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of ​​the present invention, but rather to explain it, and the scope of the technical idea of ​​the present invention is not limited by these embodiments.

[0084] The scope of protection of the present invention should be interpreted by the scope of the patent claims, and all technical ideas within the scope equivalent thereto should be interpreted as being included in the scope of the rights of the present invention.

Claims

1. Metal foil substrate; A metal oxide thin film in which a cubic metal oxide is deposited and formed on the substrate, and the (001) crystal plane direction of the metal oxide is oriented parallel to the vertical direction of the substrate surface; A first metal having a hexagonal crystal structure is deposited and formed on the metal oxide thin film, and the (001) crystal plane direction of the first metal is oriented parallel to the vertical direction of the substrate surface, and a (001) crystal plane-oriented first thin film; and A substrate characterized in that it includes a (111) crystal plane oriented second thin film, wherein a cubic second metal is deposited and formed on the first thin film, and the (111) crystal plane direction of the second metal is oriented parallel to the vertical direction of the substrate surface.

2. In paragraph 1, A substrate having an upper surface oriented in a (111) crystal plane, characterized in that the cubic metal oxide is at least one selected from MgO, CeO2, LaMnO3, Y2O3, Gd2O3, BaZrO3, NiO, LiO2, ZnO, BaO, Er2O3, PdO, Bi2O3, and IrO2.

3. In paragraph 1, A substrate having an upper surface oriented in a (111) crystal plane, characterized in that the first metal of the hexagonal crystal structure is at least one selected from among Zr, Co, Y, Ti, Mg, Be, La, Hf, Re, Ru, Os, Zn, B, Tl, Se, Te, and Sc.

4. In paragraph 1, A substrate whose upper surface is oriented in a (111) crystal plane, characterized in that the second cubic metal is an alloy of one or more kinds selected from Cu, Ni, and Ag.

5. A substrate according to any one of claims 1 to 4, wherein the upper surface is oriented in the (111) crystal plane; and A graphene laminate structure characterized by including a graphene layer formed by epitaxial growth on the substrate.

6. In paragraph 5, A graphene laminate structure characterized by further including a (111) crystal plane oriented thin film layer in which a cubic second metal is again deposited and formed on the graphene layer, and the (111) crystal plane direction of the second metal is oriented parallel to the vertical direction of the substrate surface.

7. In paragraph 6, A graphene laminate structure characterized in that it has a multilayer laminated structure in which the graphene layer and the thin film layer are sequentially repeated N times on the thin film layer.

8. An electrical and electronic device comprising a graphene laminate structure according to Article 5.

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