Substrate having single crystalline thin film formed thereon and single crystalline laminated structure comprising same

Abstract

The present invention relates to a substrate on which a single crystalline thin film is formed, and a single crystalline laminated structure comprising same and, specifically, to a substrate on which a single crystalline thin film oriented in the (111) plane is formed, and a single crystalline laminated structure comprising same, the substrate comprising: a substrate formed of a polycrystalline metal or polymer; a single crystalline first thin film which is formed by depositing a polycrystalline first metal on the top of the substrate, has a crystal orientation at grain boundaries satisfying relational expression 1 below, and has a top surface oriented in the (001) plane; a single crystalline second thin film which is formed by depositing a second metal on the top of the single crystalline thin film and has a top surface oriented in the (001) plane; a single crystalline third thin film which is formed of an oxide of the second metal by oxidizing the second thin film and has a top surface oriented in the (111) plane; and a single crystalline fourth thin film which is formed by depositing a third metal on the top of the third thin film and has a top surface oriented in the (111) plane. [Relational expression 1] 0° < FWHM2 ≤ 3° (where, FWHM2 denotes a full width at half maximum of a misorientation angle distribution curve at grain boundaries of the thin film.)

Description

Substrate having a single-crystal thin film formed thereon and a single-crystal laminated structure including the same

[0001] The present invention relates to a substrate on which a single-crystal thin film is formed and a single-crystal laminated structure including the same, and more particularly, to a substrate on which a single-crystal thin film oriented in the (111) plane is formed and a single-crystal laminated structure including the same.

[0002] Graphene is a hexagonal monolayer of carbon atoms. Graphene is chemically very stable and exhibits semi-metallic properties, with its conduction and valence bands overlapping at a single point (the Dirac point). Furthermore, graphene exhibits two-dimensional ballistic transport. This two-dimensional ballistic transport of charges within a material means that they move with virtually no resistance due to scattering. Consequently, charge mobility within graphene is extremely high. Furthermore, graphene offers numerous advantages, including a current density (approximately 108 A / cm2) that is over 100 times greater than that of copper. Therefore, research is underway to leverage these unique properties to apply graphene to various electronic devices.

[0003] Graphene was first discovered in 2004 by Professor Geim and Novoselov's team at the University of Manchester by separating atomic layers from graphite using Scotch tape, leading to their 2010 Nobel Prize in Physics. Technologies that can be utilized in industry are continuously being developed, such as the roll-to-roll method for manufacturing the world's largest 30-inch large-area graphene in 2010. However, for industrial use, it is important to uniformly implement a single-layer graphene thin film. However, conventional technologies have problems in that when using general copper foil, multilayer graphene exists in island shapes here and there or the epitaxial graphene layer does not grow well.

[0004] Meanwhile, in graphene electrode manufacturing, the surface energy of the catalyst metal is crucial for epitaxial graphene growth as close to a single layer as possible. This is because, even within the same metal, the atomic packing ratio varies depending on the orientation, and factors affecting the surface energy of the catalyst, such as dislocation density, stacking fault energy, twins, and impurities, depending on the processing condition, affect the reaction with the gas molecules or atoms to be adsorbed. In particular, if the solubility between the adsorbed element and the metal catalyst is extremely low or the reactivity is weak, it is difficult to expect the catalyst to function catalytically. For example, copper, widely used in graphene thin film formation, has a face-centered cubic (FCC) structure. However, in a CVD process at 1000°C, the maximum solubility of carbon atoms adsorbed on the copper surface as a catalyst is 0.028 at%. Therefore, controlling atomic adsorption during the process due to this weak reactivity is extremely difficult. If aggregate structures with different orientations are mixed, the energy state will be uneven, and the speed at which carbon atoms are adsorbed will vary in each area. This problem will result in graphene growing in multiple layers and becoming graphitized in some areas. Therefore, for carbon atoms to evenly settle on the copper and grow into a graphene film, a substrate with a uniform energy state and nucleation sites that will form a graphene net is effective as a catalyst. Materials that can satisfy a uniform energy state include single-crystal materials. Many studies on this subject have been conducted, such as Hori's study, using single-crystal metals with a hexagonal structure in the (111) or (100) orientation as FCC metals or single-crystal metals with the (001) plane 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 did not lead to industrialization.

[0005]

[0006] Meanwhile, the metal substrate technology with biaxial orientation of the long wire is a key technology for fabricating second-generation high-temperature superconductors. IBAD (Ion Beam Assisted Deposition) is a deposition technology that can impart biaxial orientation to the deposited material on the substrate by simultaneously depositing the material and irradiating it with an ion beam at a specific angle to cause etching. MgO, which can rapidly grow biaxially through this IBAD technology, is currently the most commonly used in high-temperature superconducting wires. MgO materials with a rock-salt structure have low surface energy and high packing density on the (001) plane, which easily form fiber textures with (001) orientation. The ion beam energy forms the orientation in the initial fiber texture. It is reported that the IBAD-MgO thin film can obtain the best biaxial orientation at room temperature when the process conditions are optimized at a certain thickness by adjusting the incident angle and power of the ion beam and the IBAD ratio.

[0007] In this regard, the inventors of the present invention have developed a single-crystal thin film, which is formed by depositing a second polycrystalline material on top of a substrate formed of a first polycrystalline material, and which exhibits crystal orientation at the grain boundaries at the level of a single crystal, as disclosed in Patent Document 1, which is a previous patent of the inventors of the present invention. However, the single-crystal thin film disclosed in Patent Document 1 has a (001) plane on its upper surface, and although it is suitable for high-temperature superconducting wires, it has limitations in application to graphene thin films, etc.

[0008] Accordingly, the inventors of the present invention developed a technique for forming a single-crystal thin film by controlling the crystal orientation of a polycrystalline substrate and controlling the crystal orientation of the polycrystalline thin film so that the (111) plane, where atoms are most densely packed, is the upper surface, and completed the present invention.

[0009] Therefore, in view of the above technical requirements, the present invention provides a substrate on which a single-crystal thin film oriented in the (111) plane is formed as a technical solution.

[0010] In addition, the present invention has as another technical problem to be solved a single-crystal laminated structure including a substrate on which a single-crystal thin film oriented in the (111) plane is formed.

[0011] In addition, the present invention has as another technical problem to solve the problem of providing an electric device and an electric wire including the single-crystal laminated structure.

[0012] In order to solve the above problem, the present invention,

[0013] A substrate formed of a polycrystalline metal or polymer;

[0014] A single-crystalline first thin film formed by depositing a polycrystalline first metal on the upper part of the substrate, wherein the crystal orientation at the crystal grain boundary satisfies the following relational expression 1 and the upper surface is crystal-oriented as the (001) plane;

[0015] A second single-crystal thin film in which a second metal is deposited and formed on top of the above single-crystal thin film and the upper surface is crystal-oriented to the (001) plane;

[0016] A single-crystalline third thin film formed by oxidizing the second thin film to form an oxide of the second metal, the upper surface of which is crystal-oriented in the (111) plane; and

[0017] A substrate is provided with a single-crystal thin film oriented in the (111) plane, characterized in that it includes a single-crystal thin film having a top surface oriented in the (111) plane by depositing and forming a third metal on top of the third thin film.

[0018] [Relationship 1]

[0019] 0°< FWHM2≤ 3°

[0020] (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the thin film grain boundary.)

[0021] In the present invention, the first metal is characterized by being any one selected from Fe, an Fe-based alloy, an Fe-based compound, Ni, a Ni-based alloy, a Ni-based compound, Ag, or Cu.

[0022] In addition, in the present invention, it is characterized in that the crystal orientation of the substrate and the first thin film satisfies the following relationship 2:

[0023] [Relationship 2]

[0024] 5°< FWHM1 - FWHM2 ≤ 20°

[0025] (However, FWHM1 and FWHM2 are the full width at half maximum of the distribution curve of misorientation angle at the grain boundaries of the substrate and thin film, respectively.)

[0026] In addition, in the present invention, it is characterized in that the second metal is any one selected from Ni, Ag, FeCo, FeNi3, Cu, and Fe.

[0027] In addition, in the present invention, it is characterized in that the third metal is one selected from Cu, Ni, Al, Ag, Pb, and Pt, Pd, Rh, Ce, Th, and Sr.

[0028] In addition, in the present invention, the substrate is characterized in that it is formed in a wire shape.

[0029]

[0030] In addition, in order to solve the above other technical problems, the present invention provides a substrate on which a single-crystal thin film oriented in the (111) plane as described above is formed; and

[0031] A single-crystal layered structure including a substrate on which a single-crystal thin film oriented in the (111) plane is formed, characterized in that the single-crystal layer includes a graphene layer formed by epitaxial growth on the substrate.

[0032]

[0033] In addition, in order to solve the above-described further technical problem, the present invention provides an electronic device including the above-described laminated structure.

[0034]

[0035] In addition, in order to solve the above-described further technical problem, the present invention provides an electric wire including the above-described laminated structure.

[0036] According to the above invention, there is an effect of providing a substrate in which a single-crystal thin film is formed by controlling the crystal orientation of a polycrystalline substrate and crystal orientation is oriented in the (111) plane where atoms are most densely packed.

[0037] In addition, the present invention can provide a single-crystal layered structure, an electric device and an electric wire including the single-crystal layered structure, including a substrate on which a single-crystal thin film oriented in the (111) plane is formed, and thus has the effect of being applicable to a large-area graphene electrode on an industrial scale.

[0038] Figure 1 illustrates the structure of a single-crystal laminated structure in which thin films having a (111) surface are laminated according to the present invention.

[0039] FIG. 2 illustrates the structure of a single-crystal substrate formed according to one embodiment of the present invention, on which a thin film having a (111) surface is laminated.

[0040] Figure 3 shows the results of a pie scan of Cu according to one embodiment of the present invention.

[0041] Figure 4 shows an XRD pattern according to one embodiment of the present invention.

[0042] Figure 5 illustrates a Cu(111) growth substrate according to one embodiment of the present invention.

[0043] Figure 6 shows the results of EBSD analysis according to one embodiment of the present invention.

[0044] Figure 7 shows the results of SEM analysis according to one embodiment of the present invention.

[0045] Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the attached drawings.

[0046] 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.

[0047] FIG. 1 illustrates the structure of a single-crystalline substrate having a thin film having a (111) plane as its upper surface, according to one aspect of the present invention. The present invention relates to a substrate having a single-crystalline thin film having a crystal orientation of the (111) plane as its upper surface. Specifically, the substrate of the present invention comprises: a substrate formed of a polycrystalline metal or polymer; a single-crystalline first thin film formed by depositing a polycrystalline first metal on the upper surface of the substrate, wherein the crystal orientation at the grain boundary satisfies the following relationship 1 and the upper surface is crystal-oriented as the (001) plane; a single-crystalline second thin film formed by depositing a second metal on the upper surface of the single-crystalline thin film and having a crystal orientation of the (001) plane; a single-crystalline third thin film formed by oxidizing the second thin film and using an oxide of the second metal, wherein the upper surface is crystal-oriented as the (111) plane; And it is characterized in that it includes a single-crystal fourth thin film in which a third metal is deposited and formed on the upper surface of the third thin film and the upper surface is crystal-oriented in the (111) plane.

[0048] [Relationship 1]

[0049] 0°< FWHM2≤ 3°

[0050] (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the thin film grain boundary.)

[0051] In the present invention, a thin film is formed by depositing a first polycrystalline metal on top of a substrate formed of a polycrystalline metal or polymer, and during the deposition, crystal nuclei larger than the grain size of the crystals of the substrate are generated, causing the crystals to grow and deposit the thin film. At this time, the first metal may be any one selected from Fe, an Fe-based alloy, an Fe-based compound, Ni, a Ni-based alloy, a Ni-based compound, Ag, or Cu.

[0052] In this case, the polycrystalline substrate can be formed so that the orientation axis direction of each crystal grain forming the substrate is random. On the other hand, when the first polycrystalline metal is deposited on the substrate, crystal nuclei are rapidly generated and grown on the substrate at the moment of deposition, and are generated larger than the size of the crystals at the grain boundaries of the substrate. At this time, when the direction of the orientation axis of the crystal grains of the thin film is aligned with the average orientation axis direction of the crystal grains of the substrate, the energy is the lowest, so that the deposition can be parallel to the average orientation axis alignment direction of the substrate.

[0053] Preferably, the size of the crystal grains formed as the first metal is deposited can be at least twice the size of the crystal grains of the substrate, and more preferably, when it is 5 to 6 times or more, the average orientation axis direction of the crystal grains of the substrate and the orientation direction of the crystal grains of the thin film can be almost identical. Thereafter, as the deposition of the first metal continues and the crystal nuclei grow and the thin film is deposited, the crystal orientation of the crystal grains of the thin film exhibits single crystallinity in which the half width of the crystal orientation difference angle at the crystal grain boundary satisfies 3° or less.

[0054] Therefore, the single-crystal first thin film on which the polycrystalline first metal is deposited is aligned in the direction of alignment of the orientation axis, that is, in the direction horizontal to the crystal axis, so that the upper surface is crystal-oriented as the (001) plane.

[0055] In the present invention, the single-crystal second thin film is epitaxially formed by depositing a second metal on top of the single-crystal first thin film, so that the upper surface is crystal-oriented to the (001) plane. At this time, the second metal may be any one selected from Ni, Ag, FeCo, FeNi3, Cu, and Fe.

[0056] In addition, in the present invention, the third thin film is formed by oxidizing the second thin film to form an oxide of the second metal. When the second thin film, which is a metal thin film, is heat-treated in an oxygen atmosphere, oxidation begins from the surface, and in the initial oxidation process, a well-aligned metal oxide surface film is formed on the surface of the metal thin film. The metal oxide formed in this way acts as a passive layer that impedes the subsequent oxidation process, and thereafter, oxidation progresses by diffusing from the metal thin film, which is the parent material, to the surface of the metal oxide formed initially, and combining with oxygen, and as the metal oxide crystal plane with the fastest oxidation rate grows as the dominant crystal plane, the vertical crystal axis direction is determined. Therefore, as the upper surface of the second thin film, which is a metal thin film, changes direction from the (001) plane to the (111) plane through the oxidation heat treatment, the third thin film by the metal oxide is formed. In this way, the metal oxide thin film produced by the oxidation process of the metal has an increased crystal grain size and improved crystallinity as the oxidation temperature increases, and grows into an epitaxial thin film whose crystallographic direction matches that of the metal thin film in the surface direction while being atomically well aligned in the (111) crystal plane, which is perpendicular to the surface.

[0057] At this time, the oxidation heat treatment is performed under an oxygen vacuum of 1x10 -4 1x10 -1Torr, can be performed at 300 to 600°C for 1 to 30 minutes. More preferably, the oxidation heat treatment is performed at an oxygen vacuum of 5×10 -3 Torr, can be performed at 500℃ for 10 minutes.

[0058] In addition, in the present invention, the fourth thin film is a single-crystal thin film in which a third metal is deposited and formed on top of the third thin film and the upper surface is crystal-oriented in the (111) plane. At this time, the third metal may be any one selected from Cu, Ni, Al, Ag, Pb, and Pt, Pd, Rh, Ce, Th, and Sr.

[0059] FIG. 2 illustrates an example of a substrate on which the single-crystal thin film is formed. On a substrate on which an MgO thin film having a (001) plane as its upper surface is formed, FeNi3 is epitaxially deposited to form an FeNi3 thin film having a (001) plane as its upper surface. Ni is epitaxially deposited again through the same process to form an Ni thin film having a (001) plane as its upper surface. Thereafter, through oxidation heat treatment, the direction of the upper surface of the Ni thin film changes from the (001) plane to the (111) plane. That is, when the Ni thin film is heat-treated in an oxygen atmosphere, oxidation begins from the surface. In the initial oxidation process, a well-aligned NiO surface film is formed on the surface of the Ni thin film. The NiO formed at this time acts as a passive layer that impedes the subsequent oxidation process. Thereafter, oxidation progresses in a manner in which the base material Ni diffuses to the initially formed NiO surface and combines with oxygen. As the oxidation temperature increases, the NiO thin film produced by the Ni oxidation process increases in crystal grain size and crystallinity, and grows while being atomically well aligned in the (111) crystal plane in the direction perpendicular to the surface. When Cu is subsequently deposited on the upper surface of the NiO thin film through heat treatment, a Cu thin film with the upper surface crystallographically oriented in the (111) plane is formed epitaxially.

[0060] Thus, the present invention relates to a substrate on which a single-crystalline thin film having an upper surface oriented in the (111) plane is formed, and by controlling the crystal orientation only through a heat treatment process on a conventional polycrystalline substrate, a single-crystalline first thin film having an upper surface oriented in the (001) plane is formed parallel to the alignment direction of the orientation axis of the polycrystalline substrate grain boundary, and after epitaxially depositing a second thin film of metal, a third thin film of metal oxide having the direction of the crystal axis converted to the (111) plane can be formed through oxidation heat treatment, and a metal thin film such as Cu is epitaxially deposited thereon, so that a single-crystalline thin film having an upper surface oriented in the (111) plane can be formed.

[0061] Also preferably, the substrate can be formed into a wire shape.

[0062] At this time, the first to fourth thin films formed on the substrate are thin films deposited and formed by heat treatment or oxidation heat treatment, and are deposited while the crystal grains of the substrate are oriented within several tens of nm from each interface, and as the thin film is deposited while the crystals grow epitaxially, a single-crystal thin film ranging from several hundred nm to several ㎛ can be formed.

[0063] In addition, various methods such as chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), spin-on-glass (SOG), plating, and others can be used as the deposition method for each of the above thin films. Preferably, the step of forming the thin film may use a CVD method using heat or plasma, which forms the thin film by vacuum deposition in order to control the structure of the thin film and improve crystal orientation, or a PVD method using thermal evaporation, electron beam, or sputtering.

[0064]

[0065] In addition, the present invention provides a single-crystalline layered structure including a substrate having a single-crystalline thin film oriented in the (111) plane formed thereon as another aspect; and a graphene layer formed by epitaxial growth on the substrate; wherein the substrate includes a substrate having a single-crystalline thin film oriented in the (111) plane formed thereon. That is, the substrate of the present invention is a substrate having a single-crystalline thin film oriented in the (111) plane, where atoms are most densely packed, and can also be used as a substrate for producing high-quality graphene. Therefore, when utilizing the substrate of the present invention, the problem of multilayer graphene existing here and there in the form of islands or an epitaxial graphene layer not growing well when using a general copper foil in the prior art is solved, and the graphene thin film can be uniformly formed as a single layer.

[0066] In addition, the present invention can provide, as another aspect, an electronic device including the laminated structure. Preferably, the electronic device may be a semiconductor device, a lithium secondary battery, a fuel cell, a solar cell, or the like.

[0067] In another aspect, the present invention can provide an electrical wire comprising the laminated structure. For example, when the substrate of the present invention is manufactured in a wire shape, the laminated structure formed by laminating graphene thereon can form an epitaxial graphene layer. Accordingly, an electrical wire comprising the laminated structure can exhibit high electrical conductivity due to the graphene layer, thereby replacing conventional copper wire and reducing its weight.

[0068]

[0069] 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.

[0070] <Example>

[0071] Deposition of FeNi3 thin films

[0072] The FeNi3 deposition process in the Cu / NiO / Ni / FeNi3 / MgO / Y2O3 / Al2O3 / Hastelloy cross-sectional structure was performed as follows.

[0073] First, a metal substrate was prepared in which Al2O3 layer, Y2O3 layer, and MgO layer were sequentially laminated on top of the Hastelloy layer, and then the metal substrate was placed in a vacuum chamber to achieve a vacuum level of 10 -6 After pumping the vacuum chamber to below 10 Torr, the metal substrate was heated by radiant heat to 400℃. The deposition rate was increased by heating a crucible containing a mixture of iron and nickel in an atomic ratio of 1:3 to a maximum deposition rate of 40Å / sec. After that, the shutter of the crucible was opened to deposit FeNi3 on the metal substrate. After the deposition was completed, the shutter was closed, and the metal substrate and the deposited FeNi3 alloy thin film were allowed to cool naturally.

[0074] Deposition of Ni thin films and formation of NiO thin films

[0075] The Ni deposition and NiO deposition processes in the Cu / NiO / Ni / FeNi3 / MgO / Y2O3 / Al2O3 / Hastelloy cross-sectional structure were performed as follows.

[0076] Ni was deposited by sputtering on the substrate of FeNi3 / MgO / Y2O3 / Al2O3 / Hastelloy manufactured above. Specifically, the substrate was heated to 700°C with a halogen lamp and then deposited for 5 minutes in an atmosphere of argon partial pressure of 5 mTorr and a deposition rate of 1 nm / sec.

[0077] Afterwards, the surface of the Ni thin film was oxidized by performing an oxidation heat treatment at an oxygen vacuum of 5 m Torr and 500°C for 10 minutes to form a NiO thin film.

[0078] Deposition of Cu thin films

[0079] The process of depositing Cu using sputtering deposition on a NiO / Ni / FeNi3 / MgO / Y2O3 / Al2O3 / Hastelloy substrate was performed as follows.

[0080] The substrate was heated to 500°C with a halogen lamp, and then deposited for 5 minutes in an atmosphere with an argon partial pressure of 5 mTorr and a deposition rate of 1 nm / sec.

[0081]

[0082] The structure of the substrate formed by the above example is shown in Fig. 2.

[0083] Figure 3 shows the XRD phi scan results of the Cu thin film according to the above embodiment, indicating the degree of alignment of the crystal axes in the horizontal direction of the substrate. A smaller full width at half maximum value indicates a better alignment of the crystal axes in the plane direction. It can be seen that the full width at half maximum of the (002) crystal plane of the Cu thin film is within 2 degrees, indicating alignment at the single crystal level.

[0084] In addition, Fig. 4 shows an XRD pattern of a thin film in which FeNi3, Ni, NiO, and Cu thin films are sequentially laminated according to the above embodiment. Referring to this, it can be confirmed that the FeNi3 thin film is oriented in the (002) plane, which is a (001) group plane, and that the Ni thin film deposited on top of the FeNi3 thin film is also epitaxially grown and crystal-oriented in the (002) plane. It can be confirmed that the NiO thin film formed by the oxidation heat treatment of the Ni thin film has its crystal orientation plane converted and crystal-oriented in the (111) plane, and that the Cu thin film formed on top of the NiO thin film is epitaxially grown and crystal-oriented on its upper surface in the (111) plane.

[0085] Fig. 5 shows a substrate having a single-crystalline Cu thin film formed according to the above embodiment, and Fig. 6 shows the results of EBSD analysis of the single-crystalline Cu thin film formed according to the above embodiment. Referring to these, it can be clearly confirmed that the single-crystalline 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.

[0086] Figure 7 shows the surface of a Cu(111) thin film measured using a SEM measuring device. The thin film surface is composed of particles of several tens of microns in size, and as can be seen from the EBSD measurement results in Figure 7, it can be seen that the Cu(111) crystal axis is parallel to the substrate vertical direction, and the crystal axes of each Cu crystal are aligned in the planar direction, and the (111) crystal-oriented surface of each particle is formed smoothly.

[0087]

[0088] 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.

[0089] 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.

[0090] 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. A substrate formed of a polycrystalline metal or polymer; A single-crystalline first thin film formed by depositing a polycrystalline first metal on the upper part of the substrate, wherein the crystal orientation at the crystal grain boundary satisfies the following relational expression 1 and the upper surface is crystal-oriented as the (001) plane; A second single-crystal thin film in which a second metal is deposited and formed on top of the above single-crystal thin film and the upper surface is crystal-oriented to the (001) plane; A single-crystalline third thin film formed by oxidizing the second thin film to form an oxide of the second metal, the upper surface of which is crystal-oriented in the (111) plane; and A substrate having a single-crystalline thin film oriented in the (111) plane formed thereon, characterized in that it includes a single-crystalline fourth thin film having a top surface oriented in the (111) plane by depositing and forming a third metal on top of the third thin film: [Relationship 1] 0°< FWHM2≤ 3° (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the thin film grain boundary.) 2. In paragraph 1, A substrate having a single-crystal thin film oriented in the (111) plane formed thereon, characterized in that the first metal is any one selected from Fe, an Fe-based alloy, an Fe-based compound, Ni, a Ni-based alloy, a Ni-based compound, Ag or Cu.

3. In paragraph 1, A substrate having a single-crystal thin film formed thereon, characterized in that the crystal orientation of the substrate and the first thin film satisfies the following relational expression 2: [Relationship 2] 5°< FWHM1- FWHM2≤ 20° (However, FWHM1 and FWHM2 are the full width at half maximum of the distribution curve of misorientation angle at the grain boundaries of the substrate and thin film, respectively.) 4. In paragraph 1, A substrate having a single-crystal thin film formed in a (111) plane, characterized in that the second metal is any one selected from Ni, Ag, FeCo, FeNi3, Cu, and Fe.

5. In paragraph 1, A substrate having a single-crystal thin film oriented in the (111) plane formed thereon, characterized in that the third metal is any one selected from Cu, Ni, Al, Ag, Pb, and Pt, Pd, Rh, Ce, Th, and Sr.

6. In paragraph 1, A substrate having a single-crystal thin film formed in a (111) plane, characterized in that the substrate is formed in a wire shape.

7. A substrate having a single-crystal thin film formed in a (111) plane according to any one of claims 1 to 6; and A single-crystalline layered structure comprising a substrate on which a single-crystalline thin film oriented in the (111) plane is formed, characterized in that the single-crystalline layer comprises a graphene layer formed by epitaxial growth on the substrate.

8. An electronic device comprising a laminated structure according to Article 7.

9. An electric wire comprising a laminated structure according to Article 7.

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